Changed by Adsorption

Landolt-Börnstein
Numerical Data and Functional Relationships in Science and Technology

New Series / Editor in Chief: W. Martienssen
Group III: Condensed Matter

Volume 42
Physics of Covered Solid Surfaces

Subvolume A
Adsorbed Layers on Surfaces
Part 2
Measuring Techniques and Surface Properties
Changed by Adsorption
Editor
H.P. Bonzel
Authors
K. Hermann, H. Ibach, K. Jacobi, M.A. Rocca, D. Sander,
M.A. Van Hove, P.R. Watson, Ch. Wöll
13
ISSN 1615-1925 (Condensed Matter)
ISBN 3-540-41224-7 Springer-Verlag Berlin Heidelberg New York
Library of Congress Cataloging in Publication Data

Zahlenwerte und Funktionen aus Naturwissenschaften und Technik, Neue Serie
Editor in Chief: W. Martienssen
Vol. III/42A2: Editor: H.P. Bonzel
At head of title: Landolt-Börnstein. Added t.p.: Numerical data and functional relationships in science and technology.
Tables chiefly in English.
Intended to supersede the Physikalisch-chemische Tabellen by H. Landolt and R. Börnstein of which the 6th ed. began publication in 1950 under title:
Zahlenwerte und Funktionen aus Physik, Chemie, Astronomie, Geophysik und Technik.
Vols. published after v. 1 of group I have imprint: Berlin, New York, Springer-Verlag
Includes bibliographies.
1. Physics--Tables. 2. Chemistry--Tables. 3. Engineering--Tables.
I. Börnstein, R. (Richard), 1852-1913. II. Landolt, H. (Hans), 1831-1910.
III. Physikalisch-chemische Tabellen. IV. Title: Numerical data and functional relationships in science and technology.
QC61.23 502'.12 62-53136
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Preface
Surface Science is understood as a relatively young scientific discipline, concerned with the physical and
chemical properties of and phenomena on clean and covered solid surfaces, studied under a variety of
conditions. The adsorption of atoms and molecules on solid surfaces is, for example, such a condition,
connected with more or less drastic changes of all surface properties. An adsorption event is frequently
observed in nature and found to be of technical importance in many industrial processes. For this reason,
Surface Science is interdisciplinary by its very nature, and as such an important intermediary between
fundamental and applied research. The beginning of Surface Science may be placed around the years
1900-1928, connected with seminal works by J.W. Gibbs, I. Langmuir, M. Knudsen, O. Stern,
M. Volmer, C. Davisson and L. Germer, H.S. Taylor, J.E. Lennard-Jones, I.N. Stranski and others. In
modern times, research activities in this field have literally exploded worldwide. Consequently, enormous
progress can be recognized and it is no exaggeration, to note a high degree of maturity in this
well-established scientific discipline. Tribute is being paid to this effect by the renowned Series of
Landolt-Börnstein whose editor-in-chief Werner Martienssen, Frankfurt am Main, has initiated several
volumes of collected scientific data in the field of Surface Science.
Indeed, the point in time has arrived where all quantitative data, that have been generated over so many
years, are worth being collected in tables and figures for critical review and reference purposes as well.
The beginning has been made with Landolt-Börnstein volume 24, entitled Physics of Solid Surfaces. This
volume, consisting of four subvolumes, appeared in 1993-96 and covers the properties of clean solid
surfaces. The present volume 42 is devoted to Covered Solid Surfaces and, in particular, to Adsorbed
Layers on Surfaces. It is as such a collection of data obtained for adsorbates on well-defined crystalline
surfaces. "Well-defined" means surfaces of known crystallographic structure and chemical composition.
These conditions can in most cases be realized by careful sample preparation in ultra-high vacuum.
Work on the present volume started in late 1997 when I was first contacted by W. Martienssen. An initial
outline of the volume was written in January of 1998. At this point I want to express my sincere gratitude
to George Comsa, Bonn, and Gerhard Ertl, Berlin, for their support by making valuable suggestions,
concerning both the outline and the choice of possible authors. In fact, the choices made at the time
proved to be excellent ones, and the consulting of G. Comsa and G. Ertl turned out to be extremely helpful
for the evolution of the present volume.
It was almost clear at the beginning, that the amount of general information and quantitative data on
Adsorbed Layers on Surfaces is enormous, too large to fit into a single volume. Hence, again several
subvolumes had to be planned. Unfortunately, the chapters anticipated for each of the subvolumes did not
arrive synchronously with the production schedule, such that the sequence of chapters actually printed in
the subvolumes deviates from that in the general outline of the whole volume. We apologize for this
inconvenience, but in the age of electronic information distribution this problem will be solved, once all
volumes are available electronically. Search routines will guide the reader to the data of his desire. Until
that time, the index of each subvolume will have to do.
The present subvolume III/42A2 deals with Measuring Techniques and Surface Properties Changed by
Adsorption.
Finally and most importantly, I would like to extend my deep appreciation to all authors of this volume for
their excellent contributions, and to the editing and production offices of Springer-Verlag for efficient
cooperation and general support.
Jülich, January 2002 The Editor

Editor
H.P. Bonzel
Forschungszentrum Jülich
Institut für Grenzflächenforschung und Vakuumphysik (IGV)
52425 Jülich
Germany
Authors
K. Hermann
Fritz-Haber-Institut der Max-Planck Gesellschaft (MPG)
Abteilung Theorie
D-14195 Berlin
Germany
4.1 Surface structure on metals and semiconductors
H. Ibach
Institut für Grenzfläch enforschung und Vakuumphysik (IGV)
Forschungszentrum Jülich
D-52425 Jülich
Germany
4.4 Surface free energy and surface stress
K. Jacobi
Fritz-Haber-Institut der Max-Planck Gesellschaft (MPG)
D-14195 Berlin
Germany
4.2 Electron work function of metals and semiconductors
M.A. Rocca
Centro di Fisica delle Superfici e Basse Temperature del CNR
Istituto Nazionale di Fisica della Materia
I-16146 Genova
Italy
4.5 Surface phonon dispersion
D. Sander
Max-Planck Institut (MPI) für Strukturphysik
D-06120 Halle
Germany
M.A. Van Hove
Lawrence Berkeley National Laboratory
Materials Science 66
Berkeley, CA 94720
and Department of Physics
University of California-Davis
Davis, CA 95616
USA
P.R. Watson
Department of Chemistry
Oregon State University
Corvallis, OR 97331
USA
Ch. Wö ll
Lehrstuhl für Physikalische Chemie I
Ruhr-Universität Bochum
D-44801 Bochum
Germany
2 Characterization of adsorbate overlayers: Measuring techniques
Landolt-Börnstein
Editorial Office
Gagernstr. 8, D-64283 Darmstadt, Germany
fax: +49 (6151) 171760
e-mail: lb@springer.de
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Contents
III/42 Physics of Covered Solid Surfaces

A: Adsorbed Layers on Surfaces
Part 2: Measuring Techniques and Surface Properties Changed by Adsorption
1 Introduction to physical and chemical properties of adlayer/substrate systems

(H.P. BONZEL) ................................................... see subvolume III/42A1
2 Characterization of adsorbate overlayers: measuring techniques (CH. WÖLL) .......... 2-1

2.1 Introduction .......................................................................... 2-1
2.1.1 Comparative information on techniques discussed in this chapter....................... 2-2
2.1.2 List of acronyms used in this chapter .................................................. 2-4
2.2 Direct methods ....................................................................... 2-4
2.2.1 Monitoring adsorption by calorimetry ................................................. 2-5
2.2.2 Quartz crystal microbalance .......................................................... 2-5
2.2.3 Chemiluminescence .................................................................. 2-5
2.2.4 Exoelectrons ......................................................................... 2-6
2.2.5 Adsorption-induced changes of surface stress ......................................... 2-6
2.2.6 Adsorption-induced changes in resistivity ............................................. 2-6
2.2.7 Reflectance ellipsometry ............................................................. 2-6
2.2.8 Change of work function ............................................................. 2-7
2.3 Techniques based on a mass spectrometer ............................................. 2-7
2.3.1 Determination of sticking coefficients using a molecular beam ......................... 2-7
2.3.2 Thermal Desorption Spectroscopy (TDS) ............................................. 2-8
2.3.3 Laser-induced Thermal Desorption (LITD) ............................................ 2-9
2.4 Techniques for a chemical analysis.................................................... 2-9
2.4.1 Secondary Ion Mass Spectroscopy (SIMS) ........................................... 2-10
2.4.2 Ion Scattering Spectroscopy (ISS) ................................................... 2-10
2.4.3 Auger Electron Spectroscopy (AES) ................................................. 2-10
2.4.4 X-ray Photoelectron Spectroscopy (XPS) ............................................ 2-11
2.5 Structural sensitive techniques ....................................................... 2-13
2.5.1 Low Energy Electron Diffraction (LEED) ............................................ 2-13
2.5.2 Diffuse Low Energy Electron Diffraction (DLEED) .................................. 2-14
2.5.3 Photoelectron Diffraction (PED) ..................................................... 2-15
2.5.4 Techniques employing X-ray standing waves (XSW) ................................. 2-16
2.5.5 Extended X-ray Absorption Fine-Structure Spectroscopy (EXAFS) ................... 2-16
2.5.6 He-atom scattering (HAS) ........................................................... 2-18
2.5.7 Scattering of Rare Gases and Molecules .............................................. 2-19
2.5.8 X-ray Diffraction .................................................................... 2-19
2.5.9 Neutron Scattering .................................................................. 2-20
2.5.10 Ion Scattering Spectroscopy (ISS) ................................................... 2-20
2.6 Imaging techniques .................................................................. 2-21
2.6.1 Field Ion Microscopy (FIM) and Field Electron Microscopy (FEM) ................... 2-21
2.6.2 Transmission Electron Microscopy (TEM) ........................................... 2-22
2.6.3 Low Energy Electron Microscopy (LEEM) ........................................... 2-22
2.6.4 Photoemission Electron Microscopy (PEEM) ........................................ 2-22
2.6.5 Miscellaneous ....................................................................... 2-23
2.6.6 Scanning Tunneling Microscopy (STM) ............................................. 2-23
2.6.7 Atomic Force Microscopy (AFM) ................................................... 2-24
2.7 Vibrational spectroscopy of adsorbed particles ....................................... 2-25
2.7.1 Electron Energy Loss Spectroscopy (EELS) .......................................... 2-26
2.7.2 Infrared Reflection-absorption spectroscopy (IRAS) .................................. 2-26
2.7.3 Surface Enhanced Raman Spectroscopy (SERS) ...................................... 2-27
2.7.4 Inelastic scattering of He-atoms ...................................................... 2-27
2.8 Techniques probing the electronic structure .......................................... 2-28
2.8.1 Ultraviolet Photoelectron Spectroscopy (UPS) ....................................... 2-28
2.8.2 Inverse photoemission (IPE) ......................................................... 2-29
2.8.3 Near Edge X-ray Absorption Fine-Structure Spectroscopy (NEXAFS) ................ 2-30
2.8.4 Resonant X-ray Emission Spectroscopy (XES) ....................................... 2-31
2.9 Nonlinear optical techniques ......................................................... 2-32
2.9.1 Second Harmonic Generation (SHG)................................................. 2-32
2.9.2 Sum Frequency Generation (SFG) ................................................... 2-33
2.10 Bulk techniques ..................................................................... 2-33
2.10.1 Nuclear Magnetic Resonance (NMR) and Electron Spin Resonance (ESR) ............ 2-33
References .......................................................................... 2-35
3 Data: Adsorbate properties ....................................... see subvolume III/42A1
3.1 Adsorption of noble gases ........................................ see subvolume III/42A1
3.1.1 Noble gases on metals and semiconductors (P. ZEPPENFELD) ....... see subvolume III/42A1
3.1.2 Noble gases on graphite, lamellar halides, MgO and NaCl
(M. BIENFAIT) .................................................... see subvolume III/42A1
3.2 Adsorption of alkali metals ....................................... see subvolume III/42A1
3.2.1 Alkali metals on metals (R.D. DIEHL, R. McGRATH) ............... see subvolume III/42A1
3.2.2 Alkali metals on semiconductors (E.G. MICHEL, R. MIRANDA) ..... see subvolume III/42A1
3.3 Adsorption of metals ............................................. see subvolume III/42A1
3.3.1 Metals on metals (H. BRUNE) ..................................... see subvolume III/42A1
3.3.2 Metals on semiconductors
(V.G. LIFSHITS, K.OURA, A.A. SARANIN, A.V. ZOTOV) ............ see subvolume III/42A1
3.4 Non-metallic atomic adsorbates on metals and semiconductors .... see subvolume III/42A3
3.4.1 Chemisorbed hydrogen on metals and semiconductors
(K. CHRISTMANN) ............................................... see subvolume III/42A3
3.4.2 C, N, O on metals and semiconductors (H. OVER) ................ see subvolume III/42A3
3.4.3 Halogens on metals and semiconductors (E.I. ALTMAN) .......... see subvolume III/42A1
3.4.4 P, S, As, Sb on metals and semiconductors
(M. ENACHESCU, M. SALMERON) ................................. see subvolume III/42A3
3.5 Surface segregation of atomic species (non-metal on metal)
(H.-J. GRABKE, CH. UEBING, H. VIEFHAUS) ....................... see subvolume III/42A3
3.6 Molecules on graphite, BN, MgO (except noble gases)
(H. WIECHERT, J. SUZANNE) ...................................... see subvolume III/42A3
3.7 Molecular diatomic adsorbates on metals and semiconductors...... see subvolume III/42A3
3.7.1 CO and N2 on metals (A. FÖHLISCH, A. NILSSON, H.P. BONZEL) ... see subvolume III/42A3
3.7.2 NO, CN, O2 on metals (W.A. BROWN) ........................... see subvolume III/42A3
3.7.3 Diatomic molecules on alloys (B. E. NIEUWENHUYS) .............. see subvolume III/42A3
3.7.4 Diatomic molecules on semiconductors (K. HORN) ................ see subvolume III/42A3
3.8 Molecular polyatomic adsorbates on metals and semiconductors ... see subvolume III/42A3
3.8.1 H2O and OH on metals (G. PIRUG) ............................... see subvolume III/42A3
3.8.2 H2O and OH on semiconductors (W. JAEGERMANN, T. MAYER) ... see subvolume III/42A3
3.8.3 NH3 and PF3 on metals and semiconductors (E. HASSELBRINK) .... see subvolume III/42A3
3.8.4 CO2, NO2, SO2, OCS, N2O, O3 (B.E. KOEL) ...................... see subvolume III/42A3
3.8.5 Substituted hydrocarbons on metals (W.T. TYSOE, D.R. MULLINS) see subvolume III/42A3
3.8.6 Linear hydrocarbons and CH4 on metals and semiconductors
(G. SOMORJAI, G. RUPPRECHTER) ................................. see subvolume III/42A3
3.8.7 Cyclic hydrocarbons on metals and semiconductors
(G. HELD, H.P. STEINRÜCK) ...................................... see subvolume III/42A3
3.8.8 Oxygenated hydrocarbons on metals and semiconductors (J. VOHS) . see subvolume III/42A3
3.8.9 Halogen-substituted hydrocarbons on metals and semiconductors
(J. FIEBERG, J.W. WHITE) ........................................ see subvolume III/42A3
3.8.10 Polyatomic chain-like hydrocarbons on metals and semiconductors
(M. GRUNZE) .................................................... see subvolume III/42A3
3.8.11 Large aromatic adsorbates on metals and semiconductors
(M. SOKOLOWSKI, E. UMBACH) .................................. see subvolume III/42A3
3.9 Adsorption on oxides (H. KUHLENBECK, H.J. FREUND) ............ see subvolume III/42A3
3.10 Adsorption on alkali halides (J. HEIDBERG) ....................... see subvolume III/42A3
3.11 Surface diffusion on metals, semiconductors, and insulators
(E.G. SEEBAUER, M.Y.L. JUNG) .................................. see subvolume III/42A1
3.12 Dynamics of activated adsorption (A.C. LUNTZ) .................. see subvolume III/42A3
4 Data: Adsorbate-induced changes of substrate properties ............................ 4.1-1

(M.A. VAN HOVE, K. HERMANN, P.R. WATSON) ................................... 4.1-1
4.1.1 Introduction................................................. 4.1-1
4.1.2 Relaxation vs. reconstruction ....................................................... 4.1-1
4.1.3 Notations and conventions .......................................................... 4.1-3
4.1.4 Organization of the tables .......................................................... 4.1-4
4.1.5 Organization of data for individual structures ........................................ 4.1-4
4.1.6 Adsorption on fcc(111) ............................................................. 4.1-6
4.1.7 Adsorption on hcp(0001) ........................................................... 4.1-6
4.1.8 Adsorption on bcc(110) ........................................................... 4.1-7
4.1.9 Adsorption on fcc (100) ............................................................ 4.1-7
4.1.10 Adsorption on bcc (100), pure or alloyed ............................................ 4.1-8
4.1.11 Adsorption on fcc (110) ............................................................ 4.1-8
4.1.12 Adsorption on hcp ( 10 1 0 ) ......................................................... 4.1-9
4.1.13 Adsorption on bcc (211) ............................................................ 4.1-9
4.1.14 Adsorption on bcc (111) ............................................................ 4.1-9
4.1.15 Adsorption on Si, Ge and C(111) ................................................... 4.1-9
4.1.16 Adsorption on Si and Ge(100) ..................................................... 4.1-10
4.1.17 Adsorption on diamond-like(311) .................................................. 4.1-10
4.1.18 Adsorption on zincblende(110) .................................................... 4.1-10
4.1.19 Adsorption on zincblende(111) and (-1-1-1) ........................................ 4.1-11
4.1.21 Adsorption on 6H-SiC(0001) ...................................................... 4.1-11
Acknowledgments ................................................................. 4.1-11
Tables ............................................................................ 4.1-12
Table 1. Techniques used for surface structure determination; listed by their acronyms ........ 4.1-12
Table 2. Structures of clean fcc(111) surfaces............................................ 4.1-14
Table 3. Adsorbate-induced structures on fcc(111) surfaces ............................... 4.1-15
Table 4. Structures of clean hcp(0001) surfaces ......................................... 4.1-31
Table 5. Adsorbate-induced structures on hcp(0001) surfaces. ............................. 4.1-31
Table 6. Structures of clean bcc(110) surfaces........................................... 4.1-43
Table 7. Adsorbate-induced structures on bcc(110) surfaces............................... 4.1-44
Table 8. Structures of clean fcc(100) surfaces ........................................... 4.1-45
Table 9. Adsorbate-induced structures on fcc(100) surfaces ............................... 4.1-47
Table 10. Structures of clean bcc(100) surfaces.......................................... 4.1-57
Table 11. Adsorbate-induced structures on bcc(100) surfaces.............................. 4.1-58
Table 12. Structures of clean alloyed bcc(100) surfaces ................................... 4.1-62
Table 13. Adsorbate-induced structures on alloyed bcc(100) surfaces....................... 4.1-63
Table 14. Structures of clean fcc(110) surfaces .......................................... 4.1-64
Table 15. Adsorbate-induced structures on fcc(110) surfaces .............................. 4.1-67
Table 16. Structures of clean hcp(10-10) surfaces........................................ 4.1-75
Table 17. Adsorbate-induced structures on hcp(10-10) surfaces............................ 4.1-76
Table 19. Adsorbate-induced structures on bcc(211) surfaces.............................. 4.1-78
Table 21. Adsorbate-induced structures on bcc(111) surfaces. ............................. 4.1-79
Table 22. Structures of clean Si; Ge and C(111) surfaces ................................. 4.1-80
Table 23. Adsorbate-induced structures on Si; Ge and C (111) surfaces ..................... 4.1-80
Table 24. Structures of clean Si and Ge (100) surfaces.................................... 4.1-86
Table 25. Adsorbate-induced structures on Si and Ge (100) surfaces........................ 4.1-87
Table 26. Structures of clean Si(311) surfaces ........................................... 4.1-91
Table 27. Adsorbate-induced structures on Si(311) surfaces ............................... 4.1-91
Table 28. Structures of clean zincblende(110) surfaces ................................... 4.1-92
Table 29. Adsorbate-induced structures on zincblende(110) surfaces ....................... 4.1-93
Table 32. Structures of clean zincblende(-1-1-1) surfaces ................................. 4.1-96
Table 33. Adsorbate-induced structures on zincblende(-1-1-1) surfaces ..................... 4.1-96
Table 36. Structures of clean 6H-SiC(0001) surfaces ..................................... 4.1-98
Table 37. Adsorbate-induced structures on 6H-SiC(0001) surfaces ......................... 4.1-98
Figures for 4.1 .................................................................... 4.1-99
References for 4.1 ................................................................ 4.1-109
4.2 Electron work function of metals and semiconductors (K. JAKOBI) ................... 4.2-1
4.2.1 Introduction ........................................................................ 4.2-1
4.2.1.1 List of abbreviations................................................................ 4.2-1
4.2.1.2 Definition of work function ......................................................... 4.2-1
4.2.1.3 Work function versus local potential ................................................ 4.2-2
4.2.1.4 Standardization of work-function change with coverage ............................. 4.2-3
4.2.1.5 Experimental methods .............................................................. 4.2-4
4.2.1.5.1 Thermionic emission (Therm) ..................................................... 4.2-4
4.2.1.5.2 Field electron emission (FEM) ..................................................... 4.2-4
4.2.1.5.3 Photoemission (PYS, ARUPS) ..................................................... 4.2-5
4.2.1.5.4 Secondary electron edge method (SE edge) ........................................ 4.2-6
4.2.1.5.5 Diode method (Diode) ............................................................. 4.2-6
4.2.1.5.6 Vibrating capacitor method (Kelvin) ............................................... 4.2-6
4.2.1.6 Data collection ..................................................................... 4.2-7
4.2.2 Rare gases ......................................................................... 4.2-7
Ne, Ar, Kr, Xe
4.2.3 Atomically chemisorbed adsorbates ................................................ 4.2-13
4.2.3.1 Hydrogen, Deuterium ............................................................. 4.2-13
4.2.3.2 Carbon and C60.................................................................... 4.2-18
4.2.3.3 Nitrogen .......................................................................... 4.2-19
4.2.3.4 Oxygen ........................................................................... 4.2-20
4.2.3.5 Sulfur ............................................................................. 4.2-29
4.2.3.6 Selenium.......................................................................... 4.2-31
4.2.3.7 Tellurium ......................................................................... 4.2-31
4.2.3.8 Chlorine .......................................................................... 4.2-32
4.2.3.9 Bromine .......................................................................... 4.2-34
4.2.3.10 Iodine ............................................................................ 4.2-35
4.2.4 Small molecules ................................................................... 4.2-35
4.2.4.1 H2 ................................................................................ 4.2-35
4.2.4.2 N2 ................................................................................ 4.2-36
4.2.4.3 O2 ................................................................................ 4.2-37
4.2.4.4. CO ............................................................................... 4.2-37
4.2.4.5 NO, N2O .......................................................................... 4.2-42
4.2.4.6 NH3, PH3, PF3, P(CH3)3, AsH3 ..................................................... 4.2-44
4.2.4.7 H2O, D2O ......................................................................... 4.2-46
4.2.4.8 H2S ............................................................................... 4.2-48
4.2.4.9 CO2, SO2, (CH3)2SO, (CH3)3PO3 ................................................... 4.2-48
4.2.4.10 C2N2, HCN ....................................................................... 4.2-49
4.2.4.11 CH3CN, HCOOH, HNCO ......................................................... 4.2-50
4.2.4.12 KOH, KCl, HCl, HBr ............................................................. 4.2-50
4.2.5 Nonpolar hydrocarbons............................................................ 4.2-51
Methane (CH4), Propane (C3H8), Ethylene (C2H4), Acetylene (C2H2),
Propylene (CH3CH:CH2), Cyclopentane (C5H10), Pentadiene (C5H8), n-hexane (C6H14),
Cyclohexane (C6H12), Cyclohexene (C6H10), 1,3-Cyclohexadiene (C6H8),
Benzene (C6H6, C6D6), Toluene (C6H5-CH3), Ethylbenzene (C6H5C2H5),
n-butylbenzene (C6H5C4H9), t-butylbenzen (C6H5C(CH3)3), m-xylene (C6H4(CH3)2),
Biphenyle (C6H5C6H5), Naphtalene (C10H8), 2-Methylnaphtalene (C10H7CH3)
4.2.6 Polar hydrocarbons ................................................................ 4.2-58
Methanol (CH3OH), Ethyleneoxide (C2H4O), Ethylenedioxide ((CH2)4O2),
Acetone (C3H6O), Furan (C4H4O), Benzenethiol (C6H5SH), Pyridine (C6H5N),
Aniline (C6H5NH2), Nitrobenzene (C6H5NO2), Cyanobenzene (C6H5CN)
4.2.7 Halohydrocarbons ................................................................. 4.2-60
Chloro-methane (ClCH3), Chloro-ethane (ClC2H5), Di-chloro-methane (Cl2CH2),
Tri-chloro-methane (Cl3CH), Tetra-chloro-methane (Cl4C), Bromo-methane (BrCH3),
Di-bromo-methane (Br2CH2), Tetra-bromo-methane (Br4C), Iodo-methane (ICH3),
Iodo-ethane (IC2H5), Chloro-tri-fluoro-methane (ClCF3),
1,2-di-chloro-ethane (ClCH2CH2Cl), 1,2-di-chloro-ethene (ClCH:CHCl),
1,2-chloro-bromo-ethane (ClCH2CH2Br), Iodo-benzene (IC6H5), Chloro-benzene (ClC6H5)
4.2.8 Other hydrocarbons ............................................................... 4.2-62
Di-ethyl-zink ((C2H5)2Zn), glycine (α-amino acetic acid) (H2NCH2CO2H),
Closo-1,2-di-carbado-decaborane (C2B10H12),
TCNQ (Tetra-cyano-quino-dimethane) (C12N4H4)
4.2.9 Alkali metals ...................................................................... 4.2-63
Li, Na, K, Rb, Cs
4.2.10 Noble metals ...................................................................... 4.2-76
Cu, Ag, Au
4.2.11 3d transition metals................................................................ 4.2-83
Ti, V, Cr, Fe, Co, Ni
Zr, Nb, Mo, Rh, Pd
La, Hf, Ta, W, Re, Os, Ir, Pt
4.2.14 Rare-earth metals.................................................................. 4.2-91
Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb
4.2.15 Group IIa metals .................................................................. 4.2-93
Be, Sr, Ba
4.2.16 Group IIIa metals ................................................................. 4.2-95
Al, Ga,
4.2.17 Group IVa elements ............................................................... 4.2-96
C, Si, Ge, Sn, Pb
4.2.18 Group Va elements ................................................................ 4.2-98
N, P, As, Sb, Bi
4.2.19 Other elements .................................................................... 4.2-99
Hg, U
Figures for 4.2 ................................................................... 4.2-100
References for 4.2 ................................................................ 4.2-118
4.3 Electron binding energy of metals and semiconductors
(R. DENECKE, N. MARTENSSON, A. NILSSON) ..................... see subvolume III/42A3
4.4 Surface free energy and surface stress (D. SANDER, H. IBACH) ....................... 4.4 -1
4.4.1 Introduction ........................................................................ 4.4 -1
4.4.2 Experimental determination of surface free energy................................... 4.4 -2
4.4.2.1 Cleavage experiments .............................................................. 4.4 -3
4.4.2.2 Pendant drop and drop weight method .............................................. 4.4 -4
4.4.2.3 Zero creep experiments ............................................................. 4.4 -5
4.4.2.4 Orientation dependence of the surface free energy ................................... 4.4 -6
4.4.2.5 Empirical relation between surface free energy and other quantities .................. 4.4 -8
4.4.3 Experimental determination of the absolute value of the surface stress ................ 4.4 -8
4.4.3.1 Lattice parameter of small particles ................................................. 4.4 -8
4.4.3.2 Surface phonons as indicator of surface stress ....................................... 4.4 -9
4.4.3.3 Absolute surface stress from the bending of thin crystal plates ....................... 4.4 -9
4.4.4 Experimental determination of changes of surface stress due to adsorption .......... 4.4 -10
4.4.5 Calculations of surface free energy and surface stress ............................... 4.4 -13
4.4.5.1 Inert gas crystals .................................................................. 4.4 -14
4.4.5.2 Ionic crystals ...................................................................... 4.4 -14
4.4.5.3 III-V compounds .................................................................. 4.4 -15
4.4.5.4 Group IV materials ................................................................ 4.4 -15
4.4.5.5 Metals ............................................................................ 4.4 -16
4.4.5.6 Calculated adsorbate-induced surface stress ........................................ 4.4 -16
4.4.6 Data .............................................................................. 4.4 -18
4.4.7 Clean surfaces .................................................................... 4.4 -19
4.4.7.1 Surface free energy from cleavage experiments ..................................... 4.4 -19
4.4.7.2 Surface free energy of metals near the melting point ................................ 4.4 -19
4.4.7.3 Temperature dependence of the surface free energy................................. 4.4 -21
4.4.7.3.1 Temperature dependence of the anisotropy of the surface free energy ............... 4.4 -22
4.4.7.4 Calculated surface free energy and surface stress for inert gas crystals ............... 4.4 -22
4.4.7.5 Calculated surface free energies and surface stress for alkali halides ................. 4.4 -23
4.4.7.6 Calculated surface free energy and surface stress of III-V compounds ............... 4.4 -23
4.4.7.7 Calculated surface free energy and surface stress for Si and Ge ..................... 4.4 -24
4.4.7.8 Calculated adsorbate-induced changes of stress on semiconductor surfaces .......... 4.4 -25
4.4.7.9 Calculated surface free energies of metals .......................................... 4.4 -26
4.4.7.10 Calculated surface stress ........................................................... 4.4 -32
4.4.7.11 Calculated adsorbate induced surface stress on Pt(111) ............................ 4.4 -34
4.4.8 Adsorbate-induced changes of surface free energy .................................. 4.4 -34
4.4.9 Adsorbate-induced changes of surface stress ....................................... 4.4 -36
4.4.9.1 Gas adsorption .................................................................... 4.4 -36
4.4.9.2 Alkali metal deposition ............................................................ 4.4 -40
4.4.9.3 Semiconductor and metal deposition ............................................... 4.4 -40
References for 4.4 ................................................................. 4.4 -44
4.5 Surface phonon dispersion (M.A. ROCCA) ........................................... 4.5-1
4.5.1 Introduction ........................................................................ 4.5-1
4.5.1.1 Background and general layout ..................................................... 4.5-1
4.5.1.2 Symmetry considerations, energy and momentum conservation and
relevant selection rules in inelastic scattering ........................................ 4.5-3
4.5.1.3 Folding of the surface Brillouin zone by symmetry reduction, mode mixing,
phonon crossing and opening of energy gaps ........................................ 4.5-3
4.5.1.4 Phonon anomalies .................................................................. 4.5-4
4.5.1.4.1 Effect of mass loading, modification of force constants and surface stress ............ 4.5-4
4.5.1.4.2 Kohn anomaly ..................................................................... 4.5-5
4.5.1.5 Dispersion of adsorbate induced modes ............................................. 4.5-6
4.5.1.6 Theoretical models ................................................................. 4.5-7
4.5.2 Data collection ..................................................................... 4.5-7
4.5.2.1 Correspondence of units ............................................................ 4.5-9
4.5.2.2 Metal surfaces ..................................................................... 4.5-9
Ag, Al, Cu, Mo, Ni, Pb, Pt, Rh, Ru, W
4.5.2.3 Elemental semiconductors and insulators ........................................... 4.5-20
C, Ge, Si
4.5.2.4 Compound semiconductors ........................................................ 4.5-22
GaAs, GaP, InAs, InP
4.5.2.5 Oxides and Salts .................................................................. 4.5-23
MgO, NaCl
Acknowledgements................................................................ 4.5-24
Figures for 4.5 .................................................................... 4.5-25
References for 5.4 ................................................................. 4.5-68
4.6 Surface optical properties (N. ESSER, W. RICHTER) ................ see subvolume III/42A3
2 Measuring techniques
CH. WÖLL
2.1 Introduction
Whereas the observation of molecular adsorption on a solid surface can be monitored by the naked eye
(corrosion of e.g. iron surfaces, formation of patina on copper,...), more detailed investigations require the
availability of rather sophisticated equipment. The diffraction of electrons represents the first method of
its kind to portray the structure of single crystalline solid surfaces [27DAVa; 27DAVb]. Even in the first
studies the adsorption of gases on the specimen has been noted and found to cause „anomalous“ beams
[27DAVb], very likely the first observation of an ordered molecular adlayer on a solid substrate. Today
electron diffraction prevails as the standard technique to characterize adsorbate covered surfaces of well-
ordered solids. As a result of the comparatively simple technical requirements this technique enjoys
widespread distribution and tremendous success in the determination of structures and relaxation-effects
on clean surfaces as well as in the investigation of adsorbate overlayers. The immense body of knowledge
present today about the application of this technique is the source not only for ongoing research in surface
science but also for the development of related techniques, e.g. the different versions of photoelectron
diffraction.
The diffraction of electrons is complemented by the oldest technique for structure determination of
bulk matter, the diffraction of X-rays. Due to the very small (typ. 1015 part/cm2) scattering cross section of
a monolayer this technique is not suitable for the determination of adsorbate structures on solid substrate
surfaces in a straightforward fashion, which also holds true for neutron scattering, another standard
technique in bulk structure determination.
Despite the tremendous success of electrons in surface science studies other probe particles also
generate diffraction patterns from surfaces. The application of neutral atoms and molecules with thermal
energies for surface diffraction studies [30EST] had been preceded by electron scattering by only a few
years. Although this method has been applied in numerous investigations, it has not developed into a
widespread technique, mostly because of the considerable experimental efforts required to generate and
detect molecular (and atomic) beams. Atoms at higher than thermal energies exhibit de Broglie
wavelengths significantly smaller than the lattice-spacing of solids and can therefore not be used for
diffraction studies. By going to even higher energies, however, the wavelength becomes so small that the
motion of the particles can be treated classically. Subsequently, the scattering of low, medium and high
energy ions has been used together with a classical trajectory analysis in a large number of works to
investigate the structure of surfaces, clean and adsorbate-covered.
In the following the different probe techniques suitable for structural analysis of adsorbed layers on
surfaces will be briefly discussed. We will begin with the conceptually most simple and direct methods,
which are principally also suited for designing sensor devices. We will proceed with slightly more
complicated yet still straightforward techniques based on a mass spectrometer and then continue with
diffraction and other structural sensitive techniques which make full use of the advanced technology
available today. Subsequently, methods sensitive to adsorbate vibration and electronic structure will be
presented. Together with a brief description of the respective technique, the major limitations will be
briefly mentioned. The description of the rather large set of measuring techniques starts with a list of
acronyms for the different methods and a table, which classifies the techniques according to a number of
different criteria. The table should be used, however, only as a rough guide, a more detailed discussion of
the respective merits and limitations will be provided in the related paragraphs.
Landolt -Börnst ein

New Series III/42A2
2-2 2 Measuring techniques [Ref. p. 2-35
2.1.1 Comparative information on techniques discussed in this chapter

For the list of acronyms used in this chapter, see page 2-4
Elemental Chemical Binding Structural Geometric Resol. Geometric Resol.
state energy order, structure [Å] structure [Å]
(1) coh.length (ordered) (disordered)
LEED - - ind. + + 0.01 (+) 0.05
HREELS (+) + ind. - (+) (+)
HAS - - ind. + + (+)
SEM,TEM - - - + +
ISS + - ind. - (+) -
TPD + (+) + - - -
SIMS + (+) - - -
SHG - - - (+) -
SFG - + - (+) -
XPS + (no H) (+) ind. - (+) XPD (+) XPD
AES + (no H) (+) - (+) (+)
UPS - (+) + (+) (+)
NEXAFS + (no H) ++ ind. - (+) orient. (+) orient.
XES + (no H) ++ - (+) (+)
STM - (+) + + 0.01 vert (+)
0.2 hor
AFM - - + + +
IRAS (+) + (ind.) - (+) orient. (+) orient.
EXAFS + - - + 0.01 +
LITD - (+) ind. - - -
PED (+) (+) + 0.01 -
XSW (+) (+) + 0.01 -
XRD - - + + 0.01 -
SERS - - - - (+) -
IPE - (+) - - -
FIM (+) (+)
FEM (+) (+)
Φ, ∆Φ - - - - -
Lando lt -Bö rnst ein

New Series III/42A2
Ref. p. 2-35] 2 Measuring techniques 2-3
Phase Electronic Inter- Vibrations Diffusion Destructive Synchrotron

transitions structure pretation required
(valence) (2)
LEED + - + - - -
HREELS - ++ ++ - -
HAS + - + + (FIR) (3) + -
SEM,TEM - (+) - - yes
ISS - (+) - - yes
TPD - + - - yes
SIMS - + - - yes
SHG (+) - - (+) -
SFG - - + (+) -
XPS (+) + - -
AES - - - - yes
UPS ++ + - - -
NEXAFS (+) + - - - yes
XES ++ + - - - yes
STM (+) (+) + (+) (+) -
AFM (+) - + - - -
IRAS - ++ ++ - -
EXAFS - + - - - yes
LITD - (+) - + yes
PED (+) - + - - -
XSW - + - - varies yes
XRD - + - - varies helpful
SERS - + + -
IPE + + - - -
FIM
FEM
Φ, ∆Φ (+) - - - - -
(1) Basically all methods can be used to roughly determine the binding energy by determining the temperature where
the molecule is desorbed from the surface.“ind“ is entered when the method is frequently applied for this purpose.
(2) Many techniques require significant theoretical and computational effort to obtain the desired information. In this
column ++ indicates that this effort is small, whereas – indicates that significant effort is required.
(3) Mainly applied to vibrations in the Far-Infrared regime (< 200 cm-1 or < 25 meV)

New Series III/42A2
2.1.2 List of acronyms used in this chapter

AES Auger Electron Spectroscopy
AFM Atomic Force Spectroscopy
DLEED Diffuse Low Energy Electron Diffraction
EXAFS Extended X-ray Absorption Fine Structure
HAS He-Atom Scattering
HREELS High-Resolution Electron Energy-Loss Spectroscopy
IPE Inverse Photoemission
IRAS Infrared Reflection Absorption Spectroscopy
ISS Ion Scattering Spectroscopy
LEED Low Energy Electron Diffraction
LEEM Low Energy Electron Microscopy
LEIS Low Energy Ion Scattering
LITD Laser-Induced Thermal Desorption
MEIS Medium Energy Ion Scattering
NEXAFS Near Edge X-ray Absorption Fine Structure
PEEM Photoelectron Electron Microscopy
PED Photoelectron Diffraction
QCM Quartz Crystal Microbalance
QMS Quadrupole Mass Spectrometer
RBS Rutherford Backscattering
SEM Scanning Electron Microscopy
SERS Surface Enhanced Raman Spectroscopy
SFG Sum Frequency Generation
SHG Second Harmonic Generation
SIMS Secondary Ion Mass Spectrometry
STM Scanning Tunneling Microscopy
TEM Transmission Electron Microscopy
TDS Thermal Desorption Spectroscopy
TPD Temperature Programmed Desorption
UPS Ultraviolet Photoelectron Spectroscopy
XANES X-ray Absorption Near Edge Structure, see NEXAFS
XES X-ray Electron Spectroscopy
XPS X-ray Photoelectron Spectroscopy
XRD X-ray Diffraction
XSW X-ray Standing Wave
Φ Work Function
2.2 Direct methods
The adsorption of a molecule on a surface, as schematically illustrated in Fig. 1, leads to changes of a

number of different quantities and properties. The main problem in surface science is that these changes
are restricted to the top substrate layer and are thus very small in relation to any changes of the bulk. As a
result, rather complicated surface sensitive techniques have been developed in the past decades to gain
information on the adsorption process and the nature of the substrate-adsorbate complex. Very often these

New Series III/42A2
methods are rather indirect, and a significant computational effort is required to obtain e.g. precise
information on adsorbate geometries from the experimental data. There are, however, a few general
methods where the required information can be obtained in a rather direct way. Correspondingly, these
techniques are in principle suited for applications as sensors. In the following we will briefly list the most
important of these conceptually very simple methods before proceeding with the methods which have
been designed for surface studies.
Fig. 1. Adsorption of a molecule on a

solid substrate. In the case shown in
the figure the process is called
associative, since the molecule is not
dissociated upon adsorption.
2.2.1 Monitoring adsorption by calorimetry

One of the most direct ways to follow an adsorption process and to quantitatively determine the excess
energy is by detection of the corresponding rise in substrate temperature. Although substrates with
thicknesses in the mm range have heat capacities which are far too large, the preparation of very thin films
makes such measurements possible. In the case of polycrystalline films evaporated onto thin glass
substrates direct measurements of heats of adsorption have been reported for a number of different
adsorbate/substrate combinations [78WED]. For single crystalline films, however, the task is considerably
more difficult, since the growth of very thin films with high structural quality poses a huge experimental
challenge. These problems, however, have in recent years been overcome and it was possible to apply the
method e.g. to the case of oxygen on Ni(100), where temperature rises originating from the adsorption of
amounts as small as 0.01 monolayers could be detected [91BOR]. Although this method is very elegant,
the severe technological limitations restrict its application to but a few cases.
Recently, a novel approach has been demonstrated for detecting the small temperature changes
accompanying the adsorption of gases on metal surfaces. In a pioneering investigation the heat evolution
in the adsorption and subsequent reaction of O2 and H2 to form water on a thin Pt-layer evaporated on a
SFM bimetallic cantilever has been studied [94GIM].
2.2.2 Quartz crystal microbalance

Another physical quantity which can in principle be used to detect adsorption is the corresponding
increase in weight. The detection of such mass-changes via a precise measurement of the resonance
frequency of a quartz crystal is a standard technique to monitor the deposition of metal films. The method
is, however, only rarely applied to the investigation of adsorbates because of experimental problems and
the difficulty to grow well-defined films on quartz substrates. Recently, however, a quartz crystal
microbalance (QCM) has been used to monitor the adsorption of noble gases and simple hydrocarbons on
surfaces of Ag-films [90KRI; 96DAL].
2.2.3 Chemiluminescence
In principle the adsorption process can be viewed as a chemical reaction and several phenomena
accompanying reactions in the gas-phase or the liquid also occur for surface reactions. One of these is

New Series III/42A2
chemiluminescence, where electronically excited product molecules decay to their ground state by
emission of photons. Of course this process requires that the adsorption energy is sufficiently large and
that non-radiative processes do not come into play. Due to the fairly small number of surface reaction sites
considerable experimental effort is required for detection. Nevertheless, chemiluminescence
accompanying adsorption has been observed in a few cases, e.g. for the adsorption of chlorine on K-
surfaces [85AND].
2.2.4 Exoelectrons
A very convenient way to follow adsorption is the detection of electrons generated during the adsorption
process. Since the reaction with the surface must be sufficiently energetic for the emitted electrons being
able to overcome the substrate work-function, the phenomenon has been observed only in a few cases, e.g.
during the oxidation of Cs- and Na-surfaces [94GRO],[92BOE].
2.2.5 Adsorption-induced changes of surface stress

The creation of a surface can give rise to significant mechanical stress, which can be related to the
difference in chemical environment for surface atoms and bulk atoms. Generally, adsorption of particles is
expected to change this stress. Since the absolute forces related to this phenomenon are rather small,
significant experimental effort is required to detect the adsorption-induced changes in surface stress. Such
measurements are, however, feasible and results have been reported for polycrystalline films evaporated
onto specially designed cantilevers [86ABE]. Recently, it has been possible to extend these measurements
to single crystalline substrates, including the oxidation of silicon [91SAN] and molecular adsorbates on
Ni(100) [94GRO].
2.2.6 Adsorption-induced changes in resistivity

One of the oldest and experimentally most straightforward ways to detect adsorption on metals – even for
weak adsorbate-substrate interaction as in the case of N2-molecules adsorbed on Cu - is the measurement
of the conductivity of thin metal films [72WIS; 87WIS]. Attaining a detailed understanding of the basic
microscopic mechanism causing this effect has been hampered by the fact that the thin films used for these
experiments generally exhibit rather poor structural quality. Recently, it has been shown theoretically, that
the change in dc-resistivity upon molecular adsorption is related to the reduction of electron-hole lifetime
in the top layers of the substrate through excitations of frustrated translations of the adsorbed molecules
[91PER; 94PER].
2.2.7 Reflectance ellipsometry

Adsorption of atomic or molecular species affects the electronic structure of the substrate and, as a
consequence, the reflectivity (or color) of the surface. Although these changes are typically very small,
independent measurements of the reflectivity for differently polarized light (s vs. p) and the phase delay
between the two polarizations allow to monitor e.g. the adsorption of noble gas adlayers on graphite with
submonolayer sensitivity [93YOU]. Recently, it has been demonstrated that the method can be combined
with an optical microscope to image in-situ the patterns formed in surface reactions using visible light
[95ROT; 96HAA].

New Series III/42A2
2.2.8 Change of work function

In case of conducting samples adsorption events are typically accompanied by a change of the work-
function, Φ, i.e. the minimum energy required to remove an electron from the probe. The microscopic
origin of this behavior is related to the formation of a dipole-adlayer, which is particularly strong if the
molecule carries a significant dipole moment (e.g. in the case of the cyclic ether trioxane, C3H6O3,
[94HOF]). But also in case of physisorbed noble gas atoms, e.g. Xe, noticeable changes in work-
function, ∆Φ, can be observed [87JAC]. A variety of methods has been used to detect these changes, some
of which are conceptually rather simple and can be used also for sensor applications (e.g. vibrating
capacitor method). Several methods for detecting work function changes are based on equipment
primarily used for other methods (e.g. UPS). Since work-function changes are rather important for both
monitoring the adsorption of adparticles and the understanding of adsorption–induced changes in
electronic structure, chapter 4.2 is devoted to this topic.
2.3 Techniques based on a mass spectrometer
2.3.1 Determination of sticking coefficients using a molecular beam
F1 F2
flag F1 F2 open open
molecular to QMS
beam sample
Pressure
to pump Time
Fig. 2. Schematics for determining the sticking coefficient using the King and Wells method [72KIN]. The diagram
on the right hand shows the mass spectrometer (QMS) signal after first opening flag F1 and then flag F2.
An important question concerning a particular adsorbate/substrate combination is whether for a given

substrate temperature the particle or molecule sticks to the surface, and what the sticking probability
amounts to. The conceptionally most simple method to answer this questions is the so-called King and
Wells method [72KIN] as illustrated in Fig. 2. A molecular beam containing either the pure substance or a
mixture with an inert (e.g. He, Ar) carrier gas impinges on the substrate and the pressure in the recipient is
measured using either a mass-insensitive pressure gauge (e.g. an ionization gauge) or a mass spectrometer.
The experiment starts by determining the pressure inside the chamber containing the clean substrate with
the molecular beam of the corresponding particle (e.g. CO) blocked by a flag (F2) with a chemically inert
surface. After opening the flag the pressure drops due to adsorption on the sample surface. The pressure is
recorded until saturation sets in. If the particle or molecule sticks to the surface with unity sticking
coefficient, the pressure inside the chamber will initially drop to zero, since all incident particles are
trapped by adsorption to the surface. If the number of free surface sites is reduced, particles are scattered
back into the vacuum chamber, giving rise to an increase of the pressure. Measurements of this kind give
rise to detailed information of the absolute value of the sticking coefficient and its dependence on
coverage, defects and coadsorbates. Although the method requires substantial technical effort, preparation

New Series III/42A2
of a well collimated molecular beam, it can be used to measure sticking probabilities on virtually all types
of substrates. Structural order is not a prerequisite, and the method can be applied to metals and
semiconductors as well as to insulators. For very small (<< 0.05) sticking coefficients the method
becomes difficult to apply due to the long measuring times and the corresponding small changes in
pressure.
The method only monitors the adsorption on a surface, a combination with a more elaborate technique
is required to find out whether adsorbates stick at the point where they first hit the surfaces or whether
they are sufficiently mobile to diffuse to defect sites [00BEC].
2.3.2 Thermal Desorption Spectroscopy (TDS)
Fig. 3. Schematic illustration of a second order desorption process in thermal

desorption spectroscopy, TDS. Upon heating the adsorbed atoms form molecules
before they desorb from the surface and are detected in a mass spectrometer (MS).
One of the key issues when investigating adsorbate overlayers on solid substrates is the question whether
the adsorption of a particle (atom, molecule) is reversible (i.e. whether the intact particle can be desorbed
from the surface by e.g. heating) or whether the interaction between adparticle and substrate is so strong
that adsorption is accompanied by fragmentation. Together with qualitative information on this behavior
also quantitative information on binding energies and desorption kinetics is needed. The most powerful
technique to answer this type of basic question is thermal desorption spectroscopy (TDS), frequently also
referred to as temperature programmed desorption (TPD). Basically, the strength of the adsorbate-surface
interaction is determined by linearly increasing the substrate temperature (typ. rate 5 K/s) and then
detecting the particles desorbing from the surface using a mass spectrometer (see the schematic drawing in
Fig. 3). Since the mass spectrometer can detect the mass of a desorbing particle, this technique can be
employed to distinguish between the desorption of the intact adparticle or its fragments. More importantly,

New Series III/42A2
the determination of the temperature at which the desorption maximum is observed allows for a rough
estimation of the energy by which the particle is bound to the surface. Although the technique is
conceptionally rather simple, there are several difficulties, related to both data acquisition and data
analysis. With regard to the former, a precise determination of binding energies requires a reliable
temperature measurement. Although a precise determination of substrate temperature presents no major
problem for metal substrates, for insulating or semiconducting materials (e.g. diamond and metal oxides)
such a measurement can require a considerable effort. There are in fact cases where different groups have
reported desorption temperatures for the same system differing by more than 100 K [97SCH]. A second
important point is the linearity of the substrate temperature as a function of time. Even small deviations
can significantly alter the shape of the TDS-curves and make a quantitative analysis very difficult if not
impossible.
Concerning the analysis of the thermal desorption spectra, a detailed understanding of the
experimentally measured desorption rates requires precise modeling of all relevant interaction energies
[99KRE]. Although in most cases the adsorbate-substrate interaction is dominant, the adparticle-adparticle
interaction can also significantly affect position and shape of the desorption maxima. Since the desorption
process is governed by thermodynamics, entropic contributions also become important. It should be noted
that in addition to obvious contributions from configurational entropy for weakly adsorbed species,
vibrational entropy plays an important role, too [97KRE].
2.3.3 Laser-induced Thermal Desorption (LITD)

When raising the substrate heating rate by using an intense laser beam, the desorption of the particles
becomes so fast that a detailed determination of binding energies is impossible. Nevertheless, laser
induced thermal desorption (LITD) has become an important tool for investigations of diffusion processes
on surfaces. For this purpose, the laser is focussed on a small spot of several µm diameter. With a first
laser pulse all adparticles within the spot area are desorbed. After termination of the laser pulse, thermal
diffusion along the surface leads to a repopulation which can be determined quantitatively using a second
laser pulse. The amount of desorbed particles is measured using a mass spectrometer, and from the
amount of particles detected within the spot after different times the diffusion coefficient can be obtained.
A large number of different systems has been investigated, a few examples are alkanes [90BRA] or CO
and K [96WES] adsorbed on Ru(0001). A major advantage of the method is the fact that it can be applied
for a large number of substrates, including semiconductors and insulators.
2.4 Techniques for a chemical analysis
When investigating adsorption phenomena a key requirement is to study the cleanliness of a given
substrate before the adsorption process and to determine the chemical compositions of the products
formed in the subsequent adsorption. For this purpose techniques which are sensitive to the presence of
different elements on a substrate surface are required. Although virtually all of the methods discussed here
can be used in one way or another to follow an adsorption process, a technique which provides direct
information on the chemical composition of a surface is very often a necessary prerequisite for fully
characterizing the behavior of a particular adsorption system. In the following we will discuss first
secondary ion mass spectroscopy, or SIMS, and then two variants of photoelectron spectroscopy, X-ray
photoelectron spectroscopy (XPS) and Auger electron spectroscopy (AES).

New Series III/42A2
2.4.1 Secondary Ion Mass Spectroscopy (SIMS)

When a beam of energetic (1-10 keV) particles, either charged or neutral, impinges on a surface, atoms
and molecular fragments are emitted. A small fraction of the ejected species is charged (either positive or
negative) and can be detected via mass spectrometer. The mass spectrum shows a distribution of
fragments typical for a given substance. In connection with the characterization of adsorbates on solid
substrates the technique is only useful when the primary flux is reduced to about 5x1012 atoms /cm2. In
that case the method is referred to as static SIMS. Although most applications of static SIMS are restricted
to polycrystalline substrates [85BEN], it occasionally finds use in the study of adsorption of molecules on
single crystalline surfaces, e.g. propene on Ru(0001). At higher fluxes significant amounts of material are
removed from the surface, and material from deeper regions of the substrate surface is ejected. The high
flux variant is called dynamic SIMS and is an important analytical method [92BRU].
Although static SIMS is applied predominantly for material characterization [92BRU], true surface
sensitivity can be achieved when combining the method with powerful and sensitive mass spectrometers
(e.g. a time-of-flight mass spectrometer). A particular advantage of SIMS is that all elements (including
H) can be detected.
2.4.2 Ion Scattering Spectroscopy (ISS)

When medium energy ions (200-3000 eV) impinge on a surface the energy exchanged with the substrate
depends on the mass of the substrate atoms hit in the collision processes. As a result the ion energy loss
can be used to determine the mass of the collision partner and thus provides direct information on the
elemental composition of the surface. For this ion scattering spectroscopy, or ISS, typically noble gas ions
(frequently also 3He) are used. Since most electron-energy analyzers can be operated also with reversed
polarity and the only additional component required for ISS-measurements is a sputter-gun, this technique
is widely accessible. One major advantage of this method is the ability to detect H-atoms, e.g. in the case
of hydrogen on a Ru(001)-substrate [93NIE]. Lateral order is not required for applying this technique. See
also the chapter on the scattering of ions.
3.4.3 Auger Electron Spectroscopy (AES)

e-
e- to electron
Kontinuum energy analyzer
Kinetic energy
Continuum

h’
h’
Photonenenergie

Fig. 4. In Auger electron spectroscopy, AES, an
electron is removed from a core level by either high-
energy electrons or X-ray photons. The excited states
decay via transition of a less strongly bound electron
h count rate
horfest into the empty core-level and the emission of a third
high-energy e -
electron. The kinetic energy of the latter is determined
Intensität using an electron energy analyzer.
One of the oldest experimental methods available for determining the electronic structure of solid
substrates is based on the excitation of electrons from a core level state (binding energy Eb) to a
continuum state either by collisions with high energy electrons (typically around 3 keV) or X-ray photons
(see Fig. 4). The core-excited electronic state is highly unstable and decays by a transition of an electron
with smaller binding energy E′b into the empty state. Two different variants of this process are observed.
In the first type the electronic transition is accompanied by emission of a second electron, the Auger

New Series III/42A2
electron, from a state with binding energy E ′b′ . The Auger electron carries a kinetic energy of
Ek = E ′b′ – ( E ′b – Eb). This Auger process competes with a second process where the first transition is
accompanied by the emission of a photon with an energy corresponding to h⋅ν = E ′b – Eb. The final state
thus carries a charge of +2 in Auger spectroscopy and of +1 in fluorescence spectroscopy. The
fluorescence process dominates Auger electron emission for atoms with Z larger than ~ 20.
Using high-energy electrons for the excitation process turns Auger electron spectroscopy (AES) into a
versatile method for determining the composition of surfaces, since the generation of electrons with
energies around 3 keV is rather straightforward. This type of excitation, however, is not well suited for the
investigation of molecular adsorbates due to the low threshold levels for electron beam damage. Thus the
more delicate adsorbates require the use of X-rays to initiate the primary excitation [76FUG; 82FUG].
The positions of the Auger-lines for the different elements are tabulated [78WAG]. The analysis of Auger-
spectra becomes very tedious, if information about details on the electronic structure of adsorbed
molecules is sought. Nevertheless, Auger spectra of molecular adsorbate species are often rich in structure
and reveal detailed information on the electronic properties of the adsorbate-substrate complex [76FUG]
as well as on the geometries of molecular adsorbates [84UMB], e.g. the tilt-angle of CO on Ni(110)
[93MAC].
In conventional Auger electron spectroscopy the adsorbate carries a charge of +2 in the final state,
since two electrons have been removed. More recently a variant of the method has been employed, where
the exciting X-ray photons are tuned to an energy where the primary photoelectron is not emitted but
excited into an empty molecular level of the particle, resulting in a final charge of +1. This resonant Auger
process can provide more detailed information on the molecular adsorbate than the nonresonant process
[90POR; 94POR].
2.4.4 X-ray Photoelectron Spectroscopy (XPS)
e- to electron
Binding energy Eb
energy analyzer
Continuum
Intensity
Fig. 5 In X-ray photoelectron spectroscopy, XPS, a
substrate is illuminated wit X-ray photons of fixed
h fixed energy. The kinetic energy of the photoelectrons is
determined using an electron energy analyzer. In a
typical XPS-analysis only the energies of the core-
electrons are considered.
In X-ray photoelectron spectroscopy the information on the electronic structure of the specimen is
obtained by carrying out an energy analysis of the photoelectrons emitted from a probe illuminated by X-
ray photons. The primary process of X-ray photon absorption in matter, see Fig. 5, consists of an
excitation of a bound electron into an unoccupied electronic state. If this final state is a continuum state
with a kinetic energy sufficiently high to overcome the substrate work function, the electron will be
emitted from the probe. With an appropriate energy analyzer, the kinetic energy EK of the electron can be
measured and used to compute the binding energy according to Eb = hν – Ek. X-ray photoelectron
spectroscopy is particularly useful for determining the chemical composition of an adsorbate overlayer
and, if the resolution of both X-ray source and analyzer is sufficient, information can also be obtained on
the partial charge of that particular atom from which the core-electron originates. This chemical shift

New Series III/42A2
makes it possible to directly distinguish physisorbed O2-molecules from chemisorbed O-atoms on Pt-
substrates [89LUN], for example.
X-ray photoelectron spectroscopy, or XPS, is less useful for obtaining detailed information on the
electronic structure of a molecular adsorbate. The chemical shift of core-electrons is mainly determined by
the partial charge of the corresponding atom and to a lesser extent by the nature of the chemical bond to
adjacent atoms. For example the binding energies of the C1s core-level of carbon atoms in the saturated
hydrocarbon ethane (C2H6), 284.4 eV, and the unsaturated ethylene (C2H4), 284.2 eV, differ by only 0.2
eV; the difference to acetylene (C2H2), 283.7 eV, is slightly larger [74DAV].
On the other hand, in favorable cases the chemical shift observed for the same atom or molecule bound
at different adsorption sites can be sufficiently large to distinguish between them. In the case of CO
adsorbed on Rh(110), for example, the difference in O1s binding energies between CO bound at a bridge
and an on-top site amounts to 1.1 eV [93DHA]; in the case of CO coadsorbed with hydrogen on Ni(100)
the difference in C1s binding energy between on-top and hollow sites also amounts to 1.1 eV [98FOE]. In
connection with intense X-ray sources, e.g. a synchrotron, X-ray spectra can be recorded in very short
times (< 6 s), enabling the determination of adsorbate coverage as a function of surface temperature in a
fashion similar to thermal desorption spectroscopy [96BAR].
It should be noted, that some care has to be taken when interpreting the chemical shifts observed in
XPS data. The common case is that these shifts are caused by differences in the partial charge at the
respective atom, thus leading to differences in the core-level binding energies. This so-called initial state
effect has to be distinguished from final state effects, where differences in the screening of the core-hole
generated in the photoabsorption process come into play. For example in the case of simple saturated
hydrocarbons adsorbed on Cu(100), a C1s-shift of about 1 eV is observed with respect to the gas-phase or
multilayer data, an effect which is mainly related to the improved screening of the core-hole by the metal
electrons in the vicinity of the substrate surface [95WIT].
With regard to molecular adsorbates the XPS-method has significant advantages over Auger electron
spectroscopy, since the extraction of quantitative information from the experimental data can be carried
out in a much more direct fashion. The X-ray absorption cross section for a given element does not
depend on its chemical environment and the area of a given X-ray photoelectron peak thus provides a
good measure of the concentration of the particular element in the probe material. The cross sections have
been calculated theoretically for all elements (except H) and are readily available in tabulated form
[76SCO]. If the transmission function of the electron energy analyzer is known, reliable information on
the stoichiometry of an adsorbed molecule can be obtained from XP-spectra. Note, however, that
diffraction effects can lead to a pronounced angular variation of the emitted photoelectron intensity; see
the paragraph on photoelectron diffraction (PED). In some cases the primary excitation process is
accompanied by rearrangements of the electronic configuration (so-called shake-up process), which give
rise to satellites at the high-energy side of the core level lines, which can then be used to derive
information on the adsorbed species (e.g. C, N and O atoms on Ni [91NIL], N2 molecules on Ni
[81HER]).
The XPS-method can be applied to all systems where charging represents no major problem. It is the
method of choice for determining the chemical composition of an adsorbate layer. Among all techniques
employed for the characterization of the chemical composition of surfaces this is the most common one. It
is estimated that worldwide several thousand XPS-machines are currently being operated.

New Series III/42A2
2.5 Structural sensitive techniques
2.5.1 Low Energy Electron Diffraction (LEED)
Fig. 6. In low energy electron diffraction, LEED, electrons with energies between 10 eV and 1000 eV (schematically
shown as plane waves, left side top) are scattered from the substrate atoms. In case of ordered substrates the
interference of the scattered waves (approximated by spherical waves, left side bottom) yields sharp diffraction beams
which give rise to characteristic diffraction patterns. The LEED pattern shown on the right side has been recorded for
a c(4√3x2√3) overlayer of heptanethiolate (CH3-(CH2)6-S-) on n Au (111) substrate at an electron incident energy
of 27 eV.
The penetration depth of electrons into solids exhibits - for a very large number of conducting or
semiconducting materials - a minimum of about 1 nm for energies of 150 eV, corresponding to a
wavelength of 0.1 nm or 1 Å. This fairly small penetration depth yields a pronounced surface sensitivity
and presents the basis for all electron-based techniques in surface science. As schematically shown in Fig.
6, the electrons, which in this energy regime can be represented by a plane wave when penetrating into the
solid, are mainly scattered from the ion cores. The superposition of spherical waves emitted from the
atoms in the adlayer and in the deeper substrate layers leads to the formation of diffracted beams. An
important issue for the application to adsorbed layers on solid substrates is the fact that the intensity of the
emitted spherical wave depends on the scattering cross section of the particular type of atoms, which in
turn increases with atomic number Z. Diffraction from adlayers consisting of elements with low Z on
substrates consisting of elements with high Z-numbers thus yields small diffraction peaks on top of intense
diffraction spots originating from the substrate. Therefore, the detection of the weak adsorbate-induced
diffraction peaks represents a formidable experimental problem. In particular the structural
characterization of atomic hydrogen overlayers on solid substrates with LEED has been a major challenge
for experimentalists. Ideal cases for this type of analysis are overlayers consisting of large Z elements on
low Z substrates, e.g. Xe overlayers on graphite substrates.

New Series III/42A2
While the position of peaks in an electron diffraction pattern only provides information on the size and the
shape of the surface unit cell, LEED can also produce precise quantitative data on the position of the
adsorbate relative to the substrate atoms. By recording the intensity of a given LEED-spot as a function of
incident electron energy, so-called I(V)-curves can be measured. Today the most convenient experimental
procedure is to record the intensity variations of all LEED-spots simultaneously with a Video-camera
[84HEI; 88HEI]. The I(V)-curves typically show a rich structure arising from interference phenomena and
contain detailed information on the precise geometrical arrangement of adsorbates on a single crystalline
substrate. A structure determination based on the complete theoretical description of an experimental
I(V)-curve represents a formidable computational effort, thus imposing severe limitations on the size of
the unit cell. While overlayers with small unit cells, i.e. less than 5 atoms per substrate unit cell for a
surface with low miller indices, can be studied in a routine fashion, overlayers of larger molecules or large
unit cells are still difficult to handle. An example where a full I(V) structure analysis has been carried out
for a larger adsorbate is the adsorption of benzene on a Ru-surface [95STE]. Note, however, that in this
case only the position of the C-atoms could be determined. The scattering cross section of the H-atoms is
so small that these contributions were omitted from the analysis.
The fact that many molecular adsorbates exhibit non-zero cross sections for electron-induced damage
poses an experimental limitation on the application of the technique. To account for this fact, single or
double channel plates are used for recording the diffraction patterns in the most recent generation of
LEED-systems. Such systems make it possible to record a single diffraction pattern with a dosage of less
than one electron per 100 adsorbate molecules [95STE].
For diffraction studies the width of the electron energy distribution does not represent a major
problem. Therefore, most instruments use thermal electron emission without any monochromator. In the
case of adsorbates forming structures with large unit cells, resulting either from many particles per unit
cell or from the large size of the adsorbed molecule [98UMB], a variant of the technique with a
significantly enhanced angular resolution is used. In addition to the determination of diffraction peak
positions and intensities, SPA-LEED (for spot profile analysis-LEED) [86SCH] allows the analysis of
spot profiles. Today LEED is the standard technique for detecting lateral order in adlayers on single
crystalline metal substrates and semiconductors. For insulators the application is not straightforward, but
charging problems can be overcome by heating the substrate or by going to very low beam currents.
2.5.2 Diffuse Low Energy Electron Diffraction (DLEED)

A structure analysis with LEED requires the presence of ordered structures, since principally geometric
parameters are calculated from diffraction peak intensities. In the absence of order, e.g. in case of
randomly distributed adsorbates, the standard analysis of LEED patterns cannot be applied. In order to
overcome this limitation, in recent years a variant of LEED, namely diffuse low energy electron
diffraction (DLEED), has been developed [96STA]. Here, the full angular distribution of scattered
electron intensity is measured and subsequently analyzed theoretically. Although the technique requires a
significantly greater effort it becomes possible to determine adsorbate geometries despite absence of
lateral order. The technique has been applied to a number of atomic adsorbates [96STA], however, the
investigation of larger molecules was restricted to only a few (ethylene/Pt(111) [97DOL], CO2/Ni(110)
[88ILL]).

New Series III/42A2
2.5.3 Photoelectron Diffraction (PED)
Fig. 7. Schematics of photoelectron diffraction, PED. The primary photoelectron is scattered by the surrounding
atoms and the subsequent superposition leads to interference and the formation of a diffraction pattern.
While in low-energy electron diffraction the electrons being used as probe particles come from outside the
sample, diffraction phenomena can also be exploited with electrons generated inside the sample, e.g. by a
photoabsorption process. For sufficiently high kinetic energies (>500 eV) the scattering of the
photoelectron by the neighboring atoms is dominated by forward scattering, i.e. the scattered intensity is
peaked in the direction of neighboring atoms (see Fig. 7). As a result, information on the local
environment of a photo-ionized atom can be studied by experimentally determining the angular
distribution of emitted photoelectrons [88FAD]. In a typical application the presence of perpendicular and
tilted CO-molecules on clean and potassium-modified Ni(110) could be demonstrated by experimentally
determining the angular distribution of the C1s photoelectrons [89WES].
For smaller photoelectron energies (< 300 eV), the forward scattering mechanism is no longer
dominant and interference effects lead to a distribution of intensity over a much larger angular regime. As
a result, data analysis is not as straightforward and requires significant theoretical support. However, if
experimental photoelectron angular distributions are recorded for a series of different photon incident
energies (so-called "scan energy photoelectron diffraction"), the theoretical analysis of the experimental
spectra yields very detailed information on the position of the adsorbate atoms. It is of particular interest
that in addition to the atomic positions, information on the type of atoms is also contained in the
experimental data. Furthermore, this chemical sensitivity makes it possible to separately determine the
positions of atoms of the same type, which are equivalent for the free molecule but become chemically
distinct when adsorbed on a surface [99WEI]. Although the theoretical analysis of the experimental data is
rather complex, recently a direct method has been proposed, which allows for a direct extraction of
geometrical data from the experimental results [93SCHb].
The application of photoelectron diffraction has the same limitations as LEED, i.e. charging for
insulating substrates requires additional effort. Note, that long-range order is not necessary for applying
this method.

New Series III/42A2
2.5.4 Techniques employing X-ray Standing Waves (XSW)

The availability of synchrotron sources of second and third generation have made possible the application
of X-ray based techniques commonly used for bulk investigations for surface studies which were not
feasible previously because of intensity problems. With regard to the determination of structural
parameters on single crystalline substrates novel approaches employing X-ray standing waves (XSW)
[93ZEG] are particularly interesting. In this technique the wavelength of the incident X-rays is chosen
such that the superposition of the incident beam and one particular Bragg spot generate a standing wave at
the surface. Atoms positioned in the node of this standing wave will absorb little or no radiation, while
those placed at the corresponding maxima will show enhanced absorption. By slightly tuning the
wavelength of the incident radiation the position of nodes and maxima shifts slightly, and a corresponding
analysis of the photoabsorption cross section of the given atoms provides detailed information on the
positions. By additionally employing a triangulation scheme the method can be used to precisely
determine the absolute position of adatoms relative to the substrate atoms. With regard to practical aspects
the most popular variant is the so-called normal-incidence XSW method, where the incident beam is
normal to the corresponding Bragg planes [93ZEG].
Recently, the method has been combined with an energy-resolved detection of the corresponding
photoelectrons, which makes it possible to determine the geometric position of one type of atom in
different chemical environments separately. For example in the case of PF3 adsorbed on Ni(111) this so
called chemical-shift normal incidence X-ray standing wave (CS-NIXSW) technique makes it possible to
determine the position of three different P-species independently [99JAC].
2.5.5 Extended X-ray Absorption Fine-Structure Spectroscopy (EXAFS)

In XPS the kinetic energy of photoelectrons emitted after excitation by photons with a fixed energy is
determined, whereas in EXAFS (extended X-ray absorption fine structure) the photoabsorption cross
section is measured as a function of X-ray photon energy. In contrast to NEXAFS (see below) in EXAFS
the absorption is measured in a fairly large interval of electron energies (typ. several 100 eV). As
schematically depicted in Fig. 8, an X-ray photon is absorbed by exciting an electron into a continuum
state. This electron travelling away from the core-excited atom is scattered by the neighboring atoms as
discussed in connection with X-ray photoelectron diffraction (XPD). Depending on the kinetic energy of
the electron, which is given by the difference between the photon energy hν, the core-level binding energy
Eb and the inner potential V of the electrons inside the probe, constructive or destructive interference will
occur at the position of the core-excited atom. As a result the X-ray absorption cross section is modulated,
it increases when the constructive interference dominates for the emitted photoelectron, and decreases
when destructive interference takes place. As a result, the exact shape of the X-ray absorption edge
depends on the geometric surrounding of the core-excited atom, and e.g. the distributions of distances to
nearest neighbors can be determined by a procedure which essentially consists of a Fourier-transformation
[95ARV; 96BAB].
The outgoing wave will in general be non-spherical. If, for example, the initial state is a p-type orbital,
the orientation of the p-lobes will depend on the direction of the incident light. By varying the angle of
incidence of the exciting X-rays the backscattering amplitude from neighbors in different directions can be
changed, thus increasing the amount of information which can be extracted from the EXAFS-data. As an
example, interatomic distances and molecular orientation could be determined for formate (HCOO–) on
Cu(110) [85PUS].

New Series III/42A2
Fig. 8. In EXAFS, the absorption of X-ray radiation is determined as a function

of photon energy. The photoelectrons generated in the photoabsorption process
at an adsorbate-atom are backscattered from substrate atoms and lead to
modulation of the absorption cross section through interference phenomena. In
the center figure the lines of equal phase of the backscattered radiation go
through the excited atom (see top) resulting in constructive interference, whereas
in the bottom figure the photoelectron kinetic energy is slightly different,
resulting in destructive interference at the position of the excited atom.
Although the EXAFS-method requires a tunable source for X-rays, which is most conveniently realized by
a synchrotron, it has significant advantages because of the rather straightforward data analysis. If X-ray
absorption is determined directly, e.g. in transmission using an X-ray sensitive detector, the method is not
intrinsically surface sensitive. In fact, bulk EXAFS has found widespread application in the determination
of interatomic distances in (disordered) bulk samples, in particular for compounds containing transition
metals. Surface sensitivity is achieved by measuring X-ray absorption indirectly via detection of
secondary electrons. This variant is frequently called SEXAFS (surface EXAFS). Note also that this
method does not require single-crystalline substrates.

New Series III/42A2
2.5.6 He-Atom Scattering (HAS)

Helium atom scattering (HAS)
1 Octane / Cu(111)
[112]
Relative intensity
20
0
-4 -2 0 2 4
K [Å-1]
Fig. 9. Left: He-atoms with thermal energies (10-60 meV) from a molecular beam source are scattered off the very
top surface charge density (left), whereas electrons penetrate several layers. As a result, He-atom scattering, HAS,
offers a unique surface sensitivity.
Right: Due to the very low incident energy He-atoms are particularly well suited for the investigation of delicate
adsorbate layers. The angular distribution has been recorded for ordered monolayers of octane (C8H18) on Cu(111).
In order to obtain well-resolved diffraction peaks from ordered adsorbate overlayers, the wavelength of
the scattered particle is required to lie in the regime of 1-10 Å. Therefore, only slow and light atoms are
well suited for this application, of which helium, the lightest readily available neutral atom, finds
widespread use. A particular advantage of 4He atoms is the fact that an adiabatic expansion of He through
a small (typ. 10-20 µm) nozzle results in the formation of a supersonic beam with a very narrow energy
distribution (values of less than 2% of the initial spread can be reached [77TOE]), so that diffraction
studies can be carried out without any monochromator.
Inspection of a typical interaction potential between a surface and a He atom demonstrates dramatic
differences in the interaction between a surface and noble gas atom on the one hand and electrons on the
other. The steep repulsive branch of the gas-surface potential prohibits any penetration of the He-atoms
into the substrate and limits the interaction to the first layer only. Electrons, on the other hand, penetrate
several layers, see Fig. 9. This fundamental difference results in a tremendous enhancement of the surface
sensitivity and makes it possible to detect single atomic and molecular adsorbates. In contrast to LEED,
however, the cross section depends very sensitively on the electronic structure of the adsorbate surface
complex. In many cases it is found that the cross-section of a molecular adsorbate like CO is significantly
larger than the corresponding gas-phase value [88YIN]. The elastic diffuse scattering signal caused by the
presence of adsorbed atoms and molecules or step edges could also be detected directly and was used to
infer on size and location of such surface defects [87LAH; 92WOE]. The pronounced surface sensitivity
of He-atom scattering can be exploited to directly determine whether adsorbates preferentially adsorb at
defect sites by monitoring the He-atom reflectivity in the course of an adsorption experiment as a function
of surface coverage [00BEC].
The high surface sensitivity of He-atom scattering is best demonstrated by the straightforward
detection of hydrogen-atom overlayers. This has first been reported for the case of H-overlayers on
Ni(110) [83RIE]. In this case the unit-cell of the adsorbate is several times larger than that of the
substrate. The corresponding additional diffraction peaks are clearly visible in He-atom scattering
[83RIE], but give rise to only weak electron diffraction (LEED) spots. The detection of such superspots is
no problem for modern state-of-the–art LEED instruments, whereas for the straightforward detection of
(1x1) H-atom overlayers on metal substrates the scattering of He-atoms is still the method of choice
[95WIT]. Recently, it has been demonstrated that He-beams can be focussed to below 1 µm using Fresnel
zone plates [99DOA] thus opening the route to spatially resolved studies and investigations of small
particles.
An advantage in connection with the investigation of molecular adlayers is the fact that light atoms
with de-Broglie wavelengths in the 0.1 nm regime have incident energies which are so small that

New Series III/42A2
scattering of thermal-energy He-atoms is strictly non-destructive. The method can thus be applied to
characterize the surface geometry of the outer, CH3-terminated surface of self-assembled monolayers of
alkanethiols [91CAM], which is difficult to study with other methods due to the small cross-section of C-
and H-atoms for electrons and X-rays.
The most striking advantage of using He-atoms as opposed to electrons is the fact that neutral atoms
are not sensitive to electric or magnetic fields. As a result insulating substrates can be investigated in a
straightforward fashion [99BRA].
2.5.7 Scattering of rare gases and molecules

The use of noble gases other than He in atom-surface scattering suffers from the fact that the
corresponding molecular beams are significantly inferior to He beams with regard to monochromaticity
and intensity. In addition for noble gas atoms heavier than He the scattering process becomes dominated
by multiphonon-excitations, thus reducing the flux in the elastic diffraction channels.
Only in a few cases have other noble gas atoms been used in diffraction studies (Ne [94RIE], Ar
[89SCH]).
The scattering of molecules to obtain structural information on surfaces is generally hampered by the
fact that the angular distributions obtained by scattering of molecules from a surface are to a large extent
governed by rotational excitations. As a result, only in a few cases have molecules been used for structural
characterizations of adlayers. Note, however, that recently it could be demonstrated that diffraction of
hydrogen molecules in different rotationally excited states can provide interesting information about
details of the charge distribution on compound surfaces [98BER].
Molecular beam techniques are a rather convenient way to obtain direct information on the atom-
surface resp. molecule surface potentials by monitoring selective adsorption processes, which can be
either mediated by diffraction [80HOI] or by rotational excitation [83YU].
2.5.8 X-ray diffraction

Despite the fact that X-ray scattering constitutes the standard technique for bulk structure determination,
quantitative studies at surfaces have so far only been carried out for selected systems. This results from the
small cross section of single atoms for X-rays. Very bright X-ray sources like synchrotrons in connection
with glancing incident angles can, however, be used to overcome these limitations and the required
surface-sensitivity can be achieved. As a consequence, X-ray diffraction, or XRD, has in recent years
become a very attractive method for obtaining detailed structural information on ordered molecular
adsorbates, even in the case of larger molecules (n-alkane thiolates [93FEN]). Since X-ray induced
damage is a general phenomenon observed for many adsorbate systems, the applicability of the technique
to a given system has to be carefully examined in particular for molecular adlayers. Note, that in the case
of metallic substrates the damage is typically not generated by the incident X-ray photons but is caused by
the secondary electrons resulting from the absorption of X-rays in the substrate and the subsequent decay
of core-excitations by primary and secondary Auger transitions.
Only very recently it has become possible to also use laboratory sources for unraveling the structure of
organic overlayers on metal surfaces. For example the ordering and the adsorption-induced intramolecular
distortions have been determined in adlayers of end-capped quarterthiophene [99MEYa] and 2-thiouracil
[99MEYb] on Ag(111).

New Series III/42A2
2.5.9 Neutron Scattering

Similar to the case of X-ray scattering the application of neutron scattering in surface science is severely
hampered by the small scattering cross section of a surface adlayer. Nevertheless, neutron scattering is an
important technique in association with the characterization of molecular adlayers of very different
composition on graphite substrates. The successful application to this special surface is due to the
availability of a particular type of graphite powder, grafoil, which consists of flat sheets of graphite
particles oriented such that a large fraction (∼30%) of the surface-planes are coplanar. Diffraction studies
have been carried out for a large number of adlayers ranging from adsorbed atoms (Ar, [77TAU]) and
diatomics to larger molecules (hexane, C6H14, [92HAN]). Apart from graphite, the only other substrate for
which neutron studies on adlayers supported by a single crystalline surface have been reported is MgO
[91LAR; 98LAR].
2.5.10 Ion Scattering Spectroscopy (ISS)

A major disadvantage of all diffraction techniques is the fact that a straightforward, direct determination
of the geometric structure of an adlayer solely from the diffraction peak intensities is not possible. As a
result, information on the structure in real space can only be obtained by various types of fitting
procedures. In this context the scattering of particles with high energies and correspondingly small de-
Broglie wave-lengths offers the possibility to directly infer on real-space structures by, e.g. channeling and
blocking. (See Fig. 10)
The energy regime between 100 eV and 10 keV is commonly called low energy ion scattering (LEIS).
In this regime the energy is sufficiently high to describe the interaction with solid substrates in terms of
classical physics. The ions incident on the adsorbate-covered surface follow classical trajectories, and
after one or more collisions the backscattered particle is detected. The determination of the surface
composition from the energy-loss of the ion has been described in paragraph 3.4.2 on Ion Scattering
Spectroscopy (ISS). For a fixed incident direction of the ions the analysis of the angular distribution of the
backscattered ions allows for a precise determination of atomic positions. Generally, a direct
determination of the structure from the angular distributions of the backscattered particles is not feasible.
With the aid of computer programs, however, it is possible to simulate the angular distributions of the
scattered ions by analysing the classical trajectories of a large number of ions scattered off a substrate with
an assumed geometry [93NIE]. After comparing the theoretical results with those obtained experimentally
the assumed geometry can be adjusted so as to minimize the deviation between experiment and
simulation. In case of hydrogen atom overlayers on Ru(001), the analysis of the ions scattered from the
H-atoms revealed that the H-atoms are adsorbed on threefold sites of the Ru-substrate, 1 Å above the
plane of the surface atoms [93NIE].
Fig. 10. In ion scattering spectros-
copy, ISS, charged atoms are
accelerated towards a substrate.
When the ions impinge on the
surface, the atoms in the first layer
generate a shadow cone which,
depending an the precise geometry,
can make atoms in deeper layers
invisible. Whereas all atoms of the
first substrate layer are visible for
the scattering geometry depicted on
the right, some substrate atoms are
located in the shadowing cone for
the scattering geometry shown on
the left.

New Series III/42A2
Of course, the interaction of the high-energy ions with the substrate also causes damage due to sputtering.
This is generally an unwanted effect in investigations of overlayers on solid substrates. Fortunately, the
detection efficiency for ions is rather large, thus in most cases the total fluency can be reduced to below
10-3 ions per surface atom, a value for which the ion-induced damage can be safely neglected. The
sputtering can, however, be employed to study depth profiles, e.g. to investigate whether dosing a
substrate with another compound leads to excessive subsurface diffusion [93NIE].
When increasing the ion energies further, the scattering cross sections become smaller, resulting in a
deeper penetration of the particles into the substrate. As a result, medium energy ion scattering (MEIS)
and Rutherford back scattering (RBS) are less surface sensitive (and thus less well-suited for the
investigation of adsorbate overlayers) but are the methods of choice when either information on deeper
layers or a very high precision of the atomic positions is needed [93NIE]. From an experimental point of
view the analysis of ions with higher energies has the disadvantage of requiring more expensive
equipment (accelerator, energy analyzer).
When applying the method to semiconductors and insulators, the appearance of charging phenomena
can strongly affect the neutralization probabilities in the scattering process and thus significantly
complicate a quantitative analysis [79Joi].
2.6 Imaging techniques
2.6.1 Field Ion Microscopy (FIM) and Field Electron Microscopy (FEM)
FEM FIM
e-
Fig. 11. In field electron

microscopy, or FEM, the negative
- + voltage applied to a metal tip
(left) is increased to the point
+ - where the electrons can tunnel
EVac from the tip into the vacuum
(bottom left).
In field ion microscopy, or FIM,
EF e- the voltage is reversed and leads
to the field-induced ionization of
rare gas atoms trapped at the tip
surface (right). Atomic resolution
can readily be achieved with FIM.
In field electron microscopy (FEM) electrons are extracted from a metallic substrate by applying a very
strong electric field, the emission pattern is recorded using a fluorescence screen. In order to reach the
required field strengths (~ 100eV/nm) very sharp metal tips are employed, the fabrication of which poses
a formidable task. Although the first real-space images of molecules adsorbed on metal surfaces have been
obtained using field electron microscopy for a phthalocyanine molecule adsorbed on a tungsten surface

New Series III/42A2
[50MUE], the method has not found widespread application for direct imaging of molecular adsorbates,
mainly due to technical difficulties in preparing the sharp metal tips.
However, it has been demonstrated that the FEM-method is capable of monitoring adsorbate motion or
diffusion on a substrate via fluctuations in the electron emission. In fact, the method has become one of
the most important tools for measuring the diffusion coefficient of adsorbates on metal surfaces
[90GOM]. In one experiment the temporal variation of the emitted electrons has been studied on the
picosecond time-scale, thus allowing the observation of the motion of a single adsorbed atom [93HEI].
Recently the method has been extended to study fluctuations in the course of a surface chemical reaction
in adsorbed molecular adlayers on a Pt-substrate [99SUC].
In field ion microscopy (FIM), basically the same setup is used as in FEM (see Fig. 11), but with a
reversed polarity (positive tip) of the applied voltage. Imaging is carried out by introducing an appropriate
gas (e.g. He, Ne) into the chamber. When the gas atoms come close to the metal tip they experience an
electric field of increasing strength, which can be made strong enough to cause field ionization. The
positive ions are then accelerated in the radially symmetric field and generate an image of the field
desorption tip with atomic resolution. Although the method cannot be applied to image adsorbates
directly, it has been the basis for one of the first methods used for chemical surface analysis, the atom
probe [68MUE]. More recently an improved version of the method, pulsed field desorption mass
spectrometry (PFDMS), has been applied to identify adsorbate products [89KRU] as well as to study
surface reactions and to determine kinetic parameters, e.g. in the case of CO and NO on Rh-crystals
[97KRU].
2.6.2 Transmission Electron Microscopy (TEM)

So far investigations of the geometric structure of adsorbate overlayers by transmission electron
microscopy have only been possible using the transmission and diffraction of very high energy electrons
(several 100 keV). The method has been successfully applied for structure determination of metallic
overlayers on semiconductor substrates (e.g. In/Si(111)[97COL], Ge/Si(111)[96LEG], (Au + Cu)/Si(111)
[91HOM]). For molecular and organic adsorbates the applicability of the method is limited because of the
rather low threshold for radiation induced damage (dissociation). For large molecules, e.g. proteins,
however, the adlayer can be coated with thin metal overlayers which can then be imaged with electron
microscopy [91AMR].
2.6.3 Low Energy Electron Microscopy (LEEM)

The use of electrons with low energy (< 200 eV) to obtain structural information on adlayers by either
direct imaging or rastering is limited by the fact that the performance of electron optical elements at such
low energies is rather poor. Bauer and coworkers, however, have developed a special type of electron
microscope, where the electrons are first accelerated to high kinetic energies, focussed, and subsequently
decelerated to low energies before they impinge on the surface [98BAU]. After the interaction they are
again accelerated to high energies and focussed on a channel plate using standard high-voltage electron
optics. Although the lateral resolution is limited to about 100 Å, steps of monatomic height are clearly
visible in the micrographs. Numerous works have been carried out for adsorbate overlayers [99LEEM],
including the motion of reaction fronts on single crystalline surfaces.
2.6.4 Photoemission Electron Microscopy (PEEM)

In conventional electron microscopy the imaged electrons are generated by reflection, diffraction or
transmission of the primary electrons directed from an external source towards the specimen. In contrast,
photoemission electron microscopy employs an external photon source to generate electrons internally by

New Series III/42A2
photoemission. By combining an ultraviolet lamp, generating photons with an energy slightly less than the
work-function of the substrate, with a conventional electron optical system, images of adsorbate-covered
regions on a surface can be obtained by employing the adsorbate-induced lowering of the work-function:
photoelectrons are emitted only on patches covered with an adsorbate, thus allowing for real-time studies
of changes in the shape of the patterns, e.g. resulting from diffusion (see e.g. the case of K on Pd(111)
[98SNA]) or reaction fronts running across a substrate surface, e.g. in the case of CO oxidation on
Pd(100) [97ASA].
The imaging-contrast described above is based on the difference in work-function and thus is not
intrinsically element-specific. When a photon source in the soft X-ray regime is available, however, maps
showing the distribution of a specific element on the surface can be generated by first recording images
for photon energies slightly above and below a characteristic absorption edge of the particular element
and then computing the difference of the two maps.
If the electron optics additionally are augmented by an energy-filter and the experiments are carried
out using the high brilliance of a third-generation synchrotron, a large variety of new imaging techniques
becomes available [98WIC], which is too expansive to be covered here in detail.
2.6.5 Miscellaneous
Many of the optical techniques, e.g. SHG, can be converted into a microscopical technique by simply
focussing the incident beam. For example in the case of SHG (see chapter on SHG) a resolution of 5 µm
has been achieved in a study on the diffusion of Sb on Ge(111) [92SCH].
2.6.6 Scanning Tunneling Microscopy (STM)

Piezo-tube
Adjustment of
Preamplifier tunneling gap
Fig. 12. In scanning tunneling microscopy, STM, the

distance between a metal tip and a conductive substrate
with a small potential difference (typ. 0.1 eV – 2 eV) is
Tunneling reduced until quantum mechanical tunneling leads to
voltage
the flow of a small current. When the tip is scanned
across the surface a feedback electronic readjusts the
Computer distance so as to keep the current constant. The
and corresponding feedback signal can then be used to
display generate a topographical image of the substrate.
Among the different microscopical techniques applied for the investigation of adsorbate layers, scanning
tunneling microscopy has so far found the most widespread application, mostly due to its fairly
straightforward implementation [93WIE]. In this technique the distance between a sharp metal tip and a
substrate is decreased until quantum-mechanical tunneling generates small currents even for small (< 2V)
voltages across the gap. When the tip is moved along the surface (see Fig. 12), this current will change
due to variations of the gap between tip and surface. With the help of a feedback system the gap can be
readjusted and the corresponding feedback signal is used to create an image of the surface. In case of
clean metal surfaces these images contain mostly topographical information, and adsorbed particles can be
imaged in a straightforward fashion provided that the motion of the particle along the surface is
substantially slower than the scanning of the tip. Generally, lowering the temperature will decrease the
diffusivity of adparticles and at cryogenic temperatures even noble gas atoms can be stably imaged
[90EIG]. It has been demonstrated that the STM-tip can also be used as a tool to displace and move

New Series III/42A2
adsorbed particles in a controlled fashion (Xe atoms [90EIG], O2-molecules [97BRI], CO-molecules
[97BAR]). The STM-tip has also been successfully used to assemble nanostructures, which in turn can be
used for further experiments [93CRO], [96CRO]. In case of adsorbates it becomes important that the
STM-images, when recorded in the so-called constant current mode, actually correspond to lines of
constant electron density at the substrate Fermi level. As a result, atomic and molecular adsorbates which
locally decrease the density of states at the Fermi level create depressions in the STM micrographs rather
than protrusions as might be expected naively.
In principle the STM can also be used to derive information on the electronic structure of the surface
by measuring the current through the tip as a function of the applied voltage (so-called I(V)-curves). The
method thus also offers the possibility to directly determine the local density of electronic states, both
above and below the Fermi edge.
By evaluation of the second derivative of the I(V)-curves it has very recently also become possible to
measure molecular vibrations of adsorbed molecules. In the case of acetylene (C2H2) adsorbed on Cu(001)
the C-H-stretch mode at 358 meV could be clearly identified [98STI].
Frequently, images recorded by STM are also used to determine information on surface
crystallography, in particular lattice constants of two-dimensional periodic structures. In principle STM
can be calibrated against the lattice-constant of the substrate under investigation; however, the imaging
process can significantly distort the adsorbate overlayer. In the case of molecular overlayers on graphite
systematic errors as large as 10% have been reported [93DAI].
Today STM is becoming a standard technique in the structural characterization of conducting surfaces
(metals, semi-conductors). For insulators the situation is hampered by the lack of conductivity, but
materials like TiO2 have successfully been imaged at higher temperatures [99BEN]. A major drawback of
STM is the lack of chemical sensitivity. Despite significant effort and several promising developments a
routine procedure is not yet in sight to reliably determine the type of atom imaged with the STM. The
technique is not limited to ultrahigh vacuum and studies at ambient pressure and in the liquid phase are
carried out routinely.
2.6.7 Atomic Force Microscopy (AFM)
Height Lateral-Force
Laser h ~ (A+B) - (C+D) F ~ (A+C) - (B+D)
Detector Cantilever
A B motion of sample
C D h F
x-, y-, z-
Scanner x x
Fig. 13. In scanning force microscopy, SFM, or atomic force microscopy, AFM, the force between a sharp tip and a
substrate is determined by measuring the deflection of a flexible cantilever. Scanning the tip across the substrates
then yields the morphology of the substrate. Several imaging modes are possible with modern instruments, including
the detection of the lateral force (on the right).

New Series III/42A2
In scanning force microscopy, or SFM (also known as atomic force microscopy, AFM), a sharp tip at the
end of a cantilever is approached towards a substrate while monitoring the force between tip and substrate.
Using specially designed cantilevers the sensitivity can be increased to a point where the attraction
(originating from van der Waals forces) between tip and substrate can be detected. Depending on the
particular requirements, the distance can be reduced further up to the point where the short-range
repulsive (instead of the long range attractive) forces dominate. Using a feedback system in a similar
fashion as in STM (see above) the tip is scanned across the surface while keeping the force between tip
and surface constant by readjusting the distance between tip and surface. Compared to STM the technique
has the advantage that electrical conductivity of the substrate is not required. With regard to the
characterization of adsorbed layers, however, atomic force microscopy, is not quite as powerful as STM,
since the resolution is somewhat limited. The resolution of single adsorbed molecules has been reported in
few cases, e.g. for alkanethiolate adlayers adsorbed on Au-substrates [92ALV]. Very recently high-
resolution images have also been obtained for the case of Xe-adlayers grown on a graphite substrate
[99ALL].
A striking advantage of AFM in comparison to STM and other surface science techniques is the fact
that AFM can be used for virtually all types of solid materials (including insulators) under ambient
conditions and for substrates immersed in liquids in a rather straightforward fashion. As a result, AFM is
becoming a standard technique for the structural characterization of materials [92BRU]. Despite
significant efforts in connection with a chemical functionalization of the scanning tip, a major limitation of
AFM is the lack of chemical sensitivity.
2.7 Vibrational spectroscopy of adsorbed particles

A11 A12 E 4 E 3
O O O O
C C C C
Ni Ni Ni Ni
Fig. 14. An adsorbed molecule shows characteristic vibrational frequencies which provide important information on
the adsorption site and on the chemical interaction with the substrate. Whereas the internal vibrations like the internal
stretch ν1 of the CO-molecule shown in the top can be compared to the corresponding values in the gas-phase, the so-
called external vibrations, ν2–ν4, exist only in for the adsorbate.
With regard to the identification of adsorbed molecular species, vibrational spectroscopy plays a key role.
For determining the stoichiometry of a molecule other methods are better suited (e.g. XPS), but the
chemical state of an adsorbed molecule can be best identified by vibrational spectroscopy. This is in part
due to the fact that a vast amount of data exists for bulk compounds. For example the comparison of C–O
stretch frequencies in metal-organic compounds like nickeltetracarbonyl, Ni(CO)4, with corresponding
data for the surface species allows important conclusions to be drawn about the nature of the molecular
adsorbate. In many cases the number of modes observed in vibrational spectroscopy provides direct
information on the symmetry of the adsorption site. It has been found that in many cases the frequency of
internal stretching modes shows a correlation with the adsorption site. For example the internal vibration

New Series III/42A2
has been demonstrated to significantly vary between the gas phase, for an on-step species e.g. on a
Pt(111)-surface and for a bridge-species on the same surface. However, this correlation should be applied
with great care since recently a number of exceptions from a simple correlation between vibrational
frequency and adsorption site has been reported (CO/Pd(110) [93WAN], CO/Ni(111) [93SCHb],
NO/Pt(111)+NO/Ni(111) [93MAT], NO/Ni(111) [93MAP], N2/Ni(110) [96BER]).
2.7.1 Electron Energy Loss Spectroscopy (EELS)

In connection with the determination of the vibrational excitations of clean and adsorbate-covered
surfaces the technique which has had the greatest impact is electron energy loss spectroscopy (EELS).
Electrons with energies of typically between 2 and 400 eV are first monochromatized, then scattered off a
surface and finally detected using an energy analyzer. During the interaction with the sample, energy can
be transferred to the sample in the form of elementary excitations (electronic transitions, substrate
phonons, adsorbate vibrations). In addition to the energy of the respective excitation the polarization of
the particular vibrational mode and the momentum (in case of ordered structures) can be determined by
recording energy loss spectra at scattering angles different from the specular. With regard to vibrational
spectroscopy the technique is mostly applied to the energy range between 10 and 400 meV, but studies at
lower energies have also been reported. Measurements at larger energy transfers probe electronic
excitations (intramolecular, inter- and intraband transitions), from which detailed information on the
electronic structure of the surface can be derived.
For electron energy loss spectroscopy, two scattering regimes with different scattering geometries can
be identified. If electrons are detected in the specular or near specular direction (to within a few degrees),
the so-called dipole scattering regime, the excitation of vibrations is governed by a dipole mechanism. In
close analogy to IR-spectroscopy (see below), in this regime only vibrations with transition dipole
moments orientated perpendicular to the surface can be observed. For example in case of hydrogen
adlayers adsorbed on W(001) only the totally symmetric modes, where the H-atom is displaced normal to
the surface, can be observed [87WOO]. For scattering angles significantly away from the specular
direction the intensity for the dipole mechanism typically drops by several orders of magnitude and
excitations dominated by another mechanism, impulsive scattering [82IBA], can be detected. In this
regime also vibrations with non-perpendicular orientations of the transition dipole moment to the surface
become visible in the experimental spectra. An example is H/W(001), for which impulsive scattering
reveals those modes where the H-atom vibrates parallel to the surface [87WOO]. Measurements in this
impulsive regime are also very important for the detection of surface vibration (phonon) dispersion
curves, which carry information on the interaction between adsorbed particles [91WOE].
The method can be directly applied to metal and semiconductor substrates; however, in the case of
insulators charging problems can make measurements very difficult. Nevertheless, it has been possible to
overcome this limitation in many cases and high-quality EEL-spectra have been obtained, e.g. for
hydrogen adlayers on diamond C(111) [94AND].
2.7.2 Infrared Reflection-Absorption Spectroscopy (IRAS)

The standard technique for probing the vibrational excitation spectrum of molecular materials in the bulk
is infrared absorption spectroscopy. Photons in the infrared regime (400 – 4000 cm-1) can be absorbed by
excitation of vibrations with appropriate frequencies. Since photons in the IR-regime are not intrinsically
surface sensitive, the application of the technique for problems related to surface science is hampered by
the small absorbance of an adsorbed monolayer. For a saturated monolayer of CO molecules, a rather
favorable case, the extinction has been found to vary between 1.7 x 10-3 for CO on Pt(111) [92HOL] and
1.4 x 10-2 for CO on Cu(111)[88RAV]. In addition, on metal surfaces electric fields are rather effectively
screened. At the surface of a metal, this screening is very strong parallel to, but less effective normal to the
surface. This effect is the basis of the so-called IR surface selection rule, which states that in

New Series III/42A2
IR-spectroscopy only vibrations exhibiting transition dipole moments orientated normal to the surface can
be detected.
An important application of this technique is the determination of orientation (e.g. tilt-angle of
molecular axis) in ultrathin organic layers on metal and semiconductor substrates, e.g. organothiols
adsorbed on Au or organosilanes adsorbed on Si. This method works by comparing spectra recorded at
grazing incidence for the monolayer (typically the spectra are recorded in ambient) to the corresponding
bulk data [92PAR].
Compared to electron energy loss spectroscopy (EELS), the technique offers a significantly higher
resolution (refined apparatuses can reach values of 0.005 cm-1 and better). Experimental halfwidths as low
as 0.025 cm-1 have been reported for physisorbed monolayers, e.g. CO-adlayers on NaCl(001) [96HEI].
Since, however, the experimental setup for recording IR-spectra of adsorbed monolayers on substrates
mounted in an UHV-apparatus is somewhat more complicated, EELS is the more versatile technique. On
the other hand, IR-spectroscopy can be applied to insulators in a straightforward way and can be used
outside vacuum if the problems related to the absorption by the ambient gas can be overcome.
Very recently synchrotrons have been used as a source for infrared radiation. Despite the significant
experimental effort, this approach extends investigations towards the far-infrared [90HIR]. A particular
exciting result is the fact that by monitoring the reflectivity of an adsorbate covered metal surface
vibrational modes can be seen which are invisible in conventional IR-spectroscopy due to the „surface
selection rule“ (see above)[94HIR]. In addition the radiation coming from single electron bunches in the
storage ring can be employed for time-resolved studies down to the nanosecond-regime [99LOB].
2.7.3 Surface Enhanced Raman Spectroscopy (SERS)

In Raman spectroscopy an intense light beam (typically from a laser source) illuminates the sample, and
the amount of inelastically scattered light is determined as a function of wavelength. From the resulting
spectra the vibrational frequencies of adsorbed species can be determined and used to identify the
adsorbates, similar to the case of IR-spectroscopy. Note, that the selection rules for Raman spectroscopy
and IR-spectroscopy are different. For application to adsorbate adlayers normal Raman spectroscopy lacks
sensitivity, although recently the method could be applied to detect vibrations on clean and adsorbate
covered semiconductor surfaces (e.g. Sb and Bi adsorbed on GaAs(110) [98HAI]). For significantly
curved („rough“) metal surfaces in certain cases a huge amplification of the signal is observed and forms
the basis for a technique which has been dubbed surface enhanced Raman spectroscopy (SERS) [85MOS].
The strong amplification is assigned to a coupling between the light and surface plasmons of the curved
metal surface and has made possible a number of studies in ultrahigh vacuum as well as on the liquid/solid
interface [99HAI].
2.7.4 Inelastic scattering of He-atoms

In addition to obtaining structural information about adsorbate overlayers on a surface, He-atom scattering
is also suited to obtain information on adsorbate vibrations. By using a time-of-flight technique the
amount of energy exchanged with the surface can be determined and used to infer on the vibrational
excitation spectrum of a surface. The technique has mostly been applied to study thermal energy (< 25
meV) external vibrations. These are particular normal modes of the adsorbed particle, where the whole
molecule performs periodic motions relative to the surface. These modes, which were first seen for CO
adsorbed on Pt(111) [86LAH], carry important information on the potential energy surface, which governs
the motion of a particle along a surface [96HOF]. For larger molecules, also internal vibrations like the
so-called xylophone-mode in n-octane are located in the thermal energy regime and can be detected with
He-atom scattering [97WIT]. The energy resolution of He-atom scattering is sufficiently high (< 0.1 meV
or < 0.8 cm–1) to determine the vibrational lifetime via an analysis of the profile of the corresponding

New Series III/42A2
loss-peaks and thus to draw important conclusions on the damping-mechanism of molecular motion
relative to a surface [98WIT], an issue directly related to wearless sliding friction [99PER].
Important information on interaction of adsorbates with the substrate can also be obtained by
comparing the surface phonon dispersion curves before and after the adsorption. In the case of hydrogen
adsorption the effects are small for most cases (e.g. H on Pt(111)[89BOR]), in some cases rather striking
differences are seen( H on W(110), [92HUL]).
Although for an adsorbate the interaction between adsorbate and substrate is of primary interest, also
the interaction between the adsorbates is of importance for a detailed understanding of e.g.
two-dimensional phase transitions. Information on the interaction between adjacent adparticles can be
derived from analyzing the corresponding phonon dispersions curves for the frustrated translations. For
example in case of CO-adlayers for most metals only weak adparticle-adparticle interactions are found
[97BRA]. The method is sufficiently sensitive to check whether e.g. Xe-Xe interactions in a physisorbed
monolayer on Cu-surfaces differ from those seen in the gas-phase [97GRA].
The ultimate resolution available today with a state-of-the-art He-atom scattering apparatus is better
than 100 µeV and allows to study diffusion of adsorbates on surfaces by analyzing the energetic width of
the quasi-elastic scattering peak [88FRE]. The method has been applied to quite different systems, e.g.
H/Pt(111) [99GRA] and Xe/Pt(111)[99ELL].
Since the probe particles used in He-atom scattering carry no charge, the method can be applied to all
kinds of substrates. Limitations apply to the maximum energy which can be detected with this technique.
So far the detection of vibrations above 30 meV has been limited to only very few cases.
2.8 Techniques probing the electronic structure
To understand the nature of the interaction between an adsorbate and a substrate it is of paramount interest
to gather precise information on the adsorption induced changes in electronic structure of both, the
adparticle and the substrate. Since very often this type of information is also the key for understanding the
theoretical aspects of adsorption phenomena a variety of techniques has been used, depending on the
particular kind of information desired.
2.8.1 Ultraviolet Photoelectron Spectroscopy (UPS)
e-
to electron
energy analyzer
h fixed
Electron energy
Continuum

Fig. 15. In ultraviolet photoelectron spectroscopy, or
UPS, photons in the UV-regime (10-100 eV) generate
photoelectrons. From the electron kinetic energy as
determined by an energy analyzer the positions of
Count rate occupied electronic states can be determined.
In the case of ultraviolet photoelectron spectroscopy, photons in the energy range of up to 100 eV are used
for the primary excitation process. As a result, information on core-level binding energies cannot be
obtained and the type of elements present on a surface cannot easily be determined. The photoelectrons
emitted from the sample upon absorption of an UV-photon originate from more weakly bound electronic

New Series III/42A2
states, and the photoelectron spectra thus provide direct information of the valence levels, see Fig. 15. In
particular for adsorbates such data allow for important conclusions on the adparticle-substrate and the
adparticle-adparticle interaction. The method also makes a more reliable identification of an adsorbed
molecule possible. As an example the distinction of adsorbed C2H4 and C2H6 (which is very difficult with
XPS, see above) causes no problem in this case, since the occupied π-orbital of C2H4 (which is absent in
C2H6) can easily be seen with UPS. In many cases the comparison of UV-spectra of adsorbed molecular
species with the corresponding data for the gas phase provides precise information about the changes of
the molecular electronic structure upon adsorption of the molecule.
Depending on the symmetry of the adsorbate, the technique can also be used to infer on the orientation
of the adsorbed molecule by using polarized photons and by employing the dipole selection rules. As an
example, the UPS-technique has been employed to decide whether a linear (unbrachned), saturated
hydrocarbon (n-alkane) is adsorbed with its C-C-C-plane normal or parallel to the substrate [97WEC].
In the case of ordered adlayers, the dispersion of adsorbate-induced valence states can be determined
with UPS by restricting the angular acceptance of the energy analyzer. From data obtained by this
so-called angular resolved ultraviolet photoelectron spectroscopy (ARUPS) method the electronic band-
structure can be determined, from which in turn important information on the adsorbate-adsorbate
interaction can be extracted [92WEI].
The technique can also be used to determine the work-function Φ and the adsorption-induced work-
function changes ∆Φ by analyzing the position of the secondary electron cut-off at low binding energies
in the UPS data [94HOF].
The application of the technique and the interpretation of the experimental results is not as
straightforward as in the case of XPS (see above). As in the other variants of photoelectron spectroscopy
the application is difficult for insulating substrates. UPS is still the standard method for obtaining
information on the electronic structure in the valence regime (binding energies < 30 eV), although – at
least in cases of metal substrates – small changes in the molecular electronic structure are observed by the
superimposed electronic structure of the substrate.
2.8.2 Inverse Photoemission (IPE)
e-
Photon energy
Fig. 16. In inverse photoemission, or IPE, an incident

electron is temporarily trapped in an unoccupied
molecular orbital typically several eV above the Fermi
edge, from where it can decay to an low-lying empty
orbital (at the Fermi edge) by photon emission.
Count rate
In principle this technique is a reversed version of ultraviolet photoelectron spectroscopy, or UPS. The
Bremsstrahlung emitted when low energy electrons are decelerated and absorbed in a sample is analyzed
using a monochromator. The resulting emission spectra (see Fig. 16) contain structures, from which the
position and dispersion of the unoccupied electronic levels at a surface can be determined by computing
the difference between the incident electron energy and the energy of the emitted photons. The technique
thus provides information complementary to UPS, where the occupied states are probed. The application
of the method to adsorbates is not straightforward since the resulting photon emission intensities are very
low and the obtainable resolution is rather limited. Despite these experimental problems, it has been
possible to determine the position and dispersion of unoccupied electronic states for a number of different

New Series III/42A2
adsorbate systems, including molecular adlayers, e.g. carbon monoxide chemisorbed on Ni(110)
[89MEM]. The method can in a straightforward fashion applied only to conducting (metal) substrates.
2.8.3 Near Edge X-ray Absorption Fine-Structure Spectroscopy (NEXAFS)
Photon enenergy h

Continuum

h variable Fig. 17. In NEXAFS-spectroscopy a core electron is
excited into an unoccupied molecular orbital by
absorption of a X-ray photon. The absorption spectrum
Absorption
(right) shows sharp maxima when the photon energy
matches the corresponding difference of the electronic
orbitals.
One major problem concerning the evaluation of the electronic structure of an adsorbate is the fact that
with the standard technique, ultraviolet photoelectron spectroscopy, or UPS, only the total sum of all
electronic states is observed. There is no way, a priori, to determine whether the electronic states giving
rise to a particular feature in the UP-spectra are localized mainly at the adsorbate (i.e. backdonation from
a metallic substrate as in the case of CO adsorbed on transition metal surfaces), or in the substrate
(e.g. donation from an adsorbed particle into the substrate) or whether it is due to states best described by
a hybridisation between molecular and adsorbate states. In particular for transition metals with their
d-bands located close to the Fermi edge the UPS-data are typically dominated by emission from these
d-states, and subtle changes are virtually impossible to detect. A typical example for such an interaction is
the case of saturated hydrocarbons, where the changes in electronic structure accompanying the so-called
CH-stretch „soft modes“ seen in EELS [78DEM] and IR-spectroscopy [93RAV; 95HOS] could not be
seen with UPS [98WIT]. Another technique, X-ray absorption spectroscopy, however, has been
successfully employed to image these states. Here the application of X-ray absorption spectroscopy in the
vicinity of the K-edges of low-Z elements (most important: C, N, O) offers significant advantages, since
by the excitation process only elements of one type (e.g. the carbon atoms) are addressed.
In X-ray photoelectron spectroscopy (XPS) (see above) the experimental information is obtained by
analyzing the kinetic energy of the photoelectrons generated by the absorption of photons of fixed energy.
In X-ray absorption spectroscopy the absorption of X-ray photons is measured as a function of photon
energy. Accordingly, the technique requires a tunable X-ray source and can only be carried out at an
electron synchrotron.
The principle of this soft X-ray absorption spectroscopy (the commonly used acronym is NEXAFS, for
near edge X-ray absorption fine structure spectroscopy) is schematically depicted in Fig. 17. For photon
energies above the ionization threshold the core-electron is excited into a continuum state corresponding
to a free electron with a positive kinetic energy. If the photon energy lies below the ionization threshold,
absorption is only possible if the photon energy matches the difference in energy between the initial state
(typically a core level, e.g. C1s, N1s, O1s) and an unoccupied molecular orbital. In that case the excitation
process does not lead to an ionized, but rather to a quasibound state. In contrast to EXAFS (see above),
here only the near edge regime (intervals of 50 eV) is investigated.
The NEXAFS-technique is mainly used for deriving two different types of information. First, the
spectroscopical data are useful in determining the electronic structure of an adsorbate. In the case of
acetylene (C2H2), for example, adsorption on a Cu-surface leads to a splitting of the two π-levels, which
are degenerated in the gas-phase. The technique can thus be used to obtain information about the
electronic structure and is complementary to ultraviolet photoelectron spectroscopy (UPS) in the sense
that unoccupied states are observed. The main advantage over UPS stems from the fact that in NEXAFS

New Series III/42A2
the matrix elements governing the excitation process are large only for final states with significant
contributions from atomic orbitals localized at the core-excited atom. As an example, in the case of
hydrocarbons adsorbed on transition metal surfaces, pure metal states are not observed, which
considerably simplifies the analysis of the experimental results [99WEI].
A second important application of this technique is the determination of molecular orientation within
an adsorbed overlayer. Since the X-rays generated in the electron synchrotron by deflecting electrons with
energies in the 1 GeV range are polarized with the E-vector orientated parallel to the plane of the
synchrotron, the X-ray absorption dichroism can be conveniently measured by recording absorption
spectra for normal and grazing incidence, respectively. From measurements at different angles of
incidence one can thus obtain the orientation of the transition dipole moment with respect to the surface
normal, from which in turn the orientation of the molecule can be derived.
For many adsorbates the adsorption process is accompanied by molecular distortions, e.g. an aplanar,
out-of-plane bend of the C-H-bonds in benzene adsorbed on transition metal surfaces [95MAI]. In the
case of hydrocarbons, such distortions are difficult to detect with photoelectron diffraction or X-ray
diffraction, because the scattering cross-section of the H-atoms for electrons and X-ray photons is very
small. NEXAFS, on the other hand, is sensitive to the accompanying changes in symmetry of the
molecular orbitals and can thus be used to determine these distortions in a semiquantitative fashion. Using
this method it could also be demonstrated that ethylene, C2H4, adsorbs on a Cu(001)-surface in an
essentially undistorted, planar adsorption geometry, whereas acetylene, C2H2, on the same surface shows a
significant tilt of the C-H-bonds away from the C-C-bond [98FUH].
NEXAFS can be applied to a large number of adsorbate/substrate combinations. If the absorption is
detected via the secondary electron yield, highly insulating substrates represent a problem. The situation
is, however, considerably better than in conventional photoelectron spectroscopy, since small (several eV)
shifts in the kinetic energy of the secondary electrons do not affect the positions of resonances in the
spectra. Charging problems are eliminated by employing the X-ray fluorescence to monitor the absorption
(Fluorescence Yield Near Edge Structure or FYNES) instead of the secondary electrons.
2.8.4 Resonant X-ray Emission Spectroscopy (XES)

h’
Kontinuum
Photon enenergy

Continuum
h’
h’
Photonenenergie

Fluorescent
h fixed Fig. 18. In X-ray emission spectroscopy, or XES, the

h fest
energy distribution of the X-ray photons emitted after the
primary absorption process is determined using a second
Intensity
Intensität monochromator.
Although NEXAFS-spectroscopy has obvious advantages over the standard technique to determine
electronic structure, namely UPS, the interpretation and theoretical analysis of the data suffers to some
extent from the fact that the final state of the excitation process is characterized by the presence of a core-
hole. The presence of such a core-hole can be described by increasing the atomic number Z by 1 (so called
equivalent cores approximation), and as a result the binding energies of the electronic states are
significantly lowered. Although the theoretical analysis of this situation can be handled by explicitly
considering the presence of the core-hole, it is not the true ground state which this spectroscopy probes.
Only recently has this problem been overcome by establishing a much more sophisticated variant of this
technique, namely resonant X-ray emission spectroscopy, XES.

New Series III/42A2
In X-ray emission spectroscopy, it is the X-ray radiation emitted when a second electron undergoes a
transition to the core-hole generated in the primary X-ray absorption process, that is detected with an
energy dispersive analyzer, see Fig. 18. Principally, this process is the same as that used in electron
microscopes for the EDX (energy dispersive X-ray detection) technique where core-holes excited by the
high-energy (typ. 10 keV up to several 100 keV) electrons give rise to X-ray fluorescence, which is
measured by energy-dispersive semiconductor detectors with a resolution of typically 100 eV. With this
kind of resolution it is only possible to determine the different elements present in a sample. When the
resolution is increased to beyond 1 eV by using a X-ray monochromator, additional information on the
electronic structure of the sample can be obtained. If furthermore soft X-ray photons are used for the
excitation process, the technique can be applied to investigate final states which are basically the same as
probed with UP-spectroscopy. The striking advantage over UPS, however, is the fact that only final states
with electron densities around a given element are imaged, e.g. in the case of saturated hydrocarbons on a
transition metal surface pure metal states are invisible. Although this technique has so far been applied to
a few systems only, it is expected that with the availability of third generation synchrotron sources the
technique will find a more widespread application.
2.9 Nonlinear optical techniques
2.9.1 Second Harmonic Generation (SHG)
SHG
SFG
Fig. 19. The two nonlinear techniques SHG and SFG employ laser radiation which is so intense that interaction with
matter leads to the combination of two photons of the same frequency (SHG, left) or of two photons of different
energy (SFG, right).
When the intensity of electromagnetic radiation becomes very intense, in addition to linear effects
(electronic and vibrational excitations, Raman scattering, etc.) nonlinear effects become important. This
can be described formally by adding higher terms to the Taylor expansion of the polarizability tensor.
Experimentally, the second quadratic polarizability term becoming nonzero results in the generation of
photons with twice the incident energy, see Fig. 19. In bulk crystals exhibiting inversion symmetry, the
second term has to be zero, but for non-centrosymmetric crystals like e.g. β-barium borate (β-BaB2O4) the
effect becomes so strong that it can be used for frequency doubling. The relevance of second harmonic
generation, or SHG, for the investigation of adsorbate layers becomes apparent when one considers that
the mere presence of the surface considerably lowers the symmetry and, in particular, implies the loss of
inversion symmetry, even if present in the bulk of the material. As a result, the surface of any substrate can
in principle give rise to a SHG-signal. After the sensitivity of SHG to adsorbed layers in the monolayer
and submonolayer regime had been demonstrated for a number of systems [89SHE; 94COR], this method
has in recent years received considerable attention. Note, however, that this method is useful only for
materials with bulk inversion symmetry, since the surface signal is otherwise dominated by that from the
bulk.
The striking advantage of this method as compared to other methods employed in surface science is
the fact that it does not require ultrahigh vacuum. Basically, the only requirement is that there are no other

New Series III/42A2
sources for the SHG-signal. Since this condition is generally fulfilled by solids with inversion symmetry,
by normal liquids (but not by liquid crystals), and by gases, adsorption phenomena at surfaces can be
studied for a large variety of systems.
Although this spectroscopic technique is not inherently structure sensitive, the symmetry of both, solid
substrate and adsorbate overlayer can be mapped by using polarized light.
One of the first SHG-experiments carried out in connection with adsorbates on solid substrates in an
ultrahigh-vacuum environment were measurements on the diffusion of CO-molecules adsorbed on a
Ni(110)-surface [91XU]. In this experiment, first a pattern of regularly spaced stripes of adsorbed
CO-molecules is generated using a laser beam. By detecting the SHG-signal diffracted from this grating
the temporal decay of the pattern could be monitored and analyzed in terms of a diffusion constant. By
orienting the diffraction pattern with regard to the substrate, anisotropies in the diffusion coefficient could
also be studied [91XU].
In later work the technique has been used to follow adsorption/desorption phenomena at the solid-gas
interface for pressures up to 1 atm. Investigations have also successfully been performed at the solid/liquid
interface, e.g. the adsorption of organothiols from an ethanolic solution on a solid Au-substrate could be
followed in real time [99DAN].
2.9.2 Sum Frequency Generation (SFG)

The technique of sum frequency generation, or SFG, is related to the SHG technique discussed above. In
contrast to SHG, where the incident laser beam consists of photons of one wavelength only, in SFG two
different types of photons with frequencies ν1 and ν2 are used. At sufficiently high intensity this will not
only generate photons with twice the energy of the incident photons, 2⋅ν1 and 2⋅ν2, but the nonlinear
effects will in addition lead to the emission of photons with an frequency equal to the sum of the different
frequencies, ν1 + ν2.
By using one wavelength in the visible part of the spectrum and a second, tunable laser in the IR-
regime, the intensity of the SFG signal can be determined as a function of IR-wavelength. Also in this case
the sensitivity to adlayers in the submonolayer coverage regime has been demonstrated [95BAI] [89SHE].
By a symmetry analysis it can be demonstrated that molecular vibrations which are both IR- and Raman-
active can be seen.
The current large interest in this method results from the fact that vibrational spectra of adsorbed
species which provide information complementary to IR can be recorded under non-vacuum conditions.
As an example, very recently the technique has been used to investigate molecular orientations and
conformations in confined systems in the context of tribological phenomena [00EIS]. In addition it should
be noted that the method can be used to study very fast processes with a time resolution down to the
pico/femto second regime. In the past the complexity of the equipment necessary to carry out SFG
experiments has limited the number of studies but recent advances in laser technology have strongly
reduced the effort (and the expenses) needed to set up an experiment.
2.10 Bulk techniques
2.10.1 Nuclear Magnetic Resonance (NMR) and Electron Spin Resonance (ESR)
Today the characterization of bulk (solid and liquid) chemical compounds, in particular in the absence of
crystalline order is dominated by nuclear magnetic resonance (NMR) spectroscopy.
Sophisticated spectrometers operating at frequencies of 850 MHz and above can be used to determine
the structure and to trace the dynamics of single atoms even in large biological molecules. The application
to molecules adsorbed on surfaces, however, is limited by the rather low sensitivity of the technique. So

New Series III/42A2
far, studies on surface phenomena on single crystal surfaces with standard NMR (i.e. for nuclear spins in
C or H atoms) have not been successfully carried out. It was possible, however, to apply standard
NMR-techniques to investigate the dynamics of a lithium isotope, 8Li, adsorbed e.g. on a Ru(0001)-
surface [96EBI].
A different situation emerges if materials with a very high specific surface are used (compare to
neutron spectroscopy). A particular important example are zeolithes [94BEL], where 1H and 13C NMR has
been directly used to study the adsorption of CO [92BRU] and benzene [92LIU]. Also powders have been
successfully investigated, e.g. reactions of different organic molecules on charcoal [95WAG].
Recently, experiments have been carried out by employing a novel scheme for detecting the NMR
resonance. By using a highly sensitive cantilever from an atomic force microscope, it has been possible to
increase the sensitivity of the method to a point where the detection of individual nuclear spins - and thus
the application to surface phenomena - comes into sight [92RUG; 94RUG].
There is another technique based on the detection of spin resonance phenomena, where instead of the
nuclear spin that of an unpaired electron is detected. Although this technique is much more limited than
NMR since only molecules (and atoms) with unpaired electrons can be investigated, the technique is
several orders of magnitude more sensitive than NMR and, at first sight, appears to be better suited for
surface applications than NMR. Unfortunately, however, it has turned out that the application of electron
spin resonance, or ESR, to surface problems is severely hampered by the fact that the unpaired electron
couples strongly to metallic substrates. As a result, ESR-measurements on adsorbed molecules are
virtually impossible [85FAR; 87ZOM]. Substrates with lower electron density and with a significant band-
gap, however, provide a better basis and recently ESR has successfully been used to study the molecular
motion of NO2 on sapphire (Al2O3)-substrates [95SCH].

New Series III/42A2
2 Measuring techniques 2-35
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Lando lt -Börnst ein

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93MAT Materer, N., Barbieri, N., Gardin, D., Starke, U., Batteas, J. K., Van Hove, M. A., Somorjai,
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93SCHb Schindler, K. M., Hofmann, P., Fritzsche, V., Bao, S., Kulkarni, S., Bradshaw, A. M.:
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97BRI Briner, B. G., Doering, M., Rust, H.-P., Bradshaw, A. M.: Mobility and trapping of
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97COL Collazo-Davila, C., Marks, L. D., Nishii, K., Tanishiro, Y.: Atomic Structure of the In on
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97GRA Graham, A. P., Bertino, M. F., Hofmann, F., Toennies, J. P., Wöll, C.: Experimental
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97KRE Kreuzer, H. J., Payne, S. H., Grunze, M., Wöll, C.: Adsorption and Desorption of N2 on
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97SCH Schaich, T., Braun, J., Toennies, J. P., Buck, M., Wöll, C.: Structural changes
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97WEC Weckesser, J., Fuhrmann, D., Weiss, K., Wöll, C., Richardson, N. V.: Photoemission from
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97WIT Witte, G., Fuhrmann, D., Wöll, C.: Low-Energy Molecular Vibrations investigated by
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98BAU Bauer, E.: LEEM basics: Surf. Rev. Lett. 5 (1998) 1275.
98BER Bertino, M. F., Glebov, A. L., Toennies, J. P., Träger, F., Pijper, E., Kroes, G. J., Mowrey,
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98FOE Föhlisch, A., Wassdahl, N., Hasselstrom, J., Karis, O., Menzel, D., Martensson, N.,
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98FUH Fuhrmann, D., Wacker, D., Weiss, K., Hermann, K., Witko, M., Wöll, C.: The adsorption
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98HAI Haier, P., Santos, P., Esser, N., Richter, W.: Interaction between Sb and Bi adsorbates on
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98LAR Larese, J. Z.: Neutron scattering studies of the structure and dynamics of methane absorbed
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98SNA Snabl, M., Ondrejcek, M., Chab, V., Chvoj, Z., Stenzel, W., Conrad, H., Bradshaw, A. M.:
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98STI Stipe, B. C., Rezaei, M. A., Ho, W.: Single-molecule vibrational spectroscopy and
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99ALL Allers, W., Schwarz, A., Schwarz, U. D., Wiesendanger, R.: Dynamic scanning force
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99BEN Bennet, R. A., Stone, P., Price, N. J., Bowker, M.: Two (1x1) reconstructions of TiO2(110):
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4 Data: Adsorbate-induced changes of substrate properties

M. A. VAN HOVE, K. HERMANN, P. R. WATSON
4.1.1 Introduction
The structure of surfaces at the atomic scale is basic to the understanding of many surface and interface
properties. The effect of adsorbates on surface structure is particularly important because adsorbate-
covered surfaces are technologically far more relevant than the clean substrate surfaces. Adsorbate-
covered surfaces are also very relevant to the vast class of interfaces between two solids or between a
solid and a fluid (liquid or gas).
This chapter lists the experimentally determined effects of adsorption on the substrate surface
structure, focusing on those cases where detailed and rather complete structures have been determined.
This implies single-crystal surfaces with mostly well-ordered adsorbates. Much of the information is
derived from the atomic coordinates and other information contained in the Surface Structure Database
(SSD), Version 3 [99W], and is complemented with more recent results from the literature. The data
were obtained with a variety of surface techniques, which are listed with their acronyms in Table 1.
The emphasis is on the atomic-scale structure as defined by atomic positions, relaxations and
reconstructions, structural models and bonding configurations. Included are both atomic and molecular
adsorbates. The data for atomic adsorbates far outnumber those for molecular adsorbates, but the effects
are rather similar, which is interesting in its own right; the tables in this chapter therefore show them side
by side for direct comparison.
Adatom positions are included in the tables so that the adsorbate-induced effects can be directly
related to the adatom. However, for adsorbed molecules only the positions of the atoms that bond to the
substrate are listed in the tables, since they have the most direct influence on the substrate. More
complete structural details can be found in the Surface Structure Database [99W].
The tables in this chapter are limited to adsorption on metal and semiconductor substrates for the simple
reason that virtually no detailed information is available from experiment about adsorbate-induced
structural effects on other substrate materials, including ionic crystals and many other compounds.
4.1.2 Relaxation vs. reconstruction

Central to adsorbate-induced changes in a substrate are the two concepts of relaxation and reconstruction,
which collectively may be called restructuring. The terms relaxation and reconstruction need to be
defined here, since various interpretations are used in the literature, especially for reconstruction.
By relaxation of a substrate surface we mean small atomic displacements from ideal or clean-substrate
positions. The displacements shall be small compared to near-neighbor distances, such that no rebonding
(bond breaking or new bond formation) takes place within the substrate. Such relaxation may induce the
formation of a two-dimensional superlattice if the displacements modify the initial substrate surface
symmetry. This is especially common in adsorption, since the adsorbate itself often creates a superlattice,

4.1-2 4.1 Surface structure on metals and semiconductors [Ref. p 4.1-109
particularly at fractional coverages less than one. For example, a ¼-monolayer of atomic adsorbate could
be arranged in a (2x2) superlattice, doubling the substrate periodicity in two surface directions; each
adatom can induce relatively small local relaxations in the substrate and within the superlattice unit cell:
these relaxations, especially layer bucklings and lateral displacements, often break the clean-substrate
periodicity while conforming to the superlattice periodicity.
Relaxations must be referenced to another structure, for which the obvious choices are the ideal bulk-
like positions or the already relaxed clean-substrate positions. Since the clean-substrate positions are not
uniquely known (each analysis gives somewhat different results), we use as an unambiguous reference
for relaxations the ideal bulk-like positions obtained by a mathematical termination of the bulk lattice.
However, we also include in this chapter, for direct comparison with the adsorbate-induced relaxations,
tables of the published structural results determined for relaxed clean surfaces.
Adsorbate-induced relaxations occur in many varieties. Of general interest are interlayer spacing
changes: since clean surfaces exhibit spacing changes relative to the ideal bulk lattice, it is useful to
consider the further changes due to adsorbates. For instance, on metals the clean-surface spacing
relaxations are often reversed by adsorption: while the clean surface usually (but not always) exhibits a
contraction of the topmost interlayer spacing, an expansion is often observed after adsorption. Also
interesting is layer buckling (also called rumpling), whereby a coplanar atomic layer loses its coplanarity
because an adsorbate pulls or pushes some substrate atoms out of the plane relative to other atoms.
Another effect is lateral relaxation, in which adsorbates shift substrate atoms parallel to the surface; a
frequent case is a radial relaxation of substrate atoms away from or toward the adsorbate site. Another
case of lateral relaxation is the collective rotation of substrate atoms around the adsorbate site; this
displacement is often called clock rotation. One could also look at all these relaxations in terms of
adsorbate-induced changes in bond lengths, which are the chemically more important quantities;
however, surface scientists have thought mostly in terms of displacement components perpendicular and
parallel to the surface, and we shall do so here as well.
By reconstruction of a substrate surface we mean large atomic displacements that cause rebonding
(bond breaking and/or new bond formation) within the substrate. Frequently, but not always, such a
reconstruction changes the two-dimensional lattice of the surface, creating or modifying or removing a
superlattice. Reconstructions are of course usually accompanied by additional small relaxations.
Reconstruction is a relative term: here reconstruction is understood with respect to the ideal bulk-
lattice termination, rather than with respect to the actual clean surface. Of particular interest in
adsorption are several cases: the induction of a new reconstruction, when none was present on the clean
surface; the removal of a clean-surface reconstruction (sometimes inelegantly called un-reconstruction or
de-reconstruction); and the change from one reconstruction to another (which could be called re-
reconstruction).
Many types of reconstruction exist at surfaces. One class of reconstruction, common on certain clean
metal surfaces, is that of missing or added atoms (e.g. missing or added rows); the remaining atoms still
occupy bulk-like positions, usually with small local relaxations from those bulk-like positions.
Microfacetting is a frequent outcome of this type of reconstruction. Adsorption often removes such
reconstructions, but can also induce them, or stabilize them. Another class consists in forming or
removing a more closely-packed surface layes, such as a quasi-hexagonally close-packed layer on top of
square-lattice substrate, as happens with some metal surfaces. Dimerization and similar types of
rebonding (e.g. π-chain formation) are commonly found on semiconductors, and these reconstructions are
frequently removed by adsorption, but can also be stabilized by adsorption. Stacking faults occasionally
are also seen on these materials. Absorption of adatoms into subsurface sites occurs for a variety of
materials and can lead to interstitial or substitutional absorption within the substrate, in which case the
remaining substrate atoms have near-bulk-like positions; absorption can also lead to other forms of
compound formation, that may not respect the substrate lattice, but rather tend toward the lattice of the
bulk compound.
As with many definitions, there exist borderline cases where our definitions of relaxation vs.
reconstruction are debatable. For example, large bond rotations with substantial atomic displacements but
without rebonding occur in surfaces such as clean GaAs(110): we classify these as not reconstructed
(relative to the ideal bulk termination, which is also nearly regenerated by certain adsorbates), although
many authors prefer to call these reconstructed. In the case of clean W(100)-c(2x2), the displacements

Ref. p. 4.1-109] 4.1 Surface structure on metals and semiconductors 4.1-3
from the ideal bulk positions are relatively small and could be called relaxations, but these may be
sufficient to cause new bond formation between W atoms, and we label this situation therefore as
reconstruction (this case has also been called displacive reconstruction in the literature).
We treat relaxations and reconstructions very differently in the tables of this chapter. With
relaxations, it is of primary interest to compare the quantitative magnitude and direction of the small
displacements, including in particular changes in interlayer spacings, such as expansions and contractions.
By contrast, with reconstructions it is of primary importance to know the qualitative type of
reconstruction, rather than the detailed atomic positions; and the type of reconstruction is more easily
understood when described in words than in numbers. Thus, our tables will in general list relaxations
numerically, but reconstructions will be explained textually, although some important structural quantities
will often be listed as well in the latter case. If more details are desired, it is suggested to consult the
Surface Structure Database [99W].
4.1.3 Notations and conventions

The individual structures listed in the tables are named using standard notations, particularly for
superlattices: we use Wood, “rect” (rectangular) or occasionally matrix notations for the superlattices,
which are defined in many books and reviews [86V, 99W]; they appear in the exact form used in the
Surface Structure Database [99W].
Adsorption sites are also labeled in a conventional way, e.g. fcc-hollow site for adsorption at an fcc-
lattice-continuation site above an fcc(111) surface. Figures are provided to clarify the more common
adsorption sites and local adsorption geometries.
For an adatom, the adsorption site coincides with the atomic position, or its projection into the
substrate: we may call this the adsorption axis. But with an admolecule this needs clarification. For a
molecule with a rotation axis perpendicular to the surface, the adsorption site coincides with the
molecular rotation axis, which we may again call adsorption axis. Thus, for CO standing perpendicular to
the surface at a high-symmetry position, the C-O axis uniquely defines the site, and the C atom (which
normally bonds to the surface) is located at that site; for ring-like benzene lying flat on the surface with
its main symmetry axis perpendicular to the surface, the empty center of the molecular ring typically lies
at a high-symmetry location and thereby defines the adsorption site, while the 6 carbon and 6 hydrogen
atoms are all removed from that site at lower-symmetry positions.
For low-symmetry adsorption, ad hoc descriptions are given in each individual case, and in these
situations the adsorbate-induced relaxations often become quite complicated (asymmetrical) and are not
listed in detail: it is suggested to consult the Surface Structure Database [99W] for further information.
Relaxations are labeled in the tables as illustrated schematically in Figs. 1 and 2, which define our
generic labeling scheme applicable to all metallic substrates. The principle is to look from the adsorption
site or axis outward, in any given layer. Consider the four coplanar and symmetrical light-grey substrate
atoms depicted in Fig. 1, which looks down onto a particular atomic layer: these symmetry-equivalent
atoms form a shell numbered s, at a radial distance rls from the (projected) adsorbate site (more precisely,
this shell is cylindrical around the adsorbate site axis, which is very often an axis of rotational symmetry).
If the local rotational symmetry is maintained, adsorption can cause these four atoms to be displaced
radially by the common distance ∆rls from the (projected) adsorbate site and rotated tangentially by a
common angle αls around that site.
Figure 2 shows a side view of several substrate layers, each of which is shown as a gray slab of non-zero
thickness, since it may be buckled: each possibly buckled layer originates in one non-buckled layer of the
ideally-terminated bulk lattice. The dashed line is the adsorption axis, i.e. the projection of the adsorbate
site down to each substrate layer. In a given layer, the first shell of atoms around that projected adsorbate
site is numbered i = 1, with possible radial displacement by ∆r1 and possible tangential rotation by α1.
The z-coordinate (perpendicular to the surface) of these nearest atoms numbered i = 1 defines the
reference plane for this given layer (shown as a heavy line in Fig. 2): by definition, it thus has buckling
amplitude b1 ≡ 0. The atoms of the second, third and farther shells have radial displacements ∆r2, ∆r3,
etc., and tangential rotations α2, α3, etc. They also can have buckling amplitudes b2, b3, etc. relative to

the reference plane of that layer. The radial displacements and bucklings are expressed in percent relative
to the values and interlayer spacings in the bulk.
4.1.4 Organization of the tables

The tables are arranged so that similar structures are close together for easiest comparison. The coarsest
subdivision is thus between metal substrates (see Sects. 4.1.6-4.1.14) and semiconductor substrates (see
Sects. 4.1.15-4.1.18).
Within the metals, the tables progress generally from the surfaces with highest symmetry and closest
packing to those with lowest symmetry and least packing of the ideal termination. The order is thus:
fcc(111), hcp(0001), bcc(110), fcc(100), bcc(100), fcc(110), hcp(10-10), bcc(211), bcc(111). Within the
semiconductors, the same principles apply, starting with elemental substrates before turning to compound
substrates: diamond(111), diamond(100), diamond(311), zincblende(110), zincblende(111), zincblende(-
1-1-1), zincblende(100), and 6H-SiC(0001).
For a given crystal face, a first table gives the clean-surface relaxations of the interlayer spacings, or
the type of clean-surface reconstruction (all relative to the ideally terminated bulk). Then, a table gives
the adsorbate-induced relaxations or reconstruction type. Within this table, the structures are grouped by
two-dimensional superlattice, starting with the smallest and highest-symmetry unit cells and progressing
to the largest and lowest-symmetry unit cells (this includes disordered adlayers where available).
For a given unit cell, the structures are listed alphabetically by substrate material and then by
adsorbate element(s).
A particular structure with several adsorbates per unit cell will appear several times in the table if the
adsorbates occupy inequivalent sites. This is because the tables focus on one type of adsorption site at a
time, for the most direct comparison, so that different adsorption sites coexisting in a single structure are
found listed in different parts of the tables.
4.1.5 Organization of data for individual structures

In the tables, when relaxations are listed, each (possibly buckled) layer is given one row, starting with the
top substrate layer (numbered 1 in Fig. 2). The absence of structural data for deeper layers in second or
subsequent rows means that they were not determined. All distances and angles are given in Ångström
and degrees, respectively.
Multiple data in a data field correspond to successive shells of atoms in a particular layer, as defined
above and in Figs. 1 and 2.
Let us explain this with two examples extracted from Tables 3 and 9, respectively (omitting a few
obvious columns):
surface clean ads- ∆dl,l+1 [%] bls [%] ∆rls [%] αls [°] d01 [Å] ∆r0 [Å]
rec. ind
rec.
Pd(111)+(3x3)- no no 2.6 ± 2.2 0.0 ± 2.2, 0, 0.8 ± 7.0 0, 0 2.16 ± 0.05 0
C6H6+2CO: 2.2 ± 2.2
C6H6 site
surface clean ads- ∆dl,l+1 [%] bls [%] ∆rls [%] αls [°] d01 [Å] ∆r0 [Å]
rec. ind
rec.
Ni(100)+ no no 3.9 ± 4.5 0 3.2 ± 3.9 ± 14.3 ± 2.6 0.12 ± 0.04
p4g(2x2)-2C 4.4 ± 4.0 0, 8.5 ± 4.5 0, 0 0, 0

The first of these two structures, Pd(111)+(3x3)-C6H6+2CO, contains 3 adsorbates in each unit cell, all
of which are adsorbed at fcc-hollow sites. In the entry shown above only the structure around the
benzene site is described (the structure around the CO adsorption sites is listed as a separate entry in the
same Table 3).
The center of the benzene molecule, which defines the adsorption site or axis, lies over an fcc-hollow
site (indicated by the heading of Table 3). The height of the C atoms of the benzene, above the first ring
of Pd atoms around the fcc-hollow site in the top metal layer, is given as d01 = 2.16 ± 0.05 Å. The second
shell of Pd atoms around that site in the top metal layer is buckled into the substrate by b1b = 2.2 ± 2.2 %,
relative to the first shell, for which (by definition) b1a = 0.0 (± 2.2) %, while its shell radius is (perhaps)
expanded by ∆r1b = 0.8 ± 7.0 % relative to bulk positions. No rotations αls are noted, and no information
about the second metal layer l = 2 is given, other than its spacing of ∆d12 = 2.6 ± 2.2 Å, measured relative
to the first shell of Pd atoms in the first Pd layer; the second Pd layer is thus, in this example, assumed to
be internally unrelaxed, i.e. not to be buckled, expanded laterally or rotated.
The second structure, Ni(100)+p4g(2x2)-2C, contains two (equivalent) C adatoms in each (2x2) unit
cell, related by p4g symmetry (i.e. glide-plane symmetry, as well as 4-fold rotation and mirror planes).
The “no” entries indicate that neither the clean Ni(100)-(1x1) nor the C-covered substrate are
reconstructed (in the sense that no Ni-Ni bonds are made or broken relative to the ideally-terminated
substrate); admittedly, this is debatable for the C-covered surface, since the Ni-Ni distances within the
first Ni layer do change appreciably.
The heading of Table 9, from which this entry was extracted, specifies adsorption at a clock-rotated
hollow site; the absence of a non-zero entry for lateral adsorbate shifts ∆r0 confirms that the C atoms are
indeed at the high-symmetry hollow sites.
The height of the C adatoms over the plane of the nearest Ni atoms is listed as d01 = 0.12 ± 0.04 Å,
indicating nearly coplanar adsorption. If there were other Ni atoms in that first layer at a different height,
i.e. buckled, the corresponding C-Ni spacing would be included in the same data field, e.g. as an
additional 0.22 ± 0.04 Å to indicate that the next shell of Ni atoms would be deeper in the surface,
buckled inward, by 0.22 - 0.12 = 0.10 Å; however, this particular structure has no buckling in the top Ni
layer (it is not allowed by symmetry), as also indicated by the absence of an entry b1b in the buckling
column.
The data imply that the first shell of four Ni atoms is probably expanded radially by ∆r1a = 3.2 ± 3.9 %
and most likely rotated by α1a = ± 14.3 ± 2.6 °, relative to the ideally-terminated Ni lattice; the initial ±
before the rotation angle specifies that both clockwise and counter-clockwise rotations occur within the
unit cell.
The spacing change (relative to the bulk value) between the first and second Ni layers is given as
∆d1,2 = 3.9 ± 4.5 %, indicating a probable expansion; note that this spacing is measured between the
planes of those Ni atoms which are closest to the (projected) adsorption site in each layer, i.e. between
first Ni shells in each layer, as shown in the general case in Fig. 2.
In the second row of data for this structure, which describes the second Ni layer, we find that a
buckling by b2b = 8.5 ± 4.5 % occurs between the first shell of Ni atoms closest to the (projected)
adsorption site (in this case the Ni atom directly below the adsorption site, for which by definition
b2a = 0 %) and the next shell of second-nearest Ni atoms: the positive value indicates that the second Ni
shell in this layer lies deeper below the surface than the first shell. Furthermore, the spacing between the
second and third layers is shown to also probably be expanded, by ∆d2,3 = 4.4 ± 4.0 %.
We illustrate next an entry for semiconductors, from Table 23, which contains some numerical data:
surface clean ads-ind d01 [Å] ∆d12 [Å] ω [°] description

rec. rec.
Si(111)+ yes no 1.85 ± 0.05 -15 ± 3 [description]
(√3x √3)R30°-In
This entry indicates that the adsorbate (In) has removed the clean-surface reconstruction. The adatom is
located at a height d01 = 1.85 ± 0.05 Å above the first shell of outermost Si atoms. The adsorption occurs
in a T4 site (as stated higher in the table and in the description included in this entry). And the spacing

between Si atoms in the outermost bilayer is contracted by ∆d12 = -15 ± 3 % relative to the bulk value.
(The rotation angle ω is not relevant to this structure.)
4.1.6 Adsorption on fcc(111)

The clean fcc(111) and hcp(0001) surfaces are the most compact and dense possible, with hexagonal
atomic arrangements. They have the least tendency to reconstruct and relax interlayer spacings. Only
Au(111) among them is known to reconstruct (to an even denser hexagonal outer layer with smaller
lattice constant). Table 2 for the clean fcc(111) surfaces shows that the topmost interlayer spacing can be
either expanded (Ag, Al, Pd, Pt), or undecided (Cu, Ni), or contracted (Rh), based on experiment. There
does exist a general trend toward contraction of the topmost interlayer spacing in many metal surfaces,
but it is only systematically verified for less-close-packed surfaces, such as fcc(110). The deeper
interlayer spacings in clean fcc(111) surfaces are less well characterized at this time: their relaxations can
be assumed to be smaller than the uncertainty of the analysis.
Table 3 lists the adsorbate-induced changes on fcc(111). Reconstructions are relatively rare, and
occur mostly with adsorbed metal atoms (especially alkali atoms) in the form of substitutional adsorption.
Phosphorus and sulfur also can produce reconstructions in some cases, of a more complex type, but also
tending toward compound formation; the structure of this ultra-thin compound layer need not be simply
related to any known bulk compound structure.
Considering the non-reconstructed cases, one finds a general trend toward expansion of the local
topmost substrate interlayer spacing, relative to the clean surface. But there is one major exception to this
trend: electropositive adsorbates (especially the alkali atoms) generally produce a contraction of this
spacing.
A similar contrasting trend is seen in the buckling induced within the top substrate layer: with
electronegative adsorbates, the trend is toward positive buckling, i.e. substrate atoms farther from the
adsorbate site tend to be deeper in the surface; the reverse is seen for electropositive adsorbates (again for
alkali atoms especially).
Radial relaxations around the adsorbate site are mostly within the error bars and probably small or
negligible in most cases; the few more decisive results are insufficient in number to establish a clear
trend. This applies even more so to the few tangential rotations that may have been observed.
Buckling in the second substrate layer shows a tendency to be the reverse of that in the first substrate
layer, particularly for the (2x2) structures with adsorption in fcc-hollow sites.
4.1.7 Adsorption on hcp(0001)

The surface structure of ideal hcp(0001) is very similar to that of fcc(111), the difference occuring in the
stacking sequence of the third and deeper metal layers. No hcp(0001) surface is known to reconstruct
when clean.
Table 4 shows clean-surface relaxations for hcp(0001). As with fcc(111), the topmost interlayer
spacing can be expanded (Be, Mg), undecided (Co), or contracted (Gd, Ru, Sc).
Compared to the fcc(111) surfaces, it seems at present that even fewer hcp(0001) surface reconstruct
upon adsorption, cf. Table 5, at least among those studied.
Trends in adsorbate-induced relaxations on hcp(0001) are less clear than on fcc(111), cf. Table 5.
Perhaps the effects seen on fcc(111) do not carry over to hcp(0001), or the effects on hcp(0001) are more
sensitive to details of the atomic arrangements within the various unit cells. A more exhaustive analysis
and comparison of the results on a single metal, Ru(0001) [97M1], also suggests that structural trends
may be difficult to extract for this one metal, and thus even more so for the class of hcp(0001) surfaces.

4.1.8 Adsorption on bcc(110)

The ideal bcc(110) surface presents a distorted hexagonal lattice of slightly lower intrinsic atomic density
than fcc(111) or hcp(0001). No clean reconstructions of these surfaces are reported, cf. Table 6. There is
a tendency toward a contraction of the outermost interlayer spacing for K, Mo and W, without clear
deviation from the bulk value for the other studied metals.
Adsorption does not cause reconstruction on bcc(110), cf. Table 7. (There have been reports of a
possible H-induced lateral shift of the top metal layer; but later studies could not confirm these results.)
Adatoms appear to favor the "center" site (which is the continuation site of the bcc lattice), even though it
is only two-fold coordinated. Adjacent to this site is a three-fold coordinated hollow site which is
preferred by hydrogen, while in one structure, Mo(110)+(2x2)-S, the adatom appears to settle midway
between those two sites. The adsorbate does not seem to induce a systematic expansion of the outermost
metal-metal interlayer spacing on bcc(110); this is somewhat surprising in view of the results on other
surfaces, but perhaps the statistics in this small group of results are not sufficient to reach a firm
conclusion.
4.1.9 Adsorption on fcc (100)

The ideal bulk-like fcc(100) surface, cf. Table 8, is atomically less dense and more "open" than the
hexagonal fcc(111) and hcp(0001) surfaces, or the bcc(110) surface. Also it is more asymmetrical
between vacuum and bulk than the hexagonal surfaces, in the sense that a surface atom has 0 nearest
neighbors on the vacuum side and 4 on the bulk side, compared with 0 and 3 for the hexagonal surfaces;
in addition the surface atoms in fcc(100) have only 4 nearest neighbors in the surface plane, as opposed to
6 in the hexagonal surfaces, so that the surface atoms in fcc(100) are relatively more affected by the out-
of-plane asymmetry. As a result one finds a slightly stronger tendency to both reconstruction and
relaxation on the square-lattice fcc(100) surface. Reconstruction of the clean surface occurs for Ir, Pt and
Au(100), as on fcc(111): in each case the top layer contracts and rearranges to form a quasi-hexagonal
layer more similar to the fcc(111) surface (but with slightly different lattice constants, yielding different
superlattices).
The relaxations of interlayer spacings on fcc(100) surfaces are more biased toward a contraction of the
top spacing. This spacing still appears to expand slightly for a few metals (Al, Pd), while no clear
relaxation is seen on others (Ag, Ni, Rh); several metals now show a contraction (Al, Pb, Pd). There is
also a tendency toward an oscillatory relaxation of the deeper interlayer spacings: alternating
contractions and expansions with decaying amplitudes.
Table 9 lists the adsorbate-induced changes on fcc(100). Adsorbates induce reconstructions of
fcc(100) perhaps more frequently than for the hexagonal surfaces, but the statistics are poor, and the
choice of metals studied probably not random. However, the adsorbates that cause reconstructions tend to
be the same as on the hexagonal surfaces: primarily alkali adatoms, some other metal adatoms that form
a one-layer alloy with the substrate, and oxygen. While sulfur induces reconstructions on fcc(111) and
fcc(110), none is evident on fcc(100). On the other hand, adsorbates can also remove a clean-surface
reconstruction (few such cases are listed in Table 9, but examples are known qualitatively by the change
in their LEED patterns).
Atomic adsorption occurs predominantly at or near four-fold coordinated hollow sites of fcc(100); the
smaller adsorbates (H, C, N) penetrate relatively deeply into that hollow and partly bond to the second
metal layer. Interlayer spacings are changed by adsorption in similar ways as on the hexagonal surfaces.
Many adsorbates (primarily the electronegative ones) cause an expansion of the outermost interlayer
spacing, while others (primarily the electropositive ones) yield contractions. The magnitude of the effect
seems to be comparable to the case on the hexagonal surfaces. Also, there are similar examples of
buckling, especially in the second metal layer. Notable is the very clear case of "clock reconstruction"
observed for C and N adsorbed on Ni(100).

4.1.10 Adsorption on bcc (100), pure or alloyed

The bcc(100) surface is in turn less dense and more open than the fcc(100) surface. In fact, the surface
atoms do not bond together on bcc(100); instead, the 4 nearest neighbors of a surface atom are all in the
second metal layer, causing very strong asymmetry between vacuum and bulk. One thus finds an even
stronger tendency toward reconstruction and relaxation on this surface, especially when clean. Table 10
shows that 2 of the 5 bcc(100) metals listed reconstruct when clean (Mo, W). The non-reconstructed
clean metal surfaces exhibit quite strong contractions of the outermost interlayer spacing, and a probable
expansion of the next deeper spacing.
Adsorbates, cf. Table 11, tend to compensate or even overcompensate for the missing half-crystal:
this is already apparent on the closer-packed surfaces, but becomes much clearer with the more open
surfaces like bcc(100) and fcc(110) (see Sect. 4.1.11 for the latter). The reconstructions tend to be
removed or replaced by other reconstructions, while the relaxation of the outermost interlayer spacing
often turns from a large contraction to a sizable expansion. Adsorption of adatoms occurs primarily
within the large hollows of this surface, with frequent bonding to the second metal layer and a large
induced buckling of that second metal layer.
Alloys with a bcc(100)-like lattice include MoRe with variable composition, listed in Tables 12 and
13. The clean surfaces behave like clean, unreconstructed bcc(100) surfaces [note that clean Mo(100)
reconstructs, while pure Re has an hcp lattice], as shown by the interlayer spacings listed in Table 12.
Oxygen adsorption causes a missing-row reconstruction, while H and C induce spacing changes (and C
can also penetrate interstitially).
4.1.11 Adsorption on fcc (110)

The tendency noted above toward more reconstructions and relaxations on more "open" surfaces is again
very evident for the fcc(110) surface. There is once more a large asymmetry for surface atoms between
the vacuum side and the bulk: each surface atom has 0 nearest neighbors in the vacuum and 5 toward the
bulk, one of which is directly below the surface atom, and the latter only has 2 nearest neighbors in the
surface plane.
Clean Ir, Pt and Au(110) all reconstruct, cf. Table 14, as for the (111) and (100) surfaces. But the
(110) surface reconstructs into missing-row structures that expose narrow facets of hexagonal symmetry.
While no other fcc(110) surfaces are known to spontaneously reconstruct when clean, the ease with which
trace amounts of adsorbates can reconstruct several of these surfaces suggests that they are energetically
close to reconstructing. Relaxations of interlayer spacings on the clean unreconstructed (and
reconstructed) fcc(110) surfaces show a clear pattern of oscillatory contractions and expansions as one
penetrates from one layer to the next.
Adsorbates can induce the removal or change of a reconstruction on fcc(110) surfaces, cf. Table 15.
The resulting reconstruction which has been studied most is that of oxygen on Cu, Ag and Ni(110), and N
on Rh(110): it consists of one-dimensional chains like -Cu-O-Cu-O-, where the Cu atoms can be most
easily viewed as adatoms on a bulk-like (but relaxed) Cu(110) surface. Another interesting type of
induced reconstruction is a simple 1:1 metallic alloy in the top layer, obtained by substitution of half the
surface atoms. A number of more complex reconstructions are also known, produced primarily with N,
O, S and P, as well as some other metallic adatoms.
Adsorbate-induced relaxation changes on unreconstructed fcc(110) surfaces are similar in magnitude
to the bcc(100) case. The larger adsorbates, S and metals, tend to occupy the higher-symmetry hollow
site at the center of the rectangle formed by 4 surface atoms, maximizing the number of nearest
neighbors, and in particular bonding directly to the second metal layer, thereby inducing a large buckling
there. Smaller adatoms, like H and O, favor 3-fold coordinated bonding sites on the flanks of those
hollows (also bonding to atoms of both the first and second substrate layers); this lowers the symmetry
and induces more complex relaxations in the substrate, such as asymmetrical lateral relaxations.

4.1.12 Adsorption on hcp (10 1 0 )
The ideal hcp ( 10 1 0 ) surface shows strong similarities with fcc (110): it also consists of ridges and
troughs of close-packed atomic chains. However, the bulk structure allows two inequivalent
terminations, with shallow and deep troughs, respectively. In all cases, it is the shallow-trough
termination that is observed. The studied cases, cf. Table 16, exhibit no reconstructions when clean, but
clear contractions and expansions of the top two interlayer spacings, respectively; the effect is largest in
Be, for which an oscillatory trend in the spacing relaxations is apparent down to the 4th interlayer
spacing.
Rather few adsorbate-induced structures on hcp ( 10 1 0 ) have been studied in detail, cf. Table 17.
They show no reconstructions, but a tendency to reduction or even reversal of the interlayer spacing
changes. An exception appears to be presented by hydrogen on Re and Ru(10-10), where the outermost
interlayer spacing remains close to the clean-surface value, while the next interlayer spacing is contracted.
4.1.13 Adsorption on bcc (211)

The ideal bcc(211) surface shows strong similarities to the fcc(110) surface, with ridges and troughs of
close-packed chains of atoms, but the troughs are wider and shallower; also the ridges are displaced
longitudinally to give a lower symmetry than fcc(110) has. No reconstruction of the clean surface is
evident, cf. Table 18, and relaxations of the interlayer spacings are similar to the case of fcc(110).
The bcc(211) surfaces appear to be prone to reconstruction due to adsorption, cf. Table 19, with
missing-row structures of different kinds being induced by H and O on Fe(211). Oxygen on W(211)
seems to reduce the clean-surface spacing relaxations, although these were not optimized in the one study
of this system.
4.1.14 Adsorption on bcc (111)

Only one study is reported on the detailed adsorbate-induced structure of bcc (111). The clean surfaces of
Fe and Mo(111) are not reconstructed. The ideal bcc (111) surface is very open, exposing 1st, 2nd and
3rd layer substrate atoms; it exhibits large interlayer spacing relaxations that are oscillatory, but the
oscillation is not simply antiphase from layer to layer, cf. Table 20.
Hydrogen on Mo(111) at a coverage of 3 monolayers, cf. Table 21, fills each of the large hollows with
3 adatoms that are located off-center on lateral, inclined bridge sites. The outermost Mo-Mo interlayer
spacing is barely affected, while the second interlayer spacing is brought back toward the bulk value from
a large contraction in the clean case.
4.1.15 Adsorption on Si, Ge and C(111)

The clean surfaces of the diamond(111) type are well known to reconstruct in a variety of complex ways,
cf. Table 22. For instance, for clean Si(111) the well-known (7x7) structure is the stable form, while the
metastable (1x1), (2x1), (5x5) and (9x9) structures have also frequently been reported. However, only the
(1x1), (7x7) and (2x1) structures have been determined in detail (but the other (nxn) structures are
expected to be straightforward generalizations of the (7x7) structure). Such reconstructions of the clean
surface strongly improve the bonding between surface atoms from a very unfavorable bulk-like
arrangement. It is then not surprising that adatoms will as a rule perturb this situation fundamentally, and
thus generate completely different surface structures.
Table 23 lists adsorbate-induced structures on Si, Ge and C(111). Hydrogen affects C(111) and
presumably Si and Ge(111) in the simplest manner: removal of the reconstruction by capping the
dangling bonds of the ideal bulk-like termination, with some residual interlayer spacing relaxations that

reflect the difference between a monolayer of H and the missing half-crystal of the bulk. The same
appears to happen with some other adatoms, in particular halide adatoms, and molecules. In these
instances, the bulk is terminated in a complete bilayer, which offers bonds perpendicular to the surface
that can be capped well by monovalent adsorbates.
The bulk diamond lattice can also be terminated between the layers of this bilayer, leaving three times
as many dangling bonds to satisfy: this can be accomplished by adding a trivalent adsorbate like As, Sb
or Bi, which then forms a layer that substitutes for the outermost half of the more stable Si bilayer. A
similar feature is part of the so-called honeycomb-chained-trimer (HCT) reconstruction due to several
metal adsorbates. Here a lateral relaxation in the lower half of the bilayer leads to trimerization of those
Si or Ge atoms. A related type of structure, called conjugate honeycomb-chained-trimer (CHCT) model,
occurs for other metal adsorbates: here it is the metal adatoms that trimerize instead of the substrate
atoms; we thus classify this as not reconstructed, since the Si-Si bonding topology is bulk-like. As Table
23 shows, a number of other reconstructions have been identified, many of which are quite complex.
4.1.16 Adsorption on Si and Ge(100)

Compared to their (111) surface, the (100) surface of diamond lattices are simpler: the main clean form
of these surfaces is the tilted-dimer (2x1) or c(4x2) reconstruction, determined on both Si and Ge, cf.
Table 24. The c(4x2) phase is regarded as the more stable form, in which alternate dimers tilt in opposite
directions. When heated, the tilting of the dimers becomes random and then on average forms a (2x1)
lattice with disordered tilts.
Several adsorbates, cf. Table 25, remove the tilted-dimer reconstruction, by simply capping dangling
bonds of the ideal bulk-like termination. This can occur with H, Co and S. At lower coverages, adatoms
(or larger molecular species) can maintain the dimer by capping its own dangling bonds, but the tilt is
removed, resulting in a symmetric dimer. Metallic adsorbates generally also maintain the dimer, while
symmetrizing it, after adsorption in a variety of configurations above and between the dimers: the
adsorption occurs in so-called bridge, top, valley, cave or pedestal sites, depending on the metal. In yet
other cases, as with Sb, the adsorbate itself forms dimers above the bulk-like substrate. Or the adsorbate
forms dimers above substrate dimers, as with Al and Ga. And, not surprisingly, more complex
reconstructions can occur on this type of surface as well.
4.1.17 Adsorption on diamond-like(311)

The clean surface of Ge(311) has a complex reconstruction, cf. Table 26. While the corresponding
structure of Si(311) is not well-established, adsorption of either H or Pb on Si(311) produces a very
different reonstruction than seen on Ge(311), cf. Table 27.
4.1.18 Adsorption on zincblende(110)

The clean (110) surfaces of zincblende compounds exhibit large relaxations (without superlattice),
sometimes called reconstruction, cf. Table 28. There is no bond breaking or making relative to the ideal
bulk termination, but mainly bond rotations with small bond length changes. In particular, the surface
exposes zigzag rows of atoms, which are coplanar (untilted) in the ideal surface, and are tilted in the
actual clean surface by angles around 25-30° from the surface plane.
Most adsorbates which have been deposited on zincblende(110) surfaces largely remove the clean-
surface relaxations, in particular canceling or even slightly reversing the clean-surface tilting, cf. Table
29. These atoms cap the dangling bonds of the ideal surface, in some cases (Sb, Bi) forming an additional
layer of zigzag atoms, thus mimicking a continuation of the bulk lattice. Aluminum, on the other hand,
substitutes for Ga in the outermost layers, penetrating to deeper substitutional sites in proportion to the
amount of adsorbate present, while maintaining the clean-surface tilting.

4.1.19 Adsorption on zincblende(111) and (-1-1-1)

The clean (111) and (-1-1-1) surfaces of zincblende reconstruct, cf. Tables 30 and 32: in the (111) case a
missing-atom (2x2) structure appears for GaAs, with extensive relaxations around the empty site; the
clean (-1-1-1) structure is rather more complex, with a large (3x3) supercell and additional disorder.
Adsorbates, however, can totally remove these complex clean-surface reconstructions, and restore a
bulk-like termination, cf. Tables 31 and 33. Sulfur and oxygen can bond at top sites on a full-bilayer-
terminated substrate, capping the dangling bonds, while the interlayer spacings in the substrate can relax.
Or S can substitute for the outer half of the external bilayer.
4.1.20 Adsorption on zincblende(100)

Clean zincblende(100) reconstructs in various arrangements of dimers, forming different superlattices like
(2x1), (4x2) and c(8x2), cf. Table 34. The one documented case of adsorbate structure, cf. Table 35, has
S adatoms removing the reconstruction of clean GaAs(100) and adsorbing at bridge sites.
4.1.21 Adsorption on 6H-SiC(0001)

Clean 4H-SiC(0001) has a bulk-like surface termination with a (1x1) unit cell and small relaxations of the
interlayer spacings, cf. Table 36. The adsorption of H, O and OH saturates the dangling bonds at top sites
of the ideal termination in a full SiC bilayer and changes the interlayer spacings by amounts smaller than
0.1Å, cf. Table 37.
Acknowledgments
This work was supported in part by the Director, Office of Science, Office of Basic Energy Sciences,
Materials Sciences Division of the U.S. Department of Energy under Contract No. DE-AC03-76SF00098.
It relied heavily on the Surface Structure Database supported by the Standard Reference Data Program of
the National Institute of Standards and Technology of the U.S. Department of Commerce, with newer
results supplied by individual authors.

Table 1. Techniques used for surface structure determination; listed by their acronyms
ALICISS Alkali ICISS

ARAES Angular Resolved Auger Electron Spectroscopy
ARPES Angular Resolved Photoelectron Spectroscopy

ARUPS Angular Resolved Ultraviolet Photoelectron Spectroscopy
ARXPS Angular Resolved X-ray Photoelectron Spectroscopy
ARXPD Angular Resolved X-ray Photoelectron Diffraction
ARPEFS Angular Resolved Photoelectron Fine Structure
At. diffr. Atom Diffraction
ATLEED Automated Tensor LEED
At. scatt. Atom Scattering
CAICISS Coaxial Impact-Collision Ion Scattering Spectroscopy

CMTA Constant-Momentum Transfer Averaging
DLEED Diffuse LEED
EAPFS Electron Appearance Potential Fine Structure

EELFS Electron Energy Loss Fine Structure
EELS Electron Energy Loss Spectroscopy
ESDIAD Electron Stimulated Desorption Ion Angular Distribution
EXAFS Extended X-ray Absorption Fine Structure
EXELFS Extended Electron Energy Loss Fine Structure
EXFAS Extended Fine Auger Structure
Fluorescence XRD Fluorescence X-ray Diffraction

FYNES Fluorescence-Yield Near-Edge Structure
GIXD Grazing-Incidence X-ray Diffraction

GIXS Grazing-Incidence X-ray Scattering
He diffr. Helium Diffraction

HEIS High-Energy Ion Spectroscopy
HREELS High-Resolution Electron Energy Loss Spectroscopy
ICISS Impact Collision Ion Scattering Spectroscopy

ISS Ion Scattering Spectroscopy
KLEED Kinematic Low-Energy Electron Diffraction

4.1 Surface structure on metals and semiconductors 4.1-13
LEIS Low-Energy Ion Spectroscopy

LEED Low-Energy Electron Diffraction
LEPD Low-Energy Positron Diffraction
MEED Medium-Energy Electron Diffraction

MEIS Medium-Energy Ion Spectroscopy
MEIS-SB MEIS with Shadowing and Blocking
Neutr. diffr. Neutron Diffraction

NEXAFS Near-Edge X-ray Absorption Fine Structure
NPD Normal Photoelectron Diffraction
OPD Off-normal Photoelectron Diffraction
PED Photoelectron Diffraction

PES Photoelectron Spectroscopy
PEXAFS Photoemission Extended X-ray Absorption Fine Structure
PLEED (Spin-) Polarized LEED
QDLEED Quasi-Dynamic Low-Energy Electron Diffraction

QKLEED Quasikinematical Low-Energy Electron Diffraction
RBS Rutherford Backscattering

RHEED Reflection High-Energy Electron Diffraction
SEELFS Surface Electron Energy Loss Fine Structure

SEXAFS Surface Extended X-ray Absorption Fine Structure
SIMS Secondary Ion Mass Spectroscopy
SPLEED Spin-Polarized LEED
TEAS Thermal Energy Atomic Scattering

TED Transmission Electron Diffraction
TOF-SARS Time-of-Flight Scattering and Recoiling Spectroscopy
XAFS X-ray Absorption Fine Structure

XANES X-ray Absorption Near-Edge Structure
XAS X-ray Absorption Spectroscopy
XPD X-ray Photoelectron Diffraction
XRD X-ray Diffraction
XSW X-ray Standing Wave

4.1-14
Table 2. Structures of clean fcc(111) surfaces.
Surface Tech- Clean dbulk ∆d12 ∆d23 ∆d34 ∆d45 ∆d56 Ref. Description
nique rec. [Å] [%] [%] [%] [%] [%]
Ag(111) MEIS no 2.36 10 ± 2 5.5 ± 2 0±6 0 0 94S6 unreconstructed surface; exhibiting strong temperature-
dependent interlayer spacings above 600K: top spacing
grows from contraction of -2.5±0.5% below 600K to
+10±2% at 1150K (wrt to bulk value); 2nd spacing
grows from +0.6% to +5.5%; 3rd spacing shows
smaller effect
Al(111) LEED no 2.338 2.22 ± 1.3 0 0 0 0 80J bulk termination with expanded top spacing
Al(111) LEED no 2.329 0.91 ± 0.5 0 0 0 0 82N1 bulk termination with expanded top spacing
Al(111) LEED no 2.338 1.7 ± 0.3 0.5 ± 0.7 0 0 0 90N multilayer relaxation: expansion of the 1st and 2nd
interlayer spacings
Al(111) LEED no 2.338 1.3 ± 0.9 0 0 0 0 94S5 unreconstructed surface with expanded top interlayer
spacing
Al(111) LEED no 2.338 3.08 ± 2.1 0 0 0 0 83M1 bulk termination with expanded top interlayer spacing
Al(111) LEED no 2.329 1.33 ± 0.4 0.04 ± 0.4 0 0 0 94B8 unreconstructed relaxed surface
Cu(111) LEED no 2.09 -0.67 ± 1 0 0 0 0 84L relaxed bulk termination
Cu(111) V- no 2.09 0.75 ± 1 0 0 0 0 95B1 relaxed bulk termination: possible slight expansion of
LEED top interlayer spacing
Cu(111) XPD no 2.09 -1.44 ± 1 0 0 0 0 97H1 unreconstructed surface with possible slight
contraction of top interlayer spacing
Ni(111) LEED no 2.035 -0.25 ± 1 0 0 0 0 93K1 unreconstructed clean surface with negligible
contraction of top interlayer spacing
Ni(111) XPD no 2.03 2.96 0 0 0 0 97H1 unreconstructed surface with expanded top interlayer
spacing
Ni(111) HEIS no 2.033 0±1 0 0 0 0 81N1 unrelaxed bulk termination
Ni(111) LEED no 2.03 -1.23 ± 1.2 0 0 0 0 75D bulk termination with top spacing contraction
Pd(111) LEED no 2.246 2.41 ± 0.9 0.63 ± 0.9 0.63 ± 1.8 0 0 94G4 unreconstructed surface with multilayer relaxations
Pd(111) HEIS no 2.25 0 ± 4.4 0 0 0 0 83K unrelaxed bulk termination
Pd(111) LEED no 2.27 0.88 ± 1.3 -1.76 ± 1.3 -1.76 ± 1.8 0 0 94B4 slight relaxation of top two interlayer spacings
Pd(111) LEED no 2.246 1.34 ± 1.3 -1.34 ± 1.3 2.23 ± 1.3 0 0 87O slight relaxation of top two interlayer spacings
Pt(111) LEED no 2.265 1.1 ± 4.4 0 0 0 0 79A bulk termination with expanded top spacing
4.1-15
nique rec. [Å] [%] [%] [%] [%] [%]
Pt(111) SP- no 2.265 0.49 ± 0.9 0 0 0 0 81F bulk termination with expanded top spacing
LEED
Pt(111) LEED no 2.26 1.33 ± 0.4 0.44 ± 1.3 -1.33 ± 1.8 0 0 94B5 unreconstructed relaxed bulk termination
Pt(111) LEED no 2.265 1.1 ± 1.3 0.22 0 0 0 95M1 unreconstructed clean surface with slight first layer
expansion
Pt(111) LEED no 2.254 1.38 ± 0.6 -0.4 ± 0.7 0.22 ± 0.9 0 0 97G1 unreconstructed surface with relaxed top two interlayer
spacings; 0.5±0.4% contracted in-plane lattice
parameter for all layers (incl. bulk)
Pt(111) MEIS no 2.268 1.41 ± 0.9 0 0 0 0 79V1 bulk termination with top spacing expansion
Pt(111) LEED no 2.265 0 ± 2.2 0 0 0 0 85H1 unrelaxed bulk termination
Rh(111) LEED no 2.196 -2.86 ± 1.4 0.16 ± 1.4 0 0 0 93W1 unreconstructed termination with relaxation of top two
interlayer spacings
Rh(111) LEED no 2.188 -1.28 ± 0.9 -1.28 ± 1.8 0.09 ± 2.3 0 0 94B5 unreconstructed relaxed bulk termination
Rh(111) LEED no 2.192 0 ± 4.6 0 0 0 0 84V unrelaxed bulk termination
Rh(111) LEED no 2.19 -1.37 ± 0.9 0 0 0 0 80H slightly relaxed bulk termination
Table 3. Adsorbate-induced structures on fcc(111) surfaces.
Surface Tech- Clean Ads- ∆dl,l+1 bls ∆rls αls d01 ∆r0 Ref. Description
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
adsorption at fcc-hollow sites (see Fig. 3)
Ni(111)+ AR- no no 4.7 ± 0.0003 0 0 0 1.837 ± 0.0008 0 91W3 atomic adsorption in fcc-hollow site with
(√3x√3) PEFS contraction between the 1st and 2nd Ni layers
R30°-Cl
Ni(111)+ HEIS no no -4.2 ± 1.5 0 0 0 1.2 0 81N2 atomic adsorption (in undetermined hollow sites;
(√3x√3) fcc assumed here); expanded top Ni-Ni interlayer
R30°-O spacing
4.1-16
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Ni(111)+ LEED no no 0 ± 1.0 0 0 0 1.08 ± 0.02 0 91M2 O adsorbed in fcc-hollow site; substrate has
(√3x√3) expanded 1st interlayer spacing; no lateral shifts or
R30°-O buckling
Ni(111)+ SE- no no 0 0 0 0 1.16 ± 0.10 0 92H1 oxygen adsorbed in fcc-hollow sites; no buckling
(√3x√3) XAFS in 1st Ni layer
R30°-O
Rh(111)+ LEED no no 0.8 ± 2.0 0 0 0 1.59 ± 0.05 0 96W atomic adsorption on unreconstructed substrate: S
(√3x√3) adsorbs on fcc-hollow site; substrate relaxations
R30°-S negligible
Rh(111)+ LEED no no -3.9 ± 3.0 0 0 0 2.22 ± 0.06 0 93B2 atomic adsorption in three fold fcc-hollow site on
(√3x√3) unreconstructed; relaxed Rh substrate
R30°-I
Pd(111)+ LEED no no 1.5 ± 0.9 0 2.5 ± 3.0 0 2.70 ± 0.03 0 94G4 atomic S in fcc-hollow site on unreconstructed;
(√3x√3) relaxed substrate; oscillitory expansion of top 4
R30°-S Pd-Pd interlayer spacings
Pd(111)+ LEED no no 6.2 ± 2.2 0 0 0 1.29 ± 0.05 0 87O molecular upright adsorption (C down) in fcc-
(√3x√3) hollow sites
R30°-CO
Pt(111)+ LEED no no 0.7 ± 1.3 0 0.6 ± 2.5 0 1.55 ± 0.03 0 97Y atomic adsorption in fcc-hollow site; buckling in
(√3x√3) top two layers of substrate
R30°-S
Ag(111)+ LEED no no -0.9 ± 0.8 -3.8 ± 1.7 0 0 3.01 ± 0.04 0 97K1 atomic overlayer in fcc-hollow sites on
(2x2)-Cs 1.2 ± 1.3 1.3 ± 0.8 0 0 unreconstructed substrate; with buckling in the first
2 substrate layers
Ag(111)+ LEED no no -0.9 ± 0.8 -4.2 ± 1.3 0 0 1.52 ± 0.02 0 96L1 atomic overlayer in fcc-hollow sites on
(2x2)-K -0.1 ± 0.8 1.3 ± 0.8 0 0 unreconstructed substrate; with buckling in the first
2 substrate layers
Ag(111)+ LEED no no -0.9 ± 0.8 -4.2 ± 0.1 0 0 2.84 ± 0.03 0 96L1 atomic overlayer in fcc-hollow sites on
(2x2)-Rb -0.5 ± 0.8 1.3 ± 0.1 0 0 unreconstructed substrate; with buckling in the first
2 substrate layers
4.1-17
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Cu(111)+ LEED no no -2.3 ± 1.9 0 -0.2 ± 5.0 0 2.07 ± 0.06 0 95M4 complex reconstruction with overlayer and
(2x2)-3Li: -2.5 ± 2.5 0.2 ± 2.6 -0.1 ± 6.7 0 substitution: two Li adatoms located on fcc and
1 Li fcc- hcp-hollow sites and one Li atom substituting for a
hollow site Cu atom in each cell
Ni(111)+ LEED no no 0.3 ± 1.5 2.0 ± 3.9 0 0 0.97 ± 0.08 0 93H1 atomic adsorption with equal occupation of fcc and
(2x2)-2H: hcp-hollow sites; forming honeycomb-like lattice;
1 H at fcc- buckling in 1st Ni layer: expansion of 2nd Ni-Ni
hollow site interlayer spacing
Ni(111)+ PED no no 5.7 ± 4.9 -1.5 ± 5.0; 0 0 1.28 ± 0.05 0 95D1 K atoms occupy atop sites; CO molecules
(2x2)- 0.0 ± 5.0 perpendicular to surface; occupying fcc and hcp-
K+2CO: hollow sites
1 CO at fcc-
hollow site
Ni(111)+ LEED no no 1.7 ± 1.5 5.9 ± 1.5 5.0 ± 4.0 2.35 1.09 ± 0.03 0 90V3 oxygen adsorbed in fcc-hollow sites; buckling and
(2x2)-O lateral shifts in 1st Ni layer: 3 Ni next to O are lifted
and rotated/outwards shifted; 1st Ni-Ni interlayer
spacing contracts; deeper layers are bulk like
Ni(111)+ SE- no no 4.4 ± 4.9 8.3 ± 4.9 0 0 1.16 ± 0.10 0 92H1 oxygen adsorbed in fcc-hollow sites; buckling in
(2x2)-O XAFS 1st Ni layer
Ni(111)+ LEED no no 5.7 ± 1.0 4.5 ± 1.0 0 0 1.11 ± 0.02 0 94S2 S in fcc-hollow site on unreconstructed relaxed
(2x2)-O 0.8 ± 1.0 -2.0 ± 1.0 0 0 substrate: buckling in the first and second Ni layers;
no evidence for rotation of hollow site
Ni(111)+ PED no no 8.5 ± 5.0 4.9 ± 10.0 0 0 1.08 ± 0.10 0 96D1 atomic O overlayer in fcc-hollow sites on
(2x2)-O unreconstructed; slightly buckled substrate
Ni(111)+ LEED no no 2.7 ± 1.5 0 2.0 ± 2.0 0 1.5 ± 0.03 0 89W overlayer in 3-fold-hollow fcc sites; expansions of
(2x2)-S 2.2 ± 1.5 0 0 0 top 2 Ni-Ni interlayer spacings; lateral radial
expansion of 3-fold site
4.1-18
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Pt(111)+ LEED no no -1.6 ± 4.4 -4.9 ± 4.4 -7.0 ± 5.5 0 1.19 ± 0.10; 0 93S4 ethylidyne species (CCH3=C2H3) formed from
(2x2)-C2H3 -1.1 ± 4.4 -3.5 ± 4.4 0.2 ± 5.5 0 1.30 ± 0.10 ethylene (C2H4) with upright C-C axis: lower C in
fcc-hollow site; upper C forms methyl group
(LEED data not sensitive to H positions); buckling
in top 2 Pt layers
Rh(111)+ LEED no no 3.1 ± 1.8 0.0 ± 1.8 0.0 ± 7.0 0 1.47 ± 0.04 0 97G3 densely packed molecular adsorption with 1 CO on
(2x2)-3CO: -0.1 ± 2.7 3.7 ± 1.8 -0.4 ± 7.0 0 top site; 1 CO on hcp-hollow site and 1 CO on fcc-
1CO at fcc- hollow site; forms a buckled hexagonal overlayer
hollow site on a relaxed substrate; substrate is buckled at the
first layer
Rh(111)+ LEED no no 4.0 ± 1.8 0.0 ± 1.8 0.0 ± 7.0 0 1.30 ± 0.04 0 98Z densely packed molecular adsorption with 1 NO
(2x2)-3NO: -1.4 ± 2.7 2.6 ± 1.8 0.0 ± 7.0 0 on top site; 1 NO on hcp-hollow site and 1 NO on
1NO at fcc- fcc-hollow site; forms a buckled hexagonal
hollow site overlayer on a relaxed substrate; substrate is
buckled at the first layer
Rh(111)+ LEED no no 4.8 ± 2.0 2.3 ± 2.3 0 0 1.24 ± 0.06 0 97S2 atomic adsorption on unreconstructed relaxed
(2x2)-O substrate; adatom at fcc-hollow site
Rh(111)+ LEED no no 5.3 ± 1.4 -1.8 ± 1.4 3.9 ± 3.8 0 1.28 ± 0.04 0 97S2 coadsorption of atomic oxygen and molecular CO
(2x2)- on relaxed substrate O on fcc-hollow site; CO on
(O+1CO): top site
O site
Rh(111)+ LEED no no 4.4 ± 1.8 0.0 ± 2.3 1.3 ± 3.8 0 1.31 ± 0.09 0 97S2 coadsorption of atomic oxygen and molecular CO
(2x2)- on unreconstructed; relaxed substrate; oxygen in
(O+2CO): fcc-hollow site; CO in top site and hcp-hollow site
O site
Pt(111)+ LEED no no 3.3 ± 1.3 4.9 ± 2.2 -6.0 ± 5.0 0 1.49 ± 0.10 0 93S4 ethylidyne species (CCH3=C2H3) formed from
(2x2)-C2H3 -1.0 ± 4.4 -3.5 ± 4.0 0.0 ± 5.0 0 ethylene (C2H4) with upright C-C axis: lower C in
fcc-hollow site; upper C forms methyl group
(LEED data not sensitive to H positions); buckling
in top 2 Pt layers
4.1-19
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Pt(111)+ LEED no no 2.4 ± 1.3 3.1 ± 0.9 1.7 ± 2.0 0 1.19 ± 0.02 0 95M1 atomic overlayer in fcc-hollow sites on
(2x2)-O -1.1 ± 1.3 -0.9 ± 0.9 0.1 ± 3.0 0 unreconstructed substrate; with buckling and lateral
relaxation in the first 2 Pt layers; slight expansion
and contraction of first two Pt-Pt interlayer
spacings; resp.
Pt(111)+ LEED no no 2.4 ± 0.9 3.1 ± 2.6 2.4 ± 1.2 0 1.26 ± 0.06 0 94M2 molecular adsorption perpendicular to surface in
(2x2)-NO 0 -0.9 ± 0.9 -5.7 ± 1.2 0 fcc 3-fold hollow sites on relaxed substrate
Pt(111)+ LEED no no 0.3 ± 2.2 3.5 ± 1.8 1.9 ± 2.5 0 1.54 ± 0.03 0 97Y atomic S adsorption on fcc-hollow sites; buckling
(2x2)-S 3.5 ± 1.8 3.5 ± 1.8 0.0 ± 3.8 0 in first layer of substrate
Ag(111)+ LEED no no 2.1 ± 0.8 -4.2 ± 1.3; 0; 0; 3.02 ± 0.03 0 97K1 atomic overlayer in fcc-hollow sites on
(3x3)-Cs -4.7 ± 1.3 0 0 unreconstructed substrate; with buckling in the first
1.2 ± 1.3 -1.7 ± 1.3; 0; 0; 3 substrate layers
-2.5 ± 1.3 0 0
0.0 ± 1.7 0; 0; 0;
-1.3 ± 2.0; 0; 0;
-1.7 ± 2.0 0 0
(3x3)-K -3.8 ± 1.3 0 0 unreconstructed substrate; with buckling in the first
-2.5 ± 1.3 0 0
-0.5 ± 3.8 0; 0; 0;
-1.3 ± 2.0; 0; 0;
-1.7 ± 2.0 0 0
4.1-20
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
(3x3)-Rb -4.2 ± 1.3 0 0 unreconstructed substrate; with buckling in the first
-2.5 ± 1.3 0 0
-0.5 ± 1.7 0; 0; 0;
-1.7 ± 1.3; 0; 0;
-0.8 ± 1.3 0 0
Pd(111)+ LEED no no 0.4 ± 2.2 0.0 ± 2.2; 0; 0; 1.22 ± 0.05; 0 94B4 molecular coadsorption of one flat-lying C6H6
(3x3)-C6H6+ -2.2 ± 2.2 3.2 ± 7.0 0 1.31 ± 0.05 (benzene) and 2 upright CO per cell; all centered
2CO: 2CO over fcc-hollow sites; both with relaxed bonds (H
sites ignored); 1st substrate layer relaxed; topmost Pd-
Pd interlayer spacing expanded to 2.32Å (average)
from bulk value of 2.25Å
Pd(111)+ LEED no no 2.6 ± 2.2 0.0 ± 2.2; 0; 0; 2.16 ± 0.05 0 94B4 molecular coadsorption of one flat-lying C6H6
(3x3)-C6H6+ 2.2 ± 2.2 0.8 ± 7.0 0 (benzene) and 2 upright CO per cell; all centered
2CO: C6H6 over fcc-hollow sites; both with relaxed bonds (H
site ignored); 1st substrate layer relaxed; topmost Pd-
Pd interlayer spacing expanded to 2.32Å (average)
from bulk value of 2.25Å
Rh(111)+ LEED no no -0.8 ± 0.1 -3.2 ± 0.05 0 0 1.18 ± 0.05 0 96C1 atomic overlayer with O adsorbed in fcc-hollow
(2x1)-O sites; possibly off-center toward top sites; top 2
substrate layers relaxed; both buckled
Rh(111)+ LEED no no 3.9 ± 2.0 1.8 ± 2.0 0 0 1.23 ± 0.04 0 97S2 atomic adsorption on unreconstructed relaxed
(2x1)-O substrate; adatom at fcc-hollow site
Ni(111)+ PED no no 3.2 ± 7.4 0 0 0 1.29 ± 0.07 0 94D1 molecular adsorption; C-O axis perpendicular to
c(4x2)-2CO: surface; CO occupy equally (0.25 ML each) fcc
1CO at fcc- and hcp-hollow sites O atom sites not determined
hollow site explicitly
Ni(111)+ LEED no no 6.1 ± 4.9 5.9 ± 4.9; complex 0; 1.25 ± 0.10; 0 94M1 molecular adsorption in mixed fcc/hcp sites; CO
c(4x2)-2CO: 4.9 ± 4.9 0 1.37 ± 0.10 tilted and bent away from nearest CO; buckled
1CO at fcc- first and second Ni layers
hollow site
4.1-21
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Ni(111)+ LEED no no 4.6 ± 2.0 7.3 ± 2.0; complex 0; 1.17 ± 0.04; 0 94M2 molecular NO perp. to surface; in both fcc and hcp
c(4x2)-2NO: 0.0 ± 2.0 0 1.32 ± 0.04 3-fold hollow sites; relaxations in first 2 substrate
1NO at fcc- layers
hollow site
Rh(111)+ LEED no no -2 -10.0; complex 0; 1.72; 0 96W atomic adsorption on unreconstructed substrate:
c(4x2)-2S: 0.2 0 1.49; equal occupation of fcc-hollow and hcp-hollow
1 S at fcc- -0.1 -1.0; complex 0; 1.72 sites; S lateral shifts in both sites towards one of
hollow site 0.5 0 the nearby Rh atoms; to make S-S distances more
equal; 1st Rh layer buckled
Rh(111)+ LEED no no -3.9 ± 3.0 0 0 0 2.22 ± 0.06 0 93B2 atomic adsorption in three fold fcc-hollow site on
(dis- unreconstructed; relaxed Rh substrate
ordered)-I
adsorption at hcp-hollow sites (see Fig. 4)
Ag(111)+ LEED no no -0.1 ± 1.4 0 0.0 ± 2.0 0 3.10 ± 0.03 0 97K1 atomic overlayer in hcp-hollow sites on
(√3x√3) -0.5 ± 1.4 0; 0; 0; unreconstructed substrate; with buckling in the
R30°-Cs 0.4 ± 1.4 0.0 ± 2.0 0 second substrate layer
Ag(111)+ LEED no no -0.5 ± 0.8 0 0.0 ± 2.0 0 2.84 ± 0.03 0 96L1 atomic overlayer in hcp-hollow sites on
(√3x√3) 0.0 ± 0.8 0; 0; 0; unreconstructed substrate; with buckling in the
R30°-K 0.9 ± 0.8 0.0 ± 2.0 0 second substrate layer
Ag(111)+ LEED no no -0.5 ± 0.8 0 0.0 ± 2.0 0 2.97 ± 0.03 0 96L1 atomic overlayer in hcp-hollow sites on
(√3x√3) 0.0 ± 0.8 0; 0; 0; unreconstructed substrate; with buckling in the
R30°-Rb 0.9 ± 0.8 0.0 ± 2.0 0 second substrate layer
Rh(111)+ LEED no no -0.2 ± 1.4 0 0.0 ± 2.0 0 2.90 ± 0.03 0 96S1 atomic adsorption on unreconstructed relaxed
(√3x√3) substrate; adatom at hcp-hollow site
R30°-Cs
R30°-K
4.1-22
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
R30°-Rb
Pt(111)+ LEED no no 1.0 ± 0.8 0 0 0 2.71 ± 0.02 0 98M4 atomic adsorption on unreconstructed relaxed
R30°-K
Cu(111)+ LEED no no -2.1 ± 1.9 0 0.2 ± 5.0 0 2.15 ± 0.06 0 95M4 complex reconstruction with overlayer and
(2x2)-3Li: -2.7 ± 2.5 0; 0; 0; substitution: two Li adatoms located on fcc and
1 Li at hcp- -0.2 ± 2.6 0 0 hcp-hollow sites and one Li atom substituting for a
hollow site Cu atom in each cell
Ni(111)+ LEED no no 1.8 ± 1.5 2.0 ± 3.9 0 0 0.97 ± 0.08 0 93H1 atomic adsorption with equal occupation of fcc and
(2x2)-2H: hcp-hollow sites; forming honeycomb-like lattice;
1 H at hcp- buckling in 1st Ni layer: H-coordinated Ni atoms
hollow site raised; expansion of 2nd Ni-Ni interlayer spacing
Ni(111)+ PED no no 5.7 ± 4.9 -1.5 ± 5.0; 0; 0; 1.28 ± 0.05 0 95D1 K atoms occupy atop sites; CO molecules
(2x2)- 0.0 ± 5.0 0 0 perpendicular to surface; occupying fcc and hcp-
K+2CO: hollow sites
1 CO at hcp-
hollow site
Pt(111)+ LEED no no -0.3 ± 1.0 -3.1 ± 0.9 0 0 2.68 ± 0.03 0 98M4 atomic adsorption on unreconstructed relaxed
(2x2)-K substrate; adatom at hcp-hollow site
Rh(111)+ LEED no no 4.6 ± 4.6 3.6 ± 4.6 0.4 ± 6.1 0 1.20 ± 0.10; 0 94B5 ethylidyne species (CCH3 = C2H3) formed from
(2x2)-C2H3 1.0 ± 4.6 0; 0; 0; 1.28 ± 0.10 ethylene (C2H4) with upright C-C axis: lower C in
0.0 ± 4.6 0.0 ± 0.2 0 hcp-hollow site; upper C forms methyl group;
buckling in top 2 Rh layers
Rh(111)+ LEED no no 6.7 ± 1.8 0.0 ± 1.8 -0.4 ± 6.1 0 1.47 ± 0.07; 0 97G3 densely packed molecular adsorption with 1 CO on
(2x2)-3CO: -3.8 ± 2.7 0; 0; 0; 1.47 ± 0.07 top site; 1 CO on hcp-hollow site and 1 CO on fcc-
1CO at hcp- -3.6 ± 1.8 0.0 ± 0.2 0 hollow site; forms a buckled hexagonal overlayer
hollow site on a relaxed substrate; substrate is buckled at the
first layer
Rh(111)+ LEED no no -1.6 ± 1.4 -1.8 ± 1.4 0.0 ± 2.0 0 2.78 ± 0.03 0 96S1 atomic adsorption on unreconstructed relaxed
(2x2)-K substrate; adatom at hcp-hollow site
4.1-23
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Rh(111)+ LEED no no 7.2 ± 1.8 0.0 ± 1.8 0.0 ± 6.1 0 1.29 ± 0.07 0 98Z densely packed molecular adsorption with 1 NO
(2x2)-3NO: -1.5 ± 2.7 0; 0; 0; on top site; 1 NO on hcp-hollow site and 1 NO on
1NO at hcp- -2.7 ± 1.8 0.0 ± 0.2 0 fcc-hollow site; forms a buckled hexagonal
hollow site overlayer on a relaxed substrate; substrate is
Rh(111)+ LEED no no -1.1 ± 3.2 -0.9 ± 3.2; -0.7 ± 6.1; 0; 1.36 ± 0.10; 0 94B4 molecular coadsorption of one flat-lying C6H6
(3x3)-C6H6+ -0.9 ± 3.2 -2.1 ± 6.1 0 1.39 ± 0.10 (benzene) and 2 upright CO per cell; all centered
2CO: 2CO over hcp-hollow sites; both with relaxed C-C
sites bonds (H ignored); 1st substrate layer relaxed
Rh(111)+ LEED no no -1.1 ± 3.2 0.9 ± 2.2; 0; 0; 2.07 ± 0.04 0 94B4 molecular coadsorption of one flat-lying C6H6
(3x3)-C6H6+ 0.9 ± 3.2 -3.9 ± 6.1 0 (benzene) and 2 upright CO per cell; all centered
2CO: C6H6 over hcp-hollow sites; both with relaxed C-C
site bonds (H ignored); 1st substrate layer relaxed
Ni(111)+ PED no no 3.2 ± 7.4 0 0 0 1.30 ± 0.07 0 94D1 molecular adsorption; C-O axis perpendicular to
c(4x2)-2CO: surface; CO occupy equally (0.25 ML each) fcc
1CO at hcp- and hcp-hollow sites O atom sites not determined
hollow site explicitly
Ni(111)+ LEED no no 6.1 ± 4.9 -4.9 ± 4.9; complex 0; 1.37 ± 0.10; 0 94M1 molecular adsorption in mixed fcc/hcp sites; CO
c(4x2)-2CO: -5.9 ± 4.9 0 1.27 ± 0.10; tilted and bent away from nearest CO; buckled
1CO at hcp- -4.6 ± 4.9 0; complex 0; 1.25 ± 0.10 first and second Ni layers
hollow site -3.9 ± 4.9; 0;
-1.5 ± 4.9 0
4.1-24
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Ni(111)+ LEED no no -1.2 ± 2.0 -7.4 ± 2.0; complex 0; 1.32 ± 0.04; 0 94M2 molecular NO perp. to surface; in both fcc and hcp
c(4x2)-2NO: 0.0 ± 2.0 0 1.17 ± 0.04; 3-fold hollow sites; relaxations in first 2 substrate
1NO at hcp- 1.32 ± 0.04 layers
hollow site
-0.7 ± 2.0 0; complex 0;
-1.5 ± 2.0; 0;
-2.5 ± 2.0 0
Rh(111)+ LEED no no -1.9 -10.3; complex 0; 1.72; 0 96W atomic adsorption on unreconstructed substrate:
c(4x2)-2S: -0.2 0 1.49; equal occupation of fcc-hollow and hcp-hollow
1 S at hcp- -0.4 0; complex 0; 1.72 sites; S lateral shifts in both sites towards one of
hollow site -0.3; 0; the nearby Rh atoms; to make S-S distances more
-1.5 0 equal; 1st Rh layer buckled
Ni(111)+ ( LEED no no 2.5 ± 3.0 -3.9 ± 3.4; 0; 0; 1.93 ± 0.05; 0 96H2 molecular C6H6 centered on hcp sites on
√7x√7) -6.9 ± 3.4 0.8 ± 5.8 ± 1.6; 2.01 ± 0.05; unreconstructed substrate; C-C bonds parallel to [-
R19°-C6H6: ± 2.5 2.01 ± 0.05 110] direction; slight ring expansion; no significant
high C buckling of benzene; strong buckling of top Ni
layer
Ni(111)+ LEED no no 2.5 ± 3.0 -3.9 ± 3.4; 0; 0; 1.97 ± 0.05; 0 96H2 molecular C6H6 centered on hcp sites on
(√7x√7) -6.9 ± 3.4 0.8 ± 5.8 ± 1.6; 2.05 ± 0.05; unreconstructed substrate; C-C bonds parallel to [-
R19°-C6H6: ± 2.5 2.05 ± 0.05 110] direction; slight ring expansion; no significant
low C buckling of benzene; strong buckling of top Ni
layer
adsorption at top sites (see Fig. 5)
Al(111)+ LEED no no -5.5 ± 2.1 0; 0; 0; 3.23 ± 0.05 0 94S5 atomic K in top site on unreconstructed but
(√3x√3) -10.7 ± 1.7 0 0 relaxed substrate: Al directly below K depressed
R30°-K into bulk; Al in next layer laterally displaced by
(90K) small shift; perpendicular relaxation between top
two Al layers
4.1-25
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Al(111)+ LEED no no -5.8 ± 0.9 0, 0; 0; 3.36 ± 0.03 0 94N2 adatoms in top sites of unreconstructed relaxed
(√3x√3) -11.4 ± 0.9 0 0 substrate: downward buckling of Al directly
R30°-Rb below Rb in top Al layer
(100K)
Rh(111)+ LEED no no 8.1 ± 2.3 0; 0; 0; 1.20 ± 0.05 0 97G3 molecular adsorption at top sites: CO upright; C
(√3x√3) 3.6 ± 2.7 0 0 down on relaxed substrate; top substrate layer
R30°-CO 1.7 ± 4.6 0 0.0 ± 7.3 0 slightly buckled
Ni(111)+ PED no no -8.6 ± 2.9 0; 0; 0; 2.87 ± 0.04 0 94D2 K atoms occupy atop sites; outer Ni layer spacing
(2x2)-K -0.5 ± 4.4 0 0 contracted but no significant buckling; K has
large vibrational amplitude parallel to surface
Ni(111)+ AR- no no -6.4 ± 2.0 0 0 0 3.02 ± 0.01 0 93H5 atomic adsorption on top sites; with contraction of
(2x2)-K PEFS first Ni interlayer spacing; negligible lateral
relaxations and buckling
Ni(111)+ LEED no no -4.2 ± 1.5 0; 0; 0; 2.82 ± 0.04 0 93K1 atomic adsorption on top sites; with buckling of
(2x2)-K -5.9 ± 1.0 0 0 the first two Ni layer and small horizontal
relaxation of the top Ni layer (within error bars)
Ni(111)+ PED no no 6.2 ± 4.9 0; 0; 0; 3.02 ± 0.05 0 95D1 K atoms occupy atop sites; CO molecules
(2x2)- 0.5 ± 5.0 0 0 perpendicular to surface; occupying fcc and hcp-
K+2CO: hollow sites
1 K at top site
Rh(111)+ LEED no no 3.1 ± 1.8 0; 0; 0; 1.83 ± 0.07 0 97G3 densely packed molecular adsorption with 1 CO
(2x2)-3CO: 0.0 ± 1.8 0.0 ± 0.2 0 on top site; 1 CO on hcp-hollow site and 1 CO on
1 CO at top -0.2 ± 2.7 3.6 ± 1.8 -0.6 ± 7.0 0 fcc-hollow site; forms a buckled hexagonal
site overlayer on a relaxed substrate; substrate is
Rh(111)+ LEED no no -1.6 ± 1.5 0; 0; 0; 2.96 ± 0.03 0 96S1 atomic adsorption on unreconstructed unrelaxed
(2x2)-Cs -1.8 ± 1.4 0 0 substrate; adatom at top site
Rh(111)+ LEED no no 4.5 ± 1.8 0; 0; 0; 1.76 ± 0.07 0 98Z densely packed molecular adsorption with 1 NO
(2x2)-3NO: 0.0 ± 1.8 0.0 ± 0.2 0 on top site; 1 NO on hcp-hollow site and 1 NO on
1 NO at top 1.2 ± 2.7 2.7 ± 1.8 0.0 ± 6.1 0 fcc-hollow site; forms a buckled hexagonal
site overlayer on a relaxed substrate; substrate is
4.1-26
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Rh(111)+ LEED no no 5.3 ± 1.4 0; 0; 0; 1.83 ± 0.05; 0 97S2 coadsorption of atomic oxygen and molecular CO
(2x2)- 1.8 ± 1.4 0.0 ± 0.1 0 1.87 ± 0.05 on relaxed substrate O on fcc-hollow site; CO on
(O+1CO): top site
CO at top
site
Rh(111)+ LEED no no 4.4 ± 2.3 0; 0; 0; 1.86 ± 0.05; 0 97S2 coadsorption of atomic oxygen and molecular CO
(2x2)- 0.0 ± 2.2 0.0 ± 0.1 0 1.86 ± 0.05 on unreconstructed; relaxed substrate; oxygen in
(O+2CO): fcc-hollow site; CO in top site and hcp-hollow
1 CO at top site
site
molecular adsorption with adatoms at low-symmetry sites
Ni(111)+ LEED no no 94G1 distorted molecular adsorption on relaxed;

(2x2)- unreconstructed substrate: C-N axis near parallel
CH3CN to surface with N near fcc 3-fold hollow site and N
near bridge site; C-C-N bond angle is 123±15°
(vs. 180° for free molecule; making methyl (CH3)
group of acetonitrile points away from surface;
Ni(111)+ PED no no 94B2 molecular adsorption; C-C axis (almost) parallel to
(dis- surface: molecule in aligned-bridge site with C
ordered)- atoms almost directly above top layer Ni atoms;
C2H4 C-C bond extended ~0.27Å relative to gas phase
molecule
adsorption at substitutional site in top substrate layer (see Fig. 6)
Ag(111)+ CA- no yes 0 0 0 0 0 0 97N2 atomic Sb adsorbate substitutional in outermost

(√3x√3) ICISS layer site
R30°-Sb
4.1-27
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Al(111)+ LEED no yes -1.9 ± 1.0 0 0 0 2.16 ± 0.03 0 94S5 atomic K in quasi-substitutional sites formed by
(√3x√3) ejection of 1/3 of top-layer Al; perpendicular
R30°-K relaxation between top two Al layers; no lateral
(300K) relaxations
Al(111)+ LEED no yes -1.7 ± 0.9 0 0 0 0.41 ± 0.1 0 96N adatoms in substitutional sites in top Al layer
(√3x√3) -0.8 ± 0.9 0 0 0
R30°-Li
Al(111)+ SE- no yes -0.0 ± 1.3 0 0 0 1.67 ± 0.03 0 91S1 Na in a sixfold substitutional site
(√3x√3) XAFS
R30°-Na
Al(111)+ XSW no yes 0 0 0 0 1.20 ± 0.2 0 92K1 Na atom in substitutional sites in top Al layer
(√3x√3)
R30°-Na
Al(111)+ LEED no yes -2.5 ± 1.1 0 0 0 1.47 ± 0.02 0 94B8 atomic adsorption in substitutional sites; replacing
(√3x√3) one third of atoms in top Al layer
R30°-Na
Al(111)+ XSW no yes 0 0 0 0 1.20 ± 0.08 0 95S2 Na atom in substitutional sites of reconstructed
(√3x√3) substrate; O atop Na atoms; substrate atom
R30°-Na+O positions assumed bulk-like
Al(111)+ LEED no yes -2.7 ± 0.9 0 0 0 2.41 ± 0.02 0 94N2 adatoms in substitutional sites in top Al layer
(√3x√3)
R30°-Rb
(300K)
Al(111)+ XSW no yes 0 0 0 0 2.39 ± 0.10 0 94S4 Rb adatoms in substitutional sites on reconstructed
(√3x√3) substrate; substrate atom positions assumed bulk-
R30°-Rb like
(300K)
Cu(111)+ LEIS no yes 0 0 0 0 0.39 ± 0.10 0 92O3 substitutional adsorption within top substrate layer;
(√3x√3) forming single layer thick surface alloy; with Sn
R30°-Sn atoms buckled outwards
4.1-28
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Pt(111)+ AL- no yes 0 0 0 0 0.22 ± 0.05 0 91O3 atomic substitutional adsorption in fcc-hollow site;
(√3x√3) ICISS approximating Pt3Sn(111) termination
R30°-Sn
Pt(111)+ LEIS no yes 0 0 0 0 0.22 ± 0.10 0 92O3 substitutional adsorption within top substrate layer;
(√3x√3) forming single layer thick surface alloy; with Sn
Pt(111)+ LEED no yes -0.2 ± 2.2 0 0 0 0.23 ± 0.05 0 93A substitutional adsorption within top substrate layer;
(√3x√3) 2.9 ± 4.4 0 0 forming single layer thick surface alloy; with Sn
Rh(111)+ AL- no yes 0.0 ± 2.3 0 0.29 ± 0.05 0 97L1 atomic substitutional adsorption in fcc-hollow site;
(√3x√3) ICISS approximating Rh3Sn (111) termination
R30°-Sn XPD
Cu(111)+ LEED no yes -2.3 ± 1.9 0 0 0 0.60 ± 0.06 0 95M4 complex reconstruction with overlayer and
(2x2)-3Li: -2.5 ± 2.5 0.2 ± 2.6 0 0 substitution: two Li adatoms located on fcc and
1 Li in subst. hcp-hollow sites and one Li atom substituting for a
site Cu atom in each cell
Pt(111)+ AL- no yes 0 0 0 0 0.22 ± 0.05 0 91O3 atomic substitutional adsorption in fcc-hollow site;
(2x2)-Sn ICISS approximating Pt3Sn(111) termination
Pt(111)+ LEED no yes -0.2 ± 2.2 0 0 0 0.30 ± 0.05 0 93A substitutional adsorption within top substrate layer;
(2x2)-Sn 2.0 ± 4.4 0 0 0 forming single layer thick surface alloy; with Sn
atoms buckled outwards
Al(111)+ XSW no yes 0 0 0 0 1.20 ± 0.2 0 92K1 Na atom in substitutional sites in top Al layer
(dis-
ordered)-Na
adsorption at substitutional site in top substrate layer and as overlayer
Ag(111)+ CA- no yes 97N2 atomic 1/4 ML Sb (2x2) overlayer adsorbed in

(2√3x2√3) ICISS hcp-hollow sites on mixed (√3x√3)R30° Ag+Sb
R30° -7Sb layer containing 1/3 ML Sb
4.1-29
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
adsorption at substitutional site in top two substrate layers
Au(111)+ LEED yes yes 94B1 ordered mixed alloy in top two layers: relaxation of
(√3x√3) top two interlayer spacings
R30°-4Pd
complex reconstruction
Al(111)+ LEED no yes 95B5 surface alloy structure: Na-Al-Na 'sandwich' on a

(2x2)-2Na reconstructed Al layer with a (2x2) vacancy
structure; lower Na in substitutional site in Al
vacancy; upper Na in fcc sites; sandwich Al in hcp
sites
Al(111)+ SE- no yes 95B5 surface alloy structure: Na-Al-Na 'sandwich' on a
(2x2)-2Na XAFS reconstructed Al layer with a (2x2) vacancy
structure; lower Na in substitutional site in Al
vacancy; upper Na in fcc sites; sandwich Al in hcp
sites
Al(111)+ XPD no yes 95F1 composite double-layer surface alloy: 1 Na atom
(2x2)-2Na substituting for a surface Al atom; 1 Na atom in a
fcc-hollow adsorption site; 1 Al atom in a hcp-
hollow adsorption site
Al(111)+ LEED no yes 96C2 ternary surface alloy: K-Al-Na 'sandwich' on a
(2x2)-Na+K reconstructed Al layer with a (2x2) vacancy
structure; Na in substitutional site in Al vacancy; K
in fcc sites above 2nd-layer Al; sandwich Al in hcp
sites
4.1-30
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Rh(111)+ LEED no yes 97L2 reconstruction with packed Rh pentagons and
(√7x√7) triangles; 3 symm.-equivalent P atoms per unit cell
R19°-3P in 8-fold coordinated sites; these form a dense;
relatively coplanar layer (buckled 0.17Å); 2nd and
3rd layers are pure Rh; buckled 0.06Å and 0.08Å
resp.; vs bulk
Cu(111)+ XSW no yes 90P2 reconstructed mixed top layer of stoichiometry
(√7x√7) SE- CuS commensurate with substrate; Cu atoms in
R19°-3S XAFS this CuS layer are coplanar; 2/3 of S lie ~0.56Å
below this Cu layer in hollow sites relative to bulk-
like substrate; other 1/3 S lie about coplanar with
top Cu; over top site of substr.
Cu(111)+ XRD no yes 97F2 complex reconstruction forming Cu4S units (1 per
(√7x√7) unit cell); each having a S atom adsorbed in the
R19°-3S fourfold site on top of a Cu tetramer; additional S
atoms are present at a level just below the Cu4
plane; the positions of these atoms relative to the
bulk are undetermined
Cu(111)+ XRD no yes 97F2 complex reconstruction forming Cu4S units (2 per
(4,1/-1,4)-6S unit cell); each having a S atom adsorbed in the
fourfold site on top of a Cu tetramer; additional S
atoms are present at a level just below the Cu4
plane; the positions of these atoms relative to the
bulk are undetermined
Ni(111)+ XSW no yes 96L4 S overlayer on 'clock-reconstructed' pseudo-(100)
(5√3x2) Ni outer layer such that S atoms have two different
rect-8S layer spacings; one from a 'dropped' layer at regular
fault-lines in the reconstruction; note: outer layer
Ni x,y coordinates are indicative only; as is exact
substrate registry
4.1-31
Table 4. Structures of clean hcp(0001) surfaces.
nique rec. [Å] [%] [%] [%] [%] [%]
Be(0001) LEED no 1.79 5.1 ± 0.4 -0.2 ± 0.5 0.2 ± 0.5 0 0 92D bulk termination with large expansion of top interlayer
spacing
Co(0001) LEED no 2.05 0.0 ± 2.4 0 0 0 0 78L bulk hcp termination
Gd(0001) LEED no 2.89 -1.4 ± 1.0 2.1 ± 1.0 0 0 0 92Q2 multilayer relaxation
Gd(0001) LEED no 2.89 -1.4 ± 0.5 1.0 ± 0.5 0 0 0 95G3 unreconstructed with multilayer relaxation
Mg(0001) LEED no 2.592 2.7 ± 0.3 0.8 ± 4.0 -0.4 ± 0.5 0 0 93S3 bulk termination with top spacing expansion
Ru(0001) LEED no 2.14 -1.8 ± 0.9 0 0 0 0 83M3 bulk termination with top spacing contraction
Sc(0001) LEED no 2.64 -1.9 ± 0.8 0 0 0 0 82T2 bulk-like termination with contraction of top interlayer
spacing
Tb(0001) LEED no 2.847 -5.3 ± 1.1 1.4 ± 1.1 0 0 0 91Q multilayer relaxation
Ti(0001) LEED no 2.34 -2.1 ± 2.1 0 0 0 0 76S1 bulk-like termination with contraction of top interlayer
spacing
Zn(0001) LEED no 2.44 -2.0 ± 2.0 0 0 0 0 75U bulk termination with top spacing contraction
Zr(0001) LEED no 2.57 -1.7 ± 1.9 0 0 0 0 79M bulk hcp termination with top spacing contraction
Table 5. Adsorbate-induced structures on hcp(0001) surfaces.
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
adsorption at fcc-hollow sites (see Fig. 7)
Ru(0001)+ LEED no no -1.8 ± 1.4 0 0 0 1.10 ± 0.06 0 87L2 atomic adsorption in fcc-hollow sites; with slight
(1x1)-H contraction of topmost Ru-Ru interlayer spacing
Zr(0001)+ LEED no yes 33.7 ± 1.9 0 0 0 0.89 ± 0.05 0 97W two O layers are present in the structure; one
(1x1)-2O: forms an overlayer in which the O bonds to 3-
1 O at fcc- fold hollow sites on the Zr surface; the other
hollow sites layer has the O atoms in tetrahedral hole sites
between the first two Zr layers
4.1-32
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Ru(0001)+ LEED no no 1.4 ± 1.9 8.9 ± 1.9 0 0 1.52 ± 0.03; 0 95O2 Cs adsorption in on-top site; pronounced
(2x2)- 1.71 ± 0.03 buckling in top substrate layer; CO in threefold
Cs+2CO: coordinated hcp and fcc sites
1 CO at fcc-
hollow site
Ru(0001)+ LEED no no -1.0 ± 1.4 0 0 0 2.90 ± 0.04 0 92G atomic adsorption in fcc-hollow site on nearly
(2x2)-K unrelaxed substrate
Ru(0001)+ LEED no no -1.4 ± 1.4 0 0 0 2.50 ± 0.04 0 94H3 atomic adsorption in fcc-hollow site on nearly
(2x2)-Na unrelaxed substrate
Ru(0001)+ LEED no no -0.5 ± 0.7 -8.8 ± 0.7 -0.7 ± 2.8 3.0 ± 2.3 1.42 ± 0.05; 0 97S4 intact molecular adsorption in top; hcp and fcc
(2x2)-3NO: -0.5 ± 1.0 2.3 ± 1.0 0.6 ± 3.5 0.8 ± 3.0 1.23 ± 0.05 sites; upright orientation with the N end down;
1 NO at fcc- significant different site-specific inner NO
hollow site bondlengths: NO(top)=1.13;
NO(hcp/fcc)=1.24/1.22Å; significant buckling
in top metal layer
Ru(0001)+ LEED no no 0.9 ± 2.3 -5.6 ± 1.4 -5.1 ± 4.5 0 1.39 ± 0.07; 0 99S1 O in hcp-hollow site; NO in top and fcc-hollow
(2x2)- 1.27 ± 0.07 sites
O+2NO:
1 NO at fcc-
hollow site
Ru(0001)+ LEED no no -0.5 ± 1.4 -3.3 ± 1.4 0.0 ± 4.5 -6.1 ± 3.0 1.39 ± 0.07; 0 99S1 O in fcc and hcp-hollow sites; NO in top site
(2x2)- 1.26 ± 0.07
2O+NO: 1 O
at fcc-hollow
site
Ru(0001)+ LEED no no 9.3 ± 0.9 4.2 ± 0.9 -5.2 ± 5.0 0 1.42 ± 0.08; 0 94N1 O atoms adsorbed in hcp and fcc sites; forming
(2x2)- 1.51 ± 0.08 honeycomb pattern; CO molecules adsorbed
2O+CO: 1 O upright in top sites; relaxations in topmost Ru
at fcc-hollow layer in both lateral and perpendicular directions
site
4.1-33
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Ru(0001)+ LEED no no -1.9 ± 2.3 -2.8 ± 1.9 0 0 3.04 ± 0.05; 0 94H2 atomic adsorption in 3-fold coordinated fcc site
(2x2)-Rb 2.98 ± 0.05 on unreconstructed substrate; anisotropic
thermal distribution of Rb; large parallel root
mean square displacement = 0.37Å
Ru(0001)+ LEED no no 1.8 ± 2.8 0.9 ± 2.8 complex 0 1.32 ± 0.2; 0 92H2 adsorption roughly on threefold fcc sites;
(2x1)-H 1.34 ± 0.2 buckling and pairing reconstruction of the first
metal layer; slight expansion of the first metal
interlayer spacing
Ru(0001)+ LEED no no -4.7 ± 0.9 -7.9 ± 0.9; complex 0; 1.79 ± 0.02; 0 94S3 S close to hcp and fcc-hollow sites shifted away
c(4x2)-2S: -0.9 ± 0.9 0 1.60 ± 0.02; from symmetric positions; buckling and lateral
1 S near fcc- -1.5 ± 0.9 0.5 ± 0.9 complex 0 1.77 ± 0.02 shifts of rows in the first substrate layer;
hollow site buckling in the second substrate layer
adsorption at hcp-hollow sites (see Fig. 8)
Ru(0001)+ LEED no no 3.7 0 0 0 1.25 0 96S2 atomic adsorption on unreconstructed relaxed

(1x1)-O substrate; adatom at hcp-hollow site;
Ru(0001)+ LEED no no -1.9 ± 1.9 0 0 0 3.15 ± 0.03 0 92O1 atomic adsorption in hcp-hollow sites of
(√3x√3) -0.9 ± 3.3 unreconstructed substrate; relaxations in top 2
R30°-Cs Ru-Ru interlayer spacings; no detectable lateral
relaxations
Ru(0001)+ LEED no no -2.8 ± 1.0 0 0 0 3.04 ± 0.03 0 92O2 adsorption of Cs and O in hcp-hollow sites;
(√3x√3) change of O-Ru bond length due to coadsorption
R30°-Cs+O: of Cs
Cs site
Ru(0001)+ LEED no no -2.8 ± 1.0 0 0 0 1.52 ± 0.07 0 92O2 adsorption of Cs and O in hcp-hollow sites;
(√3x√3) change of O-Ru bond length due to coadsorption
R30°-Cs+O: of Cs
O site
4.1-34
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Ru(0001)+ LEED no no -1.9 ± 2.3 0 0 0 2.94 ± 0.04 0 92G atomic adsorption in hcp-hollow site on nearly
(√3x√3) unrelaxed substrate
R30°-K
Ru(0001)+ LEED no no -2.4 ± 2.3 0 0 0 2.25 ± 0.05 0 95G2 atomic adsorption in 3-fold hcp-hollow site on
(√3x√3) 1.3 ± 2.3 0; 0; 0; unreconstructed substrate; buckling in 2nd
R30°-Li 2.3 ± 1.9 0 0 substrate layer
Ru(0001)+ LEED no no -0.9 ± 2.3 0 1.3 ± 2.8 0 1.10 ± 0.06 0 97S3 atomic adsorption on unreconstructed relaxed
R30°-N
Ru(0001)+ LEED no no -0.9 ± 2.3 0 0 0 2.51 ± 0.05 0 94H3 atomic adsorption in hcp-hollow site on nearly
(√3x√3) unrelaxed substrate
R30°-Na
Ru(0001)+ LEED no no -0.9 ± 2.3 0 0 0 3.03 ± 0.05 0 94H2 atomic adsorption in 3-fold coordinated hcp-
(√3x√3) hollow site on unreconstructed substrate;
R30°-Rb anisotropic thermal distribution of Rb; large
parallel root mean square displacement = 0.37Å
Ru(0001)+ LEED no no -1.0 ± 0.9 0 0 0 1.67 ± 0.02 0 94J2 S in hcp-hollow sites on unreconstructed; relaxed
(√3x√3) substrate: no lateral shifts or buckling in the
R30°-S substrate
Re(0001)+ LEED no no -4.5 ± 3.6 2.2 ± 3.1 1.4 ± 4.4 0 1.68 ± 0.04; 0 94B3 adatoms in 3-fold hcp-hollow sites; contracted
(2x2)-S 4.6 ± 3.1 0; 0; 0; 1.73 ± 0.07 average first and second substrate interlayer
2.8 ± 3.6 0 0 spacings of 2.16 and 2.18Å; resp.; compared to
2.23Å for the bulk
Cs+CO: CO coordinated hcp sites between Cs atoms
at hcp-hollow
site
4.1-35
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Cs+2CO: coordinated hcp and fcc-sites
1 CO at hcp-
hollow site
Ru(0001)+ LEED no no -1.0 ± 2.3 3.3 ± 2.3 0 0 1.05 ± 0.05; 0 97S3 atomic adsorption on unreconstructed relaxed
(2x2)-N 1.12 ± 0.05 substrate; adatom at hcp-hollow site
Ru(0001)+ LEED no no 1.8 ± 0.7 -8.8 ± 0.7 1.0 ± 2.8 -3.0 ± 2.3 1.31 ± 0.05; 0 97S4 intact molecular adsorption in top; hcp and fcc
(2x2)-3NO: 1.12 ± 0.05 sites; upright orientation with the N end down;
1NO at hcp- -2.8 ± 1.0 0; 0; 0; significant different site-specific inner NO bond
hollow site -2.3 ± 1.0 -0.8 ± 3.5 0.8 ± 3.0 lengths: NO(top)=1.13;
NO(hcp/fcc)=1.24/1.22Å; significant buckling
in top metal layer
Ru(0001)+ LEED no no -2.3 ± 1.4 3.3 ± 1.4 5.4 ± 6.4 0 1.18 ± 0.03; 0 89L5 atomic adsorption in hcp-hollow sites; slight
(2x2)-O 3.7 ± 1.4 0; 0; 0; 1.25 ± 0.03 contraction of first Ru-Ru interlayer spacing
3.7 ± 1.4 0 0 while second spacing essentially bulk-like;
buckling of first and second Ru layers
Ru(0001)+ LEED no no 95N O atoms adsorbed in hcp sites; CO molecules
(2x2)-O+CO: adsorbed in top sites; tilted by 12.6°; relaxations
O at hcp- of topmost Ru layer in both lateral and vertical
hollow site directions CO tilt could be either vibrational or
static
Ru(0001)+ LEED no no -3.3 ± 0.9 4.2 ± 0.9 5.2 ± 5.0 0 1.23 ± 0.08; 0 94N1 O atoms adsorbed in hcp and fcc sites; forming
(2x2)- 1.32 ± 0.08 honeycomb pattern; CO molecules adsorbed
2O+CO: 1 O upright in top sites; relaxations in topmost Ru
at hcp-hollow layer in both lateral and perpendicular directions
site
Ru(0001)+ LEED no no -2.8 ± 2.8 3.3 ± 2.8 6.4 ± 2.8 0 1.25 ± 0.06; 0 95O1 coadsorption of atomic oxygen and molecular
(2x2)- 1.32 ± 0.06 dinitrogen on unreconstructed; relaxed substrate;
(O+N2): O at oxygen in hcp-hollow site; N2 on top site;
hcp-hollow perpendicular to surface
site
4.1-36
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Ru(0001)+ LEED no no 0.9 ± 1.9 -6.5 ± 1.4 6.4 ± 4.3 0 1.19 ± 0.05; 0 99S1 O and NO in hcp-hollow sites
(2x2)-O+NO: 1.05 ± 0.05
O at hcp-
hollow site
Ru(0001)+ LEED no no 3.4 ± 2.3 -5.6 ± 1.4 5.1 ± 4.5 0 1.21 ± 0.07; 0 99S1 O in hcp-hollow site; NO in top and fcc-hollow
(2x2)- 1.09 ± 0.07 sites
O+2NO: O at
hcp-hollow
site
Ru(0001)+ LEED 4.6 ± 1.4 -3.3 ± 1.4 0.0 ± 4.5 6.1 ± 3.0 1.20 ± 0.07; 0 99S1 O in fcc and hcp-hollow sites; NO in top site
(2x2)- 1.07 ± 0.07
2O+NO: 1 O
at hcp-hollow
site
Ru(0001)+ LEED no no 0.2 ± 0.9 1.4 ± 0.9 4.5 ± 3.7 0 1.61 ± 0.02; 0 94J2 S in hcp-hollow sites on unreconstructed; relaxed
(2x2)-S -1.6 ± 0.9 0; 0; 0; 1.64 ± 0.02 substrate: buckling in the first and second Ru
-1.4 ± 0.9 0.0 ± 0.4 0 layers; lateral shifts in the first Ru layer
Ru(0001)+ LEED no no 2.4 ± 0.9 3.3 ± 0.9 complex 0 1.20 ± 0.02; 0 89P2 atomic adsorption in hcp-hollow sites; top 2 Ru
(2x1)-O -0.5 ± 0.9 0; complex 0; 1.27 ± 0.02 layers buckled; bulk-like first and second Ru-Ru
-1.4 ± 0.9 0 interlayer spacings (measured wrt center of mass
of the layers)
Ru(0001)+ LEED no no 3.7 ± 1.9 0.0 ± 0.9 0 0 1.26 ± 0.05; 0 99S1 O and NO in hcp-hollow sites
(2x1)-O+NO: -2.8 ± 1.4 0; 0 0; 1.26 ± 0.05
O at hcp- 0.0 ± 0.9 0
hollow site
Ru(0001)+ LEED no no 3.7 ± 1.9 0.0 ± 0.9 0 0 1.32 ± 0.04; 0 99S1 O and NO in hcp-hollow sites
(2x1)-O+NO: -2.8 ± 1.4 0; 0; 0; 1.32 ± 0.04
NO at hcp- 0.0 ± 0.9 0 0
hollow site
4.1-37
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Ru(0001)+ LEED no no -3.3 ± 0.9 -7.9 ± 0.9; complex 0; 1.73 ± 0.02; 0 94S3 S close to hcp and fcc-hollow sites shifted away
c(4x2)-2S: 0.9 ± 0.9 0 1.56 ± 0.02; from symmetric positions; buckling and lateral
1 S near hcp- -2.0 ± 0.9 0; complex 0; 1.75 ± 0.02 shifts of rows in the first substrate layer;
hollow site -0.5 ± 0.9 0 buckling in the second substrate layer
Ru(0001)+ LEED no no -4.2 ± 2.3 0.5 ± 2.3; 0; 0; 2.15 ± 0.04; 0 95S4 intact molecular adsorption in hcp sites; with
(√7x√7) 1.4 ± 2.3 4.5 ± 9.0 0.0 ± 5.0 2.07 ± 0.04 C3v(σ_v) orientation; i.e. C atoms near top and
R19°-C6H6 bridge sites; no significant buckling in top metal
layer; very strong contraction of first two metal
interlayer spacings; H ignored
Ru(0001)+ LEED no no -4.8 ± 2.3 -0.8 ± 2.3; 0; 0; 2.18 ± 0.05; 0 97S5 intact molecular C6D6 and NO adsorption in hcp
(3x3)- 0.4 ± 2.3 0.0 ± 3.3 -4.6 ± 3.6 2.20 ± 0.05 sites; benzene essentially in C3(σ_d) orientation;
C6H6+2NO: i.e. C atoms in equal positions; no significant
C6H6 at hcp- buckling in top metal layer; H ignored;
hollow site
Ru(0001)+ LEED no no -5.1 ± 2.3 0.0 ± 2.3; 0; 0; 1.33 ± 0.05; 0 97S5 intact molecular C6D6 and NO adsorption in hcp
(3x3)- -0.9 ± 2.3 0.0 ± 3.3 0.0 ± 3.6 1.33 ± 0.05; sites; benzene essentially in C3(σ_d) orientation;
C6H6+2NO: 1 1.31 ± 0.05 i.e. C atoms in equal positions; no significant
NO at one buckling in top metal layer; H ignored;
hcp-hollow
site
Ru(0001)+ LEED no no -4.0 ± 2.3 0.9 ± 2.3; 0; 0; 1.30 ± 0.05; 0 97S5 intact molecular C6D6 and NO adsorption in hcp
(3x3)- 0.0 ± 2.3 2.0 ± 3.3 -1.6 ± 3.6 1.32 ± 0.05; sites; benzene essentially in C3(σ_d) orientation;
C6H6+2NO: 1.32 ± 0.05 i.e. C atoms in equal positions; no significant
1 NO at other buckling in top metal layer; H ignored;
hcp-hollow
site
Ru(0001)+ LEED no no -4.5 ± 1.4 -1.9 ± 1.4; 0; 0; 2.21 ± 0.03; 0 97S5 intact molecular C6D6 and atomic O adsorption
(3x3)- -1.0 ± 1.4 0.6 ± 3.3 0.0 ± 2.6 2.17 ± 0.03 in hcp sites; benzene essentially in C3(σ_v)
C6H6+2O: orientation; i.e. C atoms near top and bridge
C6H6 at hcp- sites; no significant buckling in top metal layer;
hollow site clock rot. possible in top Ru layer; H ignored;
4.1-38
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Ru(0001)+ LEED no no -3.5 ± 1.4 0.9 ± 1.4; 0; 0; 1.38 ± 0.03; 0 97S5 intact molecular C6D6 and atomic O adsorption
(3x3)- -0.9 ± 1.4 -2.0 ± 4.4 3.2 ± 3.6 1.40 ± 0.03; in hcp sites; benzene essentially in C3(σ_v)
C6H6+2O: 1.36 ± 0.03 orientation; i.e. C atoms near top and bridge
1 O at one sites; no significant buckling in top metal layer;
hcp-hollow clock rot. possible in top Ru layer; H ignored;
site
Ru(0001)+ LEED no no -2.6 ± 1.4 1.0 ± 1.4; 0; 0; 1.33 ± 0.03; 0 97S5 intact molecular C6D6 and atomic O adsorption
(3x3)- 2.0 ± 1.4 -1.1 ± 4.4 -2.6 ± 3.6 1.35 ± 0.03; in hcp sites; benzene essentially in C3(σ_v)
C6H6+2O: 1.37 ± 0.03 orientation; i.e. C atoms near top and bridge
1 O at other sites; no significant buckling in top metal layer;
hcp-hollow clock rot. possible in top Ru layer; H ignored;
site
Ru(0001)+ LEED no no 0.4 ± 1.8 0; 0; 0; 1.10 ± 0.05 0 93O2 molecular adsorption in top site on
(√3x√3) 1.6 ± 1.4 0 0 unreconstructed substrate; with buckling in top
R30°-CO substrate layer
Ru(0001)+ LEED no no -4.2 ± 0.9 0; 0; 0; 2.23 ± 0.02 0 94H1 intact molecular adsorption in two different top
(√3x√3) 0.5 ± 0.9; 0; 0; sites (bilayer) on unreconstructed relaxed
R30°-2H2O: 1 -2.8 ± 0.9 0 0 substrate: significant buckling in top metal layer;
H2O at high contraction of first two metal interlayer spacings
top site
Ru(0001)+ LEED no no -1.4 ± 0.9 0; 0; 0; 2.08 ± 0.02 0 94H1 intact molecular adsorption in two different top
(√3x√3) 3.2 ± 0.9; 0; 0; sites (bilayer) on unreconstructed relaxed
R30°-2H2O: 1 2.8 ± 0.9 0 0 substrate: significant buckling in top metal layer;
H2O at low contraction of first two metal interlayer spacings
top site
Ru(0001)+ LEED 0 0 0 0 2.00 ± 0.05 0 94B7 molecular adsorption in on-top site with
(√3x√3) molecular axis perpendicular to unreconstructed
R30°-N2 substrate
4.1-39
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Ru(0001)+ LEED no no -2.8 0 0 0 3.54 ± 0.06 0 97N1 atomic overlayer in on-top sites on
(√3x√3) unreconstructed substrate; with buckling and
R30°-Xe lateral relaxation in the first metal layers
Ru(0001)+ LEED no no 0.0 ± 2.3 0; 0; 0; 3.25 ± 0.08; 0 92O1 atomic adsorption in top sites of unreconstructed
(2x2)-Cs -4.7 ± 1.9 0 0 3.15 ± 0.08 substrate; relaxations in top 2 Ru-Ru interlayer
spacings; buckling in top Ru layer; no
detectable lateral relaxations
Ru(0001)+ LEED no no -7.0 ± 1.9 0; 0; 0; 3.12 ± 0.04; 0 95O2 Cs adsorption in on-top site; pronounced
(2x2)- -8.4 ± 1.9 0 0 2.94 ± 0.04 buckling in top substrate layer; CO in threefold
Cs+CO: Cs at coordinated hcp sites between Cs atoms
top site
Ru(0001)+ LEED no no -7.5 ± 1.9 0; 0; 0; 3.13 ± 0.04; 0 95O2 Cs adsorption in on-top site; pronounced
(2x2)- -8.8 ± 1.9 0 0 2.94 ± 0.04 buckling in top substrate layer; CO in threefold
Cs+2CO: Cs coordinated hcp and fcc sites
at top site
Ru(0001)+ LEED no no 8.3 ± 0.7 0; 0; 0; 1.72 ± 0.05; 0 97S4 intact molecular adsorption in top; hcp and fcc
(2x2)-3NO: 8.4 ± 0.7; -2.9 ± 2.8; ± 3.0 1.90 ± 0.05 sites; upright orientation with the N end down;
1NO at top 0 3.4 ± 2.8 ± 2.3; significant different site-specific inner NO
site 0 bondlengths: NO(top)=1.13;
2.3 ± 1.0 2.3 ± 1.0 -0.6 ± 3.5 -0.8 ± 3.0 NO(hcp/fcc)=1.24/1.22Å; significant buckling
in top metal layer
Ru(0001)+ LEED no no 95N O atoms adsorbed in hcp sites; CO molecules
(2x2)-O+CO: adsorbed in top sites; tilted by 12.6°; relaxations
CO at top site of topmost Ru layer in both lateral and vertical
directions CO tilt could be either vibrational or
static
Ru(0001)+ LEED no no -3.3 ± 0.9 0; 0; 0; 1.98 ± 0.08; 0 94N1 O atoms adsorbed in hcp and fcc sites; forming
(2x2)- -4.2 ± 0.9 0.5 ± 0.5 0 1.89 ± 0.08 honeycomb pattern; CO molecules adsorbed
2O+CO: CO upright in top sites; relaxations in topmost Ru
at top site layer in both lateral and perpendicular directions
4.1-40
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Ru(0001)+ LEED no no -6.1 ± 2.8 0; 0; 0; 1.93 ± 0.06; 0 95O1 coadsorption of atomic oxygen and molecular
(2x2)- -3.3 ± 2.8 0.1 ± 2.8 0 1.86 ± 0.06 dinitrogen on unreconstructed; relaxed substrate;
(O+N2): N2 at oxygen in hcp-hollow site; N2 on top site;
top site perpendicular to surface
Ru(0001)+ LEED no no 4.2 ± 1.9 0; 0; 0; 1.75 ± 0.04; 0 99S1 O and NO in hcp-hollow sites
(2x2)-O+NO: 6.5 ± 1.4 0.0 ± 0.4 0 1.89 ± 0.04
O at top site
Ru(0001)+ LEED no no 5.1 ± 1.4 0; complex 0; 1.76 ± 0.07; 0 99S1 O in fcc and hcp-hollow sites; NO in top site
(2x2)- 3.3 ± 1.4 0 1.89 ± 0.07
2O+NO: NO
at top site
Ru(0001)+ LEED no no 5.6 ± 2.3 0; 0; complex 1.74 ± 0.06; 0 99S1 O in hcp-hollow site; NO in top and fcc-hollow
(2x2)- 5.6 ± 1.4 ± 0.5 1.86 ± 0.06 sites
O+2NO: ± 0.5
1 NO at top
site
adsorption at both fcc-hollow and near-hcp sites
Ru(0001)+ LEED no no 95S3 1 S atom in fcc site; 3 S atoms close to hcp sites;
(√7x√7) shifted away from symmetric positions;
R19°-4S buckling in the first substrate layer correlated
with the number of coordinated S atoms; nearly
identical bond lengths for all S-Ru bonds
adsorption at octahedral interstitial sites within 1st substrate spacing (see Fig. 10)
Ti(0001)+ LEED no no 4.3 ± 2.1 0 0 0 -1.22 ± 0.05; 0 76S2 atomic interstitial in octahedral sites between first
(1x1)-N 1.22 ± 0.05 and second Ti layers; slight expansion of Ti-Ti
spacing; forms trilayer of TiN compound
exposing (111) face
4.1-41
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Zr(0001)+ LEED no no 0.4 ± 1.9 0 0 0 -1.33 ± 0.10; 0 88W1 atomic adsorption in octahedral interstitial sites
(1x1)-C 1.33 ± 0.10 between 1st and 2nd Zr layers; inducing slight
expansion between these Zr layers
Zr(0001)+ LEED no no -0.8 ± 0.9 0 0 0 -1.30 ± 0.05; 0 87W4 atomic adsorption in octahedral interstitial sites
(1x1)-N 1.30 ± 0.05 between 1st and 2nd Zr layers; inducing slight
contraction between these Zr layers
adsorption at tetrahedral sites within 1st substrate spacing (see Fig. 11)
Zr(0001)+ LEED no no 33.7 ± 1.9 0 0 0 -1.22 ± 0.05; 0 97W two O layers are present in the structure; one
(1x1)-2O: 2.22 ± 0.05 forms an overlayer in which the O bonds to 3-
1 O interstitial fold hollow sites on the Zr surface; the other
layer has the O atoms in tetrahedral hole sites
between the first two Zr layers
adsorption at octahedral interstitial sites within 1st and 2nd substrate spacings
Zr(0001)+ LEED no yes 95W1 interstitial O in octahedral sites: 0.25ML O

(2x2)-2O between 1st & 2nd Zr layers; 0.25ML between
2nd & 3rd Zr layers; these two (2x2) O arrays
are displaced laterally from one another by a unit
translational vector of the substrate; lowering the
overall symmetry
adsorption at low-symmetry or mixed sites
Re(0001)+ LEED no no 94B3 sulfur adatoms; adsorbed near 3-fold hcp-hollow

(2√3x2√3) sites; form expanded hexamers crowning one 3-
R30°-6S Re-atom hump per unit cell; alternating S-S
distances in the ring are 3.32Å and 2.95Å;
average first substrate interlayer spacing is 2.21Å
4.1-42
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Ru(0001)+ LEED no no 97N1 multi-site atomic overlayer on unrecon-structed
(3x3)-4Kr substrate; with buckling and lateral relaxation in
the first metal layers: I Kr per cell in hcp or fcc-
hollow site; 3 Kr per cell in lower-symmetry
sites; see comments
Ru(0001)+ LEED no no 98K O atoms occupy 3/4 of hcp-hollow sites; sitting
(2x2)-3O slightly off-hollow; 1st substrate layer is
buckled: Ru atoms bonded to 3 O atoms are
depressed inward relative to those bonded to 2 O
atoms by 0.02 ± 0.03 Å; 2nd substrate layer is
also buckled: Ru atoms below adatom vacancy
are raised by 0.08 ± 0.03 Å over the others
Ru(0001)+ LEED no no 98G2 same as above; but buckling in 1st Ru layer is
(2x2)-3O reversed to -0.03 ± 0.02 Å
Ru(0001)+ LEED no no 98K similar to Ru(0001)+(2x2)-3O: Cs occupies O
(2x2)-Cs+3O vacancy sites; reversing the buckling in the 1st
Ru layer; and reducing the average spacing
between 1st and 2nd Ru layers 0.05 ± 0.03 Å
compared to the O-only case
adsorption at interstitial sites near vacancy sites
Be(0001)+ LEED no yes 99P 1/3 of top-layer Be atoms are missing and each is
(√3x√3) replaced by 3 H atoms in bridge sites around the
R30°-3H vacancy; 1st and 2nd Be-Be spacings are
expanded by 0.6 ± 1.1 and 1.65 ± 1.3 %; resp.
4.1-43
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
adsorption at interstitial sites in lattice reconstructed to fcc
Zr(0001)+ LEED no yes 85H2 O atoms in octahedral holes within fcc

(2x2)-O reconstructed Zr; with layer stacking AcBaCb...
(O atoms in lower case); O atoms form (2x2)
0.25ML interstitial layers
Table 6. Structures of clean bcc(110) surfaces.
nique rec. [Å] [%] [%] [%] [%] [%]
Fe(110) LEED no 2.029 0.5 ± 2.0 0 0 0 0 80S bulk termination with possible slight expansion of
topmost interlayer spacing
K(110) LEED no 3.72 -0.7 ± 0.3 0 0 0 0 92I lateral shear displacement of 0.23Å between top 2
surface layers; preserving the 2-dimensional
periodicity
Mo(110) LEED no 2.227 -1.7 ± 1.8 0 0 0 0 81M bulk termination with contracted top layer spacing
Mo(110) LEED no 2.224 -4.0 ± 0.6 0.2 ± 0.8 0 0 0 97A3 bulk-like terminated surface with moderate inward
relaxation of top layer
Nb(110) HEIS no 2.338 0.0 ± 4.3 0 0 0 0 90W3 bulk terminated structure with no detectable
relaxations
V(110) LEED no 2.141 -0.5 ± 0.5 0 0 0 0 81A slightly contracted bulk termination
W(110) LEED no 2.23 0.0 ± 4.5 0 0 0 0 76V1 unrelaxed bulk termination
W(110) HEIS no 2.23 0.0 ± 1.8 0.0 ± 1.8 0 0 0 87S2 bulk-like termination
W(110) AR- no 2.238 1.0 ± 2.2 0 0 0 0 93K2 unreconstructed surface with small expansion of top
XPD interlayer expansion possible
W(110) LEED no 2.236 -3.1 ± 0.6 0.0 ± 0.9 0.0 ± 1.0 0 0 97A1 bulk-like terminated surface with small inward
relaxation of the top layer
4.1-44
Table 7. Adsorbate-induced structures on bcc(110) surfaces.
Surface Tech- Clean ads- ∆dl,l+1 bls ∆rls αls d01 ∆r0 Ref. Description
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
adsorption at center sites (see Fig. 12)
Cr(110)+ LEED no no 4.7 ± 0.0003 0 0 0 1.837 ± 0 94J1 bcc Cr(110) film grown epitaxially on
(1x1)-0.7ML- 0.0008 Cu(100); film is about 11Å thick; Cr(110) is
Cu overlain with 0.7±0.2 monolayer of
pseudomorphic bcc Cu (with 0.3ML
vacancies); in-plane lattice constant fit to
2.44±0.07Å
W(110)+ XPD no no 1.9 ± 2.2 0 0 0 2.07 ± 0.05 0 97T2 atomic Fe adsorption in center sites (extending
(1x1)-Fe substrate lattice) on unreconstructed substrate
Fe(110)+ LEED no no 81S1 atomic S at center site; top substrate layer
(2x2)-S laterally relaxed
Mo(110)+ LEED no no 94T atomic overlayer near distorted center hollow
(2x2)-S site; i.e. bridging two nearest neighbors but
shifted 0.04Å perp. to bridge toward 3-fold
coordinated hollow site; substantial relaxations
up to 0.3Å in top 2 substrate layers
adsorption at 3-fold coordinated sites (see Fig. 13)
Mo(110)+ LEED no no -2.0 ± 0.4 0 0 0 1.10 ± 0.30 0.14 ± 0.48 97A3 H adsorbed close to quasi threefold
(1x1)-H coordinated site; Mo surface exhibits moderate
contraction of first interlayer distance; deeper
layer distances are bulk-like
W(110)+ LEED no no -1.7 ± 0.5 0 0 0 1.20 ± 0.30 0.19 ± 0.36 97A1 H adsorbed in quasi-threefold coordinated site;
(1x1)-H W surface undergoes no reconstruction upon H
adsorption; only small contraction of first
interlayer spacing
4.1-45
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Fe(110)+ LEED no no 0.0 ± 2.0 -2.0 ± 1.2 0; 0; 1.09 ± 0.20 0.18 ± 0.33 93H1 atomic adsorption in threefold-coordinated
(2x2)-2H 0 0 sites with displacement towards twofold-
1.0 ± 2.9 -1.0 ± 0.8 0; 0; coordinated bridge sites; forming distorted
0 0 honeycomb-like lattice; substrate relaxation of
c(2x2) type: buckling in 1st and 2nd Fe layers
Mo(110)+ LEED no no -3.5 ± 0.7 0.9 ± 0.4; 0; 0; 1.02 ± 0.20 0.23 ± 0.20 97A2 H forms a honeycomb like adlayer occupying
(2x2)-2H 2.7 ± 0.4 0 0 positions close to threefold coordinated hollow
-0.2 ± 0.7 -1.4 ± 0.7; 0; 0; sites; adsorbate induces moderate buckling of
-1.4 ± 0.7 0 0 two topmost Mo layers; contraction of first
interlayer distance
Fe(110)+ LEED -1.0 ± 2.5 0 0 0 0.90 ± 0.10 0.25 85M2 atomic adsorption in 3-fold coordinated hollow
(2x1)-H sites
Fe(110)+ LEED -1.0 ± 2.5 0 0 0 1.00 ± 0.05 0.25 85M2 atomic adsorption in 3-fold coordinated hollow
(3x1)-2H sites; two H per unit cell
nique rec. [Å] [%] [%] [%] [%] [%]
Ag(100) LEED no 2.043 0.0 ± 4.9 0.0 ± 1.5 0 0 0 91L no multilayer relaxation
Al(100) LEED no 2.025 0.0 ± 1.5 0 0 0 0 76V2 unrelaxed bulk termination
Al(100) MEED no 2.022 1.5 ± 4.9 0 0 0 0 83M2 bulk termination with possible slight top contraction
Al(100) LEED no 2.025 2.6 ± 0.2 0.0 ± 0.3 -0.5 ± 0.4 0 0 95B3 unreconstructed surface with multilayer relaxations
Au(100) LEED no 2.04 0.0 ± 4.9 0 0 0 0 82L metastable unreconstructed surface
Au(100)- LEED no 2.04 -1.5 ± 2.0 -2.0 ± 2.0 0 0 0 94W5 impurity-stabilized unreconstructed surface; with
(1x1) possible contraction of top two interlayer spacings
Au(100)- XRD yes 2.04 91O1 incommensurate hexagonal top layer; with 20%
(incommen expanded spacing to 2nd layer (due to variable
surate 'hex') registries); top 4 layers are found corrugated by 14; 7;
3; 1 % (defined as maximum thickness of layer)
Co(100) LEED no 1.77 -4.0 ± 2.8 0 0 0 0 78M bulk termination with top spacing contraction
4.1-46
nique rec. [Å] [%] [%] [%] [%] [%]
Cu(100) LEED no 1.805 -1.1 ± 2.8 1.7 ± 2.8 1.5 ± 2.8 0 0 83D1 bulk termination with multilayer relaxations
Cu(100) LEED no 1.81 -1.7 ± 1.1 1.1 ± 1.1 0 0 0 86A bulk termination with multilayer relaxations
Cu(100) SP- no 1.805 -1.2 ± 1.1 0.9 ± 1.1 0 0 0 87L1 bulk termination with multilayer relaxations
LEED
Cu(100) MEIS no 1.807 -2.4 ± 0.8 1.0 ± 1.0 0 0 0 91J multilayer relaxation
Cu(100) LEED no 1.807 -0.4 ± 5.5 -0.4 ± 5.5 0 0 0 93M3 relaxed bulk termination
Ir(100)- LEED yes 1.92 -3.6 ± 0.5 0 0 0 83H unreconstructed metastable surface with top spacing
(1x1) contraction
Ir(100)- LEED yes 1.92 81V quasi-hexagonal commensurate buckled top-layer
(5x1) reconstruction with 'two-bridges' registry
Ir(100)- LEED yes 1.92 83L quasi-hexagonal commensurate buckled top-layer
(5x1) reconstruction with 'two-bridges' registry
Ni(100) LEED no 1.76 1.1 ± 1.1 0 0 0 0 75D bulk termination with slight top spacing expansion
Ni(100) MEIS no 1.76 -8.9 ± 0.5 0 0 0 0 83F bulk termination with top spacing contraction
Ni(100) LEED no 1.762 -1.1 ± 1.0 0 0 0 0 89O contraction of top interlayer spacing
Ni(100) LEED no 1.762 -1.3 ± 1.0 0 0 0 0 94L2 relaxed; unreconstructed surface
Ni(100) SIMS no 1.762 -4.7 ± 3.4 -1.3 ± 9.1 0 0 0 94X relaxed; unreconstructed surface
Ni(100) LEED no 1.762 0.5 ± 0.6 -0.1 ± 0.6 0 0 0 94N3 unreconstructed relaxed substrate
Pb(100) LEED no 2.463 -8.0 ± 1.2 3.1 ± 1.2 -3.0 ± 1.2 -2.0 ± 4.0 0 90L1 multilayer relaxation
Pd(100) LEED no 1.945 0.3 ± 2.6 0 0 0 0 80B essentially unrelaxed bulk termination
Pd(100) LEED no 1.945 3.1 ± 1.5 -1.0 ± 1.5 0 0 0 90Q multilayer relaxation
Pd(100) LEED no 1.945 4.9 ± 1.5 0.3 ± 0.5 -0.8 ± 1.0 0 0 96B multilayer relaxation
Pt(100)- HEIS no 1.96 0.2 ± 2.6 0 0 0 0 81D unreconstructed metastable structure with slight top
(1x1) spacing expansion
Rh(100) LEED no 1.9 0.5 ± 1.1 0 0 0 0 80H unrelaxed bulk termination
Rh(100) LEED no 1.902 0.5 ± 1.0 0.0 ± 1.5 0 0 0 88O bulk termination with possible slight top interlayer
expansion
Rh(100) LEED no 1.902 -1.2 ± 1.6 0.0 ± 1.6 0 0 0 93B3 bulk termination with slight top interlayer contraction
4.1-47
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
adsorption at hollow sites (see Fig. 14)
Pd(100)+ Transm. no no 0 0 0 0 0.30 ± 0.05 0 88B atomic adsorption in 4-fold hollow site
(1x1)-H (D) Channe
ling
Pt(100)+ LEED yes no 2.0 ± 5.1 0 0 0 1.79 ± 0.10 0 94A partial pseudomorphic monolayer covering
(1x1)-Cu about 50% of unreconstructed substrate;
probably in islands with 1ML; best fit with
mix of 50% bare Pt(100)-(1x1)
Al(100)+ LEED no no 0.35 ± 0.50 0 0 0 2.57 ± 0.01 0 95B3 atomic Na in hollow site on
c(2x2)-Na unreconstructed and essentially unrelaxed
(100K) substrate
Cu(100)+ GIXD no no -5.5 0 0 0 2.18 ± 0.08 0 97M2 atomic adsorption on unreconstructed
c(2x2)-Bi substrate; adatom at fcc-hollow site
Cu(100)+ XSW no no 3.9 ± 2.2 0 0 0 1.53 ± 0.04 0 89P1 atomic adsorption in hollow site with
c(2x2)-Cl expanded top Cu-Cu interlayer spacing
Cu(100)+ AR- no no 11.3 ± 1.2 0 0 0 1.60 ± 0.005 0 91W4 atomic adsorption in hollow site; with
c(2x2)-Cl PEFS 0.5 ± 1.5 0; 0; 0; multilayer relaxation and 2nd Cu layer
2.3 ± 0.7 0 0 buckling
Cu(100)+ LEED no no 2.4 ± 1.7 0 0 0 1.60 ± 0.03 0 83J atomic adsorption in hollow site of
c(2x2)-Cl unreconstructed substrate
Cu(100)+ LEED no no -0.4 ± 2.2 0 0 0 1.96 ± 0.08 0 93M3 Li atoms in fourfold hollow sites
c(2x2)-Li
Cu(100)+ SE- no no 4.4 ± 2.8 0 0 0 0.40 ± 0.05 0 93L2 atomic overlayer in 4-fold hollow sites;
c(2x2)-N XAFS 0 0; 0; 0; outward expansion of first Cu layer;
-5.5 ± 2.8 0 0 possible corrugation of second Cu layer
Cu(100)+ LEED no no 7.9 ± 2.8 0 0 0 0.00 ± 0.05 0 87Z atomic overlayer coplanar with top Cu
c(2x2)-N layer in 4-fold hollow sites
4.1-48
Surface Tech-Clean Ads- ∆dl,l+1 bls ∆rls αls d01 ∆r0 Ref. Description
niquerec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Cu(100)+ LEED no no 7.4 0 0 0 0.06 0 89Z N almost coplanar with 1st Cu layer;
c(2x2)-N 0 0; 0; 0; buckling in 2nd Cu layer (Cu below N
-5.0 0 0 pushed down
Ni(100)+ SE- no no 11.3 ± 2.8 0 0 0 1.60 ± 0.02 0 90Y atomic adsorption at a 4-fold hollow site
c(2x2)-Cl XAFS top Ni layer relaxes outward
XSW
Ni(100)+ SE- no no 2.3 0 0 0 1.55 0 97T1 atomic overlayer in 4-fold hollow sites on
c(2x2)-Cl XAFS unreconstructed substrate; with lateral
relaxations in the first 2 metal layers
Ni(100)+ LEED no no -0.3 0 0 0 1.92 0 97J1 atomic adsorption on unreconstructed
c(2x2)-Li 0.4 0; 0; 0; relaxed substrate; adatom at fourfold
1.5 0 0 hollow site
Ni(100)+ XRD no no -1.7 ± 1.7 0 0 0 0.84 ± 0.70 0 98D2 K removes clock-reconstruction of
c(2x2)-N+ 1.7 ± 1.7 0; 0; 0; Ni(100)+pmg(2x2)-2N
(disord.)-K 3.4 ± 1.7 0 0
Ni(100)+ LEED no no -0.7 ± 0.6 0 0 0 2.38 ± 0.04 0 94N3 atomic adsorption in 4-fold hollow sites of
c(2x2)-Na -0.1 ± 0.6 0; 0; 0; unreconstructed relaxed substrate;
0 0 0 negligible buckling in 2nd Ni layer
-0.9 ± 1.1 0 0 0
Ni(100)+ MEIS no no 5.1 ± 5.7 0 0 0 0.86 ± 0.10 0 83F atomic adsorption in 4-fold hollow sites
c(2x2)-O
Ni(100)+ LEED no no 6.7 ± 1.1 0 0 0 0.77 ± 0.02 0 89O oxygen adsorbed in hollow site; buckling
c(2x2)-O -1.2 ± 1.1 0; 0; 0; in 2nd Ni layer; top Ni-Ni interlayer
-2.0 ± 1.1 0 0 spacing expanded
Ni(100)+ SIMS no no 12.3 ± 3.4 0 0 0 0.85 ± 0.10 0 94X overlayer in hollow sites on relaxed;
c(2x2)-O -14.3 ± 9.1 0; 0; 0; unreconstructed substrate; 2nd Ni layer
-11.3 ± 5.7 0 0 buckled
Ni(100)+ AR- no no 4.0 ± 1.7 0 0 0 1.31 ± 0.03 0 86B atomic adsorption in hollow sites
c(2x2)-S PEFS
4.1-49
niquerec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Ni(100)+ LEED no no 1.9 ± 1.7 0 0 0 1.30 ± 0.02 0 90S2 sulfur in hollow site; expansion of top Ni-
c(2x2)-S -1.5 ± 1.7 0; 0; 0; Ni interlayer spacing; contraction of 2nd
-0.6 ± 1.7 0 0 Ni-Ni spacing; second Ni layer buckled
Ni(100)+ XPD no no 5.7 ± 5.7 0 0 0 1.38 ± 0.10 0 92S1 atomic atomic adsorption in 4-fold hollow
c(2x2)-S sites; with expansion of top Ni-Ni spacing
Pd(100)+ LEED no no 0.2 ± 3.0 0 0 0 2.54 ± 0.02 0 96B atomic adsorption in 4-fold hollow site;
c(2x2)-K 2.1 ± 1.0 0; 0; 0; possible slight buckling in 2nd Pd layer
2.1 ± 1.0 0 0
Pd(100)+ LEED no no 2.6 ± 0.8 0 0 0 1.24 ± 0.02 0 96K1 adsorption of S on fourfold hollow sites;
c(2x2)-S multilayer substrate relaxations
Cu(100)+ XRD no no 0 0 1.6 ± 0.7 0 1.19 ± 0.10 0 90V2 4-fold site; lateral expansion of top Cu
(2x2)-S layer
Cu(100)+ MEIS no no 0 0 1.6 ± 0.7 0 1.30 ± 0.02 0 90J2 S in 4-fold hollow; site laterally expanded;
(2x2)-S no vertical buckling in 2nd Cu layer
Cu(100)+ LEED no no 2.7 ± 2.8 0 0 0 1.28 ± 0.03 0 90Z2 4-fold hollow site for S; lateral expansion
(2x2)-S 1.6 ± 2.8 0; 0; 0; of site; buckling in 2nd layer (atom below
-4.0 ± 2.8; 0; 0; S pushed down)
-4.0 ± 2.8 0 0
Cu(100)+ AR- no no 1.8 0 2.2 0 1.28 ± 0.03 0 92S2 atomic adsorption in 4-fold hollow sites
(2x2)-S PEFS 0 0; 0; 0; with lateral relaxation of the first Cu layer
-0.6; 0; 0; and vertical buckling of the second Cu
-1.8 0 0 layer
Ni(100)+ LEED no no 4.7 ± 1.1 0 0 0 0.80 ± 0.05 0 90O1 oxygen in hollow site; expansion of top
(2x2)-O -3.2 ± 1.1 0; 0; 0; Ni-Ni interlayer spacing; second Ni layer
-2.3 ± 1.1; 0; 0; buckling
-5.7 ± 1.1 0 0
Ni(100)+ SIMS no no 8.4 ± 6.8 0 0 0 0.85 ± 0.10 0 94X overlayer in hollow sites on relaxed;
(2x2)-O -3.2 ± 1.1 0; 0; 0; unreconstructed substrate; 2nd Ni layer
-14.8 ± 6.8; 0; 0; buckled
-14.8 ± 6.8 0 0
4.1-50
niquerec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Ni(100)+ LEED no no 2.7 ± 2.8 0 0 0 1.25 ± 0.03 0 90O2 sulfur in hollow site; 1st Ni-Ni interlayer
(2x2)-S -2.4 ± 2.8 0; 0; 0; spacing expanded; second Ni layer
-4.0 ± 2.8; 0; 0; buckling
-4.0 ± 2.8 0 0
Pd(100)+ LEED no no 6.7 ± 1.0 0 0.0 ± 2.0 0 0.83 ± 0.02 0 96K1 adsorption of O on fourfold hollow sites;
(2x2)-O -3.1 ± 0.8 0; 0; 0; multilayer substrate relaxations; no lateral
-2.6 ± 0.8; 0; 0; relaxations of substrate atoms; significant
-6.2 ± 0.8 0 0 buckling allowed by symmetry
Pd(100)+ LEED no no 6.3 ± 0.8 0 0.0 ± 2.0 0 1.13 ± 0.02 0 96K1 adsorption of S on fourfold hollow sites;
(2x2)-S -1.6 ± 0.8 0; 0; 0; multilayer substrate relaxations; no lateral
-3.1 ± 0.8; 0; 0; relaxations of substrate atoms; significant
-4.2 ± 0.8 0 0 buckling allowed by symmetry
Rh(100)+ LEED no no -0.6 ± 2.1 0 0 0 0.95 ± 0.04 0 88O hollow site adsorption with slight top Rh-
(2x2)-O Rh interlayer contraction
Ni(100)+ LEED no no -4.3 ± 2.3 0 0 0 2.68 ± 0.05 0 93F3 atomic adsorption in hollow sites;
c(4x2)-K 4.3 ± 4.3 0; 0; 0; buckling of 2nd Ni layer; lateral shift in 1st
4.3 ± 4.3 0 0 Ni layer
Rh(100)+ LEED no no -0.6 ± 2.1 0 0 0 2.87 ± 0.06 0 89v2 4-fold symmetric hollow site adsorption
c(4x2)-Cs
Cu(100)+ XRD no no 0.7 ± 1.0 0 0 0 2.10 ± 0.40 0 93M1 disordered fourfold hollow adsorption of
(disordered)- atomic K; with little vertical relaxation of
K 0.18ML top two interlayer spacings and no lateral
displacements
Ni(100)+ LEED no no -2.6 ± 2.3 0 0 0 2.66 ± 0.03 0 93W5 disordered atomic adsorption at K
(disordered)- 2.6 ± 2.6 0; 0; 0; coverages of 0.04,0.08; 0.14,0.17,0.22 and
K 1/4ML 2.6 ± 2.6 0 0 0.25: K in hollow sites; adsorption height:
2.72,2.735,2.675,2.675,2.675 and 2.66Å;
resp.; buckling of 2nd Ni layer: Ni atom
directly below K moves up by
0.075,0.06,0.075,0.060,0.060,0.045Å;
resp.
4.1-51
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
adsorption at off-hollow sites
Ni(100)+ LEED no no 2.3 0 0 0.80 ± 0.03 0.1 83D2 atomic adsorption 0.1Å laterally away
c(2x2)-O from 4-fold hollow site towards bridge site
Rh(100)+ LEED no no 2.3 -0.5 0 0 1.3 0.27 93L4 atomic adsorption in quasi fourfold
c(2x2)-S hollow sites; S atoms shifted towards
bridge sites; relaxation of the first 2 Rh
layers and slight buckling of 2nd Rh layer
Rh(100)+ LEED no no 1.8 0 -3.6 0 1.35 0.27 93L4 atomic adsorption in quasi fourfold
(2x2)-S -0.7 0.0; 0 0 hollow sites; S atoms shifted towards
3.2 bridge sites; relaxation of the first 2 Rh
layers and buckling of 2nd Rh layer;
lateral shift of atoms in 1st Rh layer
Ni(100)+ LEED no no -5.2 ± 2.8 0 0 0 0.86 ± 0.03 0.45 ± 0.10 91S2 disordered hollow site adsorption in off
(disordered)- 4.0 ± 2.8 4.0 ± 2.8 0 0 center position (pseudobridge); 2nd layer
O buckled; sideshift of Ni atoms close to O
of up to 0.15Å possible; local minimum
for 4-fold-site with 1st layer buckling
Ni(100)+ LEED no no -1.3 0 0 0 1.2 0.6 91S2 disordered hollow site adsorption in off
(disordered)-S center position (pseudobridge); 2nd layer
buckled; side shift of Ni atoms close to O
of up to 0.15Å possible; local minimum
for 4-fold-site with 1st layer buckling
admolecules at top sites (see Fig. 15)
Ni(100)+ AR- no no 2.7 ± 1.7 0 0 0 0 2.01 ± 0.03 93Z molecular NH3 adsorbed at top site on
(disordered)- PEFS relaxed substrate; H ignored
NH3
4.1-52
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
adsorption at hollow and other sites
Cu(100)+ LEED no no 86H atomic adsorption (3Pb per supercell) at

c(5√2x√2) and near hollow sites; forming 3-Pb-wide
R45°-3Pb strips (domains) of c(2x2) structure with
compressed domain boundaries; no
buckling in Pb layer or relaxations in
substrate detected
Ni(100)+ LEED no no 97J2 atomic adsorption on unreconstructed
c(5√2x√2) substrate; antiphase boundary structure of
R45°-3Li c(2x2) domains; all Li atoms occupy
hollow sites
Cu(100)+ XRD no no 98M1 domain-wall overlayer structure; inducing
c(9√2x√2) relaxations in substrate
R45°-5Bi
Cu(100)+ LEED no no 94G2 commensurate quasi-hexagonal Mn
c(8x2)-7Mn overlayer: one Mn per cell over hollow site
of unreconstructed substrate; Mn layer
strongly buckled (0.53Å); and slightly
relaxed laterally; top Cu layer slightly
buckled (0.04Å)
adsorption at clock-rotated hollow site
Ni(100)+ LEED no no 3.9 ± 4.5 0 3.2 ± 3.9 ± 14.3 0.12 ± 0.04 0 91G carbon adsorbed in fcc-hollow site;
p4g(2x2)-2C ± 2.6 clockwise rotation of top Ni layer atoms
4.4 ± 4.0 0; 0; 0; around hollow (shift in <010> directions
8.5 ± 4.5 0 0 by 0.45Å); buckling of 2nd Ni layer (Ni
directly below C moves up)
4.1-53
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Ni(100)+ PED no no -2.8 ± 5.7 0 4.8 ± 7.9 ± 17.4 0.10 ± 0.10 0 91K carbon adsorbed in hollow site; clock
p4g(2x2)-2C ± 7.1 rotation of 4 Ni neighbors by 0.55Å;
expansion of top Ni-Ni interlayer spacing
Ni(100)+ PED no no -2.8 ± 5.7 0 4.8 ± 7.9 ± 17.4 0.10 ± 0.10 0 91K N adsorbed in hollow site; clock rotation
p4g(2x2)-2N ± 7.1 of 4 Ni neighbors by 0.55Å; top Ni-Ni
interlayer expansion
Ni(100)+ XRD no no 3.4 ± 4.0 0 2.9 ± 0.1 ± 15.0 0.03 ± 0.13 0 99D N adsorbed in hollow site; clock rotation
p4g(2x2)-2N ± 0.5 of 4 Ni neighbors by 0.30Å; top Ni-Ni
interlayer expansion
adsorption at substitutional sites in top substrate layer (see Fig. 16)
Cu(100)+ LEED no yes 4.0 ± 2.8 0 0 0 0.10 ± 0.05 0 87W2 substitutional adsorption; forming buckled
c(2x2)-Au monolayer of mixed alloy
Cu(100)+ LEED no yes -0.9 ± 1.7 0 0 0 0.30 ± 0.02 0 93W7 ordered mixed Mn-Cu top layer with Mn
c(2x2)-Mn buckled outwards
Cu(100)+ PED no yes -9.7 ± 4.4 0 0 0 0.40 ± 0.04 0 96T1 2-dimensional surface alloy of Mn and
c(2x2)-Mn Cu; Mn replaces every other Cu atom in
outermost layer; Mn buckled outwards
Cu(100)+ LEED no yes 0.0 ± 1.7 0 0 0 0.02 ± 0.03 0 88W2 substitutional adsorption; forming buckled
c(2x2)-Pd monolayer of mixed alloy
Ni(100)+ LEED no yes 0.0 ± 1.7 0 0 0 0.25 ± 0.02 0 93W7 ordered mixed Mn-Ni top layer with Mn
c(2x2)-Mn buckled outwards by 0.25Å; small
relaxations of top 3 interlayer spacings
Ni(100)+ LEIS no yes 0 0 0 0 0.44 ± 0.05 0 94L1 ordered surface alloy with Sn buckled
c(2x2)-Sn above Ni
Pd(100)+ LEED no yes -15.4 ± 2.6 0 0 0 0.20 ± 0.05 0 90T2 mixed top layer; with Mn buckled
c(2x2)-Mn outward
Al(100)+ SE- no yes 2.9 ± 5.5 0 0 0 0.61 ± 0.10 0 92A mixed top Al/Na layer: Na on top sites of
c(2x2)-Na XAFS next Al layer; top-layer Al atoms between
(300K) Na atoms; buckled outward
4.1-54
niquerec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Cu(100)+ GIXD no yes 2.9 ± 5.5 0 0 0 0.61 ± 0.10 0 97M2 adatom at substitutional site; in random
(disordered)- configuration
Bi 0.3ML
adsorption at substitutional sites in 2nd substrate layer
Au(100)+ LEED yes yes 93B4 single (1x1) Fe layer under single Au layer;
(1x1)-Fe+ acting as surfactant
(1x1)-Au
adsorption at hollow sites of missing-row substrate
Cu(100)+ PED no yes 90A missing row reconstruction with O

(2√2x√2) incorporated at kink sites at nearly same
R45°-2O height as 1st Cu layer
Cu(100)+ LEED no yes 90Z1 O in 4-fold coordinated site with 1 Cu
(2√2x√2) neighbor missing; missing Cu row in (1,-
R45°-2O 1) direction; lateral shift of top Cu atoms
adjacent to rows (pairing; 0.3Å) and lifting
up (0.01Å); buckling in 2nd Cu layer
(0.1Å); Cu below O is lifted
Cu(100)+ SE- no yes 93L1 missing-row reconstruction; with O in 4-
(2√2x√2) XAFS fold coordinated sites with 1 Cu neighbor
R45°-2O missing; SEXAFS results consistent with
earlier LEED results on lateral and
perpendicular relaxations in top Cu layer
(Cu expands into missing rows)
4.1-55
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
adsorption at substitutional sites of laterally shifted top substrate layer
Al(100)+ SE- no yes 92A mixed top Al/Na layer: Na on top sites of
c(2x2)-Na XAFS next Al layer; top-layer Al atoms between
(300K) Na atoms; buckled outward by 1.41Å
adsorption in troughs of missing-row reconstruction
Ag(100)- XRD no yes 98M3 every other [110] row in top Ag layer
(2x1)+ missing; with 1st Ag-Ag interlayer
(disordered)- spacing reduced by -3.6 ± 2.4 %; K
K substitute for missing Cu; but 1.17 ± 0.05
Å above remaining top-layer Cu atoms;
in 2nd Ag layer a lateral displacement of
Ag by 0.04 ± 0.003 Å toward K sites is
seen
Cu(100)- LEED no yes 93M2 missing row type reconstruction; Li
(2x1)+ positions unknown
(disordered)-
Li
adsorption in substitutional and near-hollow overlayer sites
Cu(100)+ LEED no yes 95M3 complex reconstruction with overlayer

(3x3)-5Li and substitution: small pyramids of 4 Cu
atoms capped by single Li atoms; the
pyramids being separated and joined by
pairs of substitutional Li atoms
4.1-56
niquerec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Cu(100)+ LEED no yes 95M5 complex reconstruction with overlayer
(4x4)-10Li and substitution: 4 Li adatoms forming a
square cluster located on top of islands of
9 Cu atoms; which islands are separated
and joined by rows of substituting Li
atoms
Ni(100)+ LEED no yes 97J1 four Li adatoms forming a square cluster
(4x4)-10Li located on top of islands of nine Cu atoms;
the islands are separated and joined by
rows of substituting Li atoms
Ni(100)+ LEED no yes 97J1 9 Li adatoms forming a square cluster
(5x5)-17Li located on top of islands of 16 Cu atoms;
the islands are separated and joined by
rows of substituting Li atoms
Al(100)+ XPD; no yes 97F1 formation of mixed Yb-Al top layer by

(√5x√5) LEED substitutional adsorption of Yb; residual
R27°-Yb first-layer Al atoms are strongly displaced
from equilibrium position; also expansion
of first interlayer spacing
Pd(100)+ LEED no yes 94V2 atomic adsorption: PdO oxide monolayer
(√5x√5) with Pd atoms placed on 3 different
R27°-4O adsorption sites: 1 Pd sits on top; 2 Pd on
bridge; 1 Pd on hollow sites per unit cell;
significant expansion in interlayer spacing
and rumpling in the oxide layer
4.1-57
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Cu(100)+ LEED no yes 96G2 Pb chains in [1,-1,0] direction; replacing
c(4x4)-3Pb every other Cu row; 3 Pb per unit cell: 1
Pb substitutional in hollow site; 2 Pb in
intermediate asymmetrical sites;
remaining Cu between Pb chains relaxed;
small corrugation in first pure substrate
layer
Pd(100)+ LEED no yes 97O1 top layer is 100% Pd; 2nd layer is 50% Pd
p4g(2x2)-2Al and 50% Al; 3rd layer and beneath is
100% Pd at ideal fcc positions; clock-
reconstruction in top layer; buckling in
2nd layer (Pd outward)
nique rec. [Å] [%] [%] [%] [%] [%]
Fe(100) LEED no 1.433 -1.6 ± 2.8 0 0 0 0 77L1 bulk termination with contraction of top layer spacing
Fe(100) LEED no 1.433 -4.9 ± 2.1 4.9 ± 2.1 0 0 0 87W1 bulk termination with multilayer relaxation
Fe(100) MEIS no 1.433 -4.5 ± 2.8 3.5 ± 2.8 0 0 0 89H2 bulk termination with multilayer relaxation
Mo(100)- LEED yes 1.574 -11.7 ± 6.4 0 0 0 0 75I2 bulk termination with contraction of top interlayer
(dis- spacing
ordered)
Mo(100)- LEED yes 1.574 -9.5 ± 1.9 -1.0 ± 1.9 0 0 0 80C bulk termination with multilayer relaxation
(dis-
ordered)
Mo(100)- LEED yes 1.575 -5.4 ± 1.3 1.6 ± 1.3 0.3 ± 1.3 0 0 75I2 bulk termination with contraction of top interlayer
(dis- spacing
ordered)
Ta(100) LEED no 1.65 -0.9 ± 1.8 1.2 ± 1.8 0 0 0 82T1 bulk termination with multilayer relaxation
Ta(100) PED no 1.649 -10.0 ± 5.0 0 0 0 0 89B1 contraction of first interlayer spacing
4.1-58
nique rec. [Å] [%] [%] [%] [%] [%]
V(100) LEED no 1.514 -6.9 ± 0.7 1.1 ± 0.7 0 0 0 82J bulk termination with 2-layer relaxation
W(100)- LEED yes 1.58 -6.3 ± 6.3 0 0 0 0 76V1 bulk termination with top layer spacing contraction
(dis-
ordered)
W(100)- LEED yes 1.58 -7.6 ± 1.9 0 0 0 0 80M1 bulk termination with top layer spacing contraction
(dis-
ordered)
W(100)- LEED yes 1.58 -6.3 1.9 0 0 0 88P2 multilayer relaxation
(dis-
ordered)
W(100)- LEED yes 1.58 -9.2 ± 6.3 0 0 0 0 88P1 disordered version of W(100)-c(2x2) reconstruction;
(dis- with top-layer W atoms randomly displaced laterally
ordered) by 0.16Å in 4 equivalent [011] directions
W(100)- LEED yes 1.58 -3.2 ± 3.2 0 0 0 0 78B zig-zag displacive reconstruction of top layer
c(2x2)
W(100)- XRD yes 1.58 -3.8 ± 10.1 0 0 0 0 88A zig-zag chain reconstruction with lateral relaxations in
c(2x2) 1st and 2nd layers
W(100)- LEED yes 1.58 -7.0 ± 1.9 1.3 ± 1.9 0 0 0 89L1 reconstructed zigzag; reconstruction with lateral
c(2x2) displacements
W(100)- LEED yes 1.583 -6.2 ± 1.6 0 0 0 0 92S3 zig-zag chain relaxation with lateral displacements in
c(2x2) 1st layer
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
adsorption at hollow sites (see Fig. 17)
Cr(100)+ LEED no no 28 0 0 0 0.16 0 92J atomic adsorption in 4-fold hollow sites;

(1x1)-N -3.0 0 0 0 with large expansion of top Cr-Cr spacing
4.1-59
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Fe(100)+ MEIS no no 11.2 ± 2.8 0 0 0 0.38 ± 0.04 0 89H2 atomic adsorption in 4-fold hollow sites
(1x1)-O 0.7 ± 2.8 0 0 0 (assumed); with expansion of top 2 Fe-Fe
spacings\
Fe(100)+ LEED no no 7.7 ± 7.0 0 0 0 0.48 ± 0.10 0 77L2 atomic adsorption deep in 4-fold hollow
(1x1)-O sites
Fe(100)+ LEED no no 8.2 ± 2.8 0 0 0 0.45 ± 0.04 0 87J atomic adsorption in 4-fold hollow sites;
(1x1)-O 2.7 ± 2.8 0 0 0 with expansion of top 2 Fe-Fe spacings\
Mo(100)+ LEED yes no 0.0 ± 6.4 0 0 0 1.16 ± 0.10 0 75I1 atomic adsorption in 4-fold hollow sites on
(1x1)-Si unrelaxed substrate
Cr(100)+ LEED no no 11.6 ± 2.8 0 0 0 0.36 ± 0.04 0 98S2 atomic overlayer in bcc-hollow sites on
c(2x2)-N -6.4 ± 2.8 0, 0, 0, unreconstructed substrate; expansion and
-9.0 ± 2.8 0 0 (slight) contraction of top 2 substrate
interlayer spacings; resp.; with buckling in
the second metal layer
Cr(100)+ AR- no no -9.0 ± 1.4 0 0 0 1.17 ± 0.02 0 88T1 atomic adsorption in hollow sites with top
c(2x2)-S PEFS 2.1 ± 2.1 0 0 0 Cr-Cr spacing relaxation (no detectable
-1.4 ± 2.1 0 0 0 layer buckling)
-2.1 ± 4.9 0 0 0
Fe(100)+ LEED no no 0.0 ± 7.0 0 0 0 0.48 ± 0.10 0 78J decomposed CO as atomic C and O
c(2x2)-C+O randomly positioned in hollow sites of a
(chemically c(2x2) lattice; LEED shows c(2x2) (C and
disordered) O indistinguishable)
Fe(100)+ LEED no no 7.7 ± 3.5 0 0 0 0.27 ± 0.05 0 82I atomic adsorption in 4-fold hollows
c(2x2)-N
Fe(100)+ XPD no no 0 0 0 0 1.02 0 97H2 atomic adsorption in hollow sites on
c(2x2)-P unreconstructed unrelaxed substrate
Fe(100)+ LEED no no 0 0 0 0 1.05 ± 0.05 0 77L3 atomic adsorption in hollow sites
c(2x2)-S
Fe(100)+ AR- no no -2.1 ± 1.4 0 0 0 1.10 ± 0.02 0 88Z atomic adsorption in hollow sites with
c(2x2)-S PEFS multilayer relaxation (no detectable layer
buckling)
4.1-60
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Mo(100)+ LEED yes no -6.7 ± 3.2 0 0 0 0.47 ± 0.03 0 95J atomic adsorption in hollow site; with
c(2x2)-C 7.9 ± 2.5 -9.5 ± 2.5 0 0 buckling in 2nd Mo layer; with shortest C-
Mo bond to 2nd Mo layer
Mo(100)+ LEED yes no -1.6 ± 3.8 0 0 0 1.03 ± 0.10 0 95J atomic adsorption in hollow site; with
c(2x2)-S buckling in 2nd Mo layer
-2.9 ± 3.8 -3.1 ± 3.8 0 0
W(100)+ LEED yes no 8.7 ± 3.8 0 0 0 0.41 ± 0.05 0 95B4 atomic adsorption in four fold hollow sites;
c(2x2)-N -9.0 ± 3.8 -17.1 ± 3.8 0 0 second W layer buckled (outward under
adsorbate)
W(100)+ LEIS yes no -0.5 ± 2.5 0 0 0 1.02 ± 0.02 0 94O2 atomic overlayer on undistorted four-fold
c(2x2)-S hollow site; top W-W spacing relaxed to
near bulk value
Mo(100)+ LEED yes no 95J atomic adsorption in quasi hollow site; with
(3√2x√2) buckling and lateral relaxation in the first 2
R45°-2S Mo layers
Mo(100)+ LEED yes no 95J atomic adsorption: 1 S in hollow and 2 S in
c(4x2)-3S quasi hollow sites (at different heights) per
unit cell; buckling in 2nd Mo layer; lateral
relaxations in the first two Mo layers
W(100)+ D- yes no 0.0 ± 6.3 0 -9.6 ± 5.0 0 0.59 ± 0.10 0 86R atomic adsorption in hollow sites with
(disordered)- LEED lateral W relaxations towards O position
O
adsorption at bridge sites (see Fig. 18)
W(100)+ LEED yes no -1.3 ± 12.7 0 0 0 1.17 ± 0.04 0 85P atomic adsorption in bridge sites of both
(1x1)-2H azimuthal orientations (2H per unit cell)
4.1-61
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
interstitial adsorption between two topmost substrate layers (see Fig. 19)
Ta(100)+ LEED yes no 85T atomic O adsorption under bridge in top Ta

(3x1)-O layer and above bridge in second Ta layer
(4-fold coordinated interstitial site); top Ta
layer buckled
adsorption on missing-row reconstructed substrate
W(100)- LEIS yes yes 89M3 missing-row reconstruction of substrate

(2x1)+ oxygen is disordered in 2nd layer top sites
(disordered)-
O
dimerization in top substrate layer
W(100)+ LEED yes yes 92S3 adsorption site of H not determined; dimer
c(2x2)-H reconstruction with lateral displacements in
1st layer; contraction of 1st interlayer spacing
by 4.5%
4.1-62
Table 12. Structures of clean alloyed bcc(100) surfaces.
nique rec. [Å] [%] [%] [%] [%] [%]
Mo75Re25 LEED no 1.564 -11.9 ± 0.6 5.1 ± 0.9 -3.7 ± 0.8 3.9 ± 1.1 -2.5 ± 1.3 96H1 unreconstructed; relaxed surface: strong oscillatory
(100)-(1x1) relaxation of interlayer spacings; top layer is pure
(chem. Mo; oscillatory segregation in deeper layers
disordered
alloy)
Mo85Re15 LEED no 1.567 -11.5 ± 0.6 4.7 ± 0.7 -3.3 ± 0.8 3.2 ± 0.8 -2.1 ± 1.0 97K2 deep multilayer relaxation; layer dependent
(100)-(1x1) stoichiometry: c1(Mo)=100%±15%;
(chem. c2(Mo)=72%±13%; c3(Mo)=90%±13%;
disordered c4(Mo)=88%±16%
alloy)
Mo95Re05 LEED no 1.57 -11.1 ± 0.8 4.4 ± 0.9 -3.0 ± 1.0 2.3 ± 1.0 -1.8 ± 1.1 97K2 deep multilayer relaxation; layer dependent
(100)-(1x1) stoichiometry: c1(Mo)=91%±13%;
(chem. c2(Mo)=85%±16%; c3(Mo)=89%±14%;
disordered c4(Mo)=98%±20%
alloy)
4.1-63
Table 13. Adsorbate-induced structures on alloyed bcc(100) surfaces.
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
adsorption on unreconstructed bcc(100)-like substrate
Mo75Re25(100) LEED no no 96H1 unreconstructed; relaxed substrate: H in all bridge

+ (1x1)-2H sites; oscillating concentration profile of clean surface
(chem. remains due to low adsorption temperature; clean-
disordered surface relaxation of first two interlayer spacings is
alloy) lifted; relaxation of deeper interlayer spacing remains
Mo75Re25(100) LEED no no 96K2 occupation of hollow sites by C atoms; 1st interlayer
+ (1x1)-C spacing similar to MoC(100); c1(Mo)=76%±23%;
(chem. c2(Mo)=66%±22%; c3(Mo)=82%±20%
disordered
alloy)
Mo75Re25(100) LEED no no 96H1 unreconstructed; relaxed substrate: C resides both
+ (1x1)-2C deep in hollow sites of top layer and interstitially in
(chem. octahedral sites below top layer atoms; C causes
disordered expansion of top two interlayer spacings; oscillatory
alloy) layer relaxation below these layers; Mo segregation
in top two layers
adsorption on reconstructed bcc(100)-like substrate
Mo75Re25(100) LEIS no yes 94O1 missing row reconstruction of substrate with O

-(2x1)+ (2x1)- adsorbed on top of second layer substrate atoms;
2O (chem. substrate: disordered alloy with surface segregation:
disordered 1st metal layer Mo concentration >= 0.96; Re
alloy) depletion in 2nd and enrichment in 3rd metal layers;
resp.
4.1-64
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Mo75Re25(100) LEED no yes 95H1 missing row reconstruction; 3-fold coordinated O on
-(2x1)+ (2x1)- sides of remaining rows; Mo segregation toward O-
2O (chem. coordinated sites; expansion of first interlayer
disordered distance by 7.7%
alloy)
nique rec. [Å] [%] [%] [%] [%] [%]
Ag(110) LEED no 1.445 -6.6 ± 1.5 0 0 0 0 82N2 bulk termination with top spacing contraction
Ag(110) HEIS no 1.44 -7.6 ± 2.8 4.2 ± 2.8 0 0 0 84K bulk termination with multilayer relaxation
Ag(110) MEIS no 1.446 -9.5 ± 2.1 6.0 ± 2.8 0 0 0 87H2 relaxations in top two interlayer spacings
Ag(110) LEED no 1.445 -7.4 ± 2.0 0.6 ± 2.0 -2.4 ± 2.0 -0.4 ± 2.0 0 89L4 multilayer relaxations
Ag(110) ICISS no 1.445 1.0 ± 1.5 -4.0 ± 2.0 0 0 0 92B1 multilayer relaxations
Al(110) LEED no 1.428 -10.0 ± 7.0 0 0 0 0 72L bulk termination; with suggested 10% relaxation of top
interlayer spacing
Al(110) LEED no 1.43 -9.1 ± 7.0 0 0 0 0 77G relaxed bulk termination
Al(110) LEED no 1.425 -8.5 ± 0.8 5.2 ± 1.1 0 0 0 84A bulk termination with multilayer relaxation
Al(110) LEED no 1.43 -8.4 ± 1.0 5.6 ± 1.1 2.3 ± 1.3 1.8 ± 1.5 0 84N bulk termination with multilayer relaxation
Au(110)- LEED yes 1.44 85M1 missing-row reconstruction with multilayer relaxation;
(1x2) 2nd row pairing and 3rd row buckling
Au(110)- LEIS yes 1.44 86M missing-row reconstruction with relaxation of top layer
(1x2) spacing
Au(110)- MEIS yes 1.44 86C2 missing-row reconstruction with multilayer relaxation;
(1x2) including 3rd-layer buckling
Au(110)- XRD yes 1.443 90V1 missing-row reconstruction; with multilayer
(1x2) relaxations down to 4th layer
Cu(110) HEIS no 1.278 -5.3 ± 1.6 3.3 ± 1.6 0 0 0 83S bulk termination with multilayer relaxations
Cu(110) LEED no 1.278 -8.4 ± 0.6 2.3 ± 0.8 0 0 0 83A bulk termination with multilayer relaxations
4.1-65
nique rec. [Å] [%] [%] [%] [%] [%]
Cu(110) LEED no 1.276 -9.2 ± 3.9 2.3 ± 3.9 0 0 0 83D1 bulk termination with multilayer relaxations
Cu(110) MEIS no 1.278 -7.5 ± 1.6 2.5 ± 1.6 0 0 0 86C3 bulk termination with multilayer relaxations
Cu(110) ICISS no 1.28 -10.2 ± 7.8 0 0 0 0 86Y2 bulk termination with top layer contractions
Cu(110) LEED no 1.278 -9.4 ± 1.6 4.9 ± 1.6 0 0 0 87B bulk termination with multilayer relaxations
Cu(110) LEIS no 1.278 -3.1 ± 3.1 0 0 0 0 89V1 contraction of the 1st interlayer spacing
Cu(110) XRD no 1.278 -7.8 ± 0.5 1.8 ± 0.5 0 0 0 93H2 unreconstructed surface with relaxations of top 2
interlayer spacings
Ir(110)- LEED yes 1.359 86C1 missing-row reconstruction with multilayer
(1x2) relaxations; row-pairing in second layer and buckling
in third layer
Ir(110)- TOF- yes 1.358 90S1 missing-row reconstruction exposing (111) facets; with
(1x3) SARS relaxations in first 2 layers
Ir(110)- LEIS yes 1.357 92H3 missing-row reconstruction with multilayer relaxations
(1x3)
Ni(110) MEIS no 1.245 -4.0 ± 0.8 0 0 0 0 79V2 bulk termination with top spacing contraction
Ni(110) LEED no 1.245 -8.4 ± 0.8 3.1 ± 1.0 0 0 0 84G1 bulk termination with multilayer relaxations
Ni(110) HEIS no 1.245 -4.1 ± 0.8 0 0 0 0 84T3 bulk termination with top spacing contraction
Ni(110) LEED no 1.245 -9.8 ± 1.6 3.8 ± 1.6 0 0 0 85X1 bulk termination with multilayer relaxations
Ni(110) LEED no 1.245 -8.6 ± 0.5 3.1 ± 0.6 -0.4 ± 0.7 0 0 85A bulk termination with multilayer relaxations
Ni(110) MEIS no 1.246 -9.0 ± 1.0 3.5 ± 1.4 0 0 0 86Y1 bulk termination with multilayer relaxations
Ni(110) LEED no 1.245 -8.4 ± 1.6 3.6 ± 1.6 1.2 ± 1.6 0 0 87R1 bulk termination with multilayer relaxations
Pb(110) MEIS no 1.75 -15.8 ± 2.3 0 0 0 0 86F2 bulk termination with top spacing contraction
Pb(110) LEED no 1.74 -16.4 ± 1.7 3.5 ± 5.7 -4.4 ± 1.7 0 0 89L3 multilayer relaxation down to 3rd interlayer spacing
Pb(110) LEED no 1.75 -19.4 ± 2.9 4.6 ± 4.6 -6.9 ± 2.9 0 0 90B multilayer relaxation down to 3rd interlayer spacing
Pd(110) LEED no 1.37 -5.8 ± 2.9 0.7 ± 2.2 0 0 0 85B1 bulk termination with multilayer relaxation
Pd(110)- LEED no 1.37 -5.1 ± 2.2 0 0 0 0 85B1 alkali-impurity stabilized missing-row reconstruction
(1x2)
Pd(110) LEED no 1.37 -5.1 ± 1.5 2.9 ± 1.5 0 0 0 87S1 relaxations in top two interlayer spacings
Pd(110) LEED no 1.376 -1.0 ± 1.5 5.2 ± 1.5 0 0 0 93W3 unreconstructed surface with multilayer relaxations
Pt(110)- MEIS yes 1.39 88F1 missing-row reconstruction with multilayer relaxation;
(1x2) including 3rd-layer buckling
4.1-66
nique rec. [Å] [%] [%] [%] [%] [%]
Pt(110)- LEED yes 1.39 88F2 missing-row reconstruction with multilayer relaxation;
(1x2) including 2nd- and 4th-layer pairing; and 3rd- and 5th-
layer buckling
Pt(110)- LEED yes 1.387 88S missing-row reconstruction with multilayer relaxation;
(1x2) including 2nd- and 4th-layer pairing and 3rd-layer
buckling
Pt(110)- XRD yes 1.387 90V1 missing-row reconstruction; with multilayer
(1x2) relaxations down to 4th layer
Pt(110)- PED yes 1.387 91H2 missing-row reconstruction; with top spacing
(1x2) contraction
Pt(110)- TOF- yes 1.387 91M1 missing-row reconstruction; with multilayer
(1x2) SARS relaxations down to 3rd layer
Pt(110)- RHEE yes 1.387 92K2 missing-row reconstruction; multilayer relaxation
(1x2) D
Pt(110)- LEED yes 1.39 88F2 (1x3) reconstruction; probably impurity-stabilized;
(1x3) missing-row reconstruction with multilayer relaxation;
including 2nd-layer pairing; and 3rd- and 4th-layer
buckling
Pt(110)- XRD yes 1.387 93R missing-row reconstruction with multilayer relaxation
(1x3)
Pt(110)- TOF- yes 1.387 91M1 2-missing-rows reconstruction; leaving partial low
(1x3) SARS 2nd-layer ridge within 3-wide trough; this structure is
thought to be impurity-stabilized
Rh(110) LEED no 1.34 -0.8 ± 1.5 0 0 0 0 80H relaxed bulk termination
Rh(110) LEED no 1.345 -6.9 ± 1.0 1.9 ± 1.0 0 0 0 87N unreconstructed surface with relaxations of top two
interlayer spacings
Rh(110) LEED no 1.345 -6.7 ± 1.5 2.2 ± 2.2 0 0 0 94B6 unreconstructed substrate with multilayer relaxation
Rh(110)- LEED yes 1.345 93C3 missing-row reconstruction with multilayer relaxation;
(1x2) metastable reconstruction after desorption of O from
Rh(110)-p2mg(2x2)-2O
4.1-67
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
adsorption at center sites of unreconstructed substrate (see Fig. 20)
Cu(110)+ LEED no no -0.6 ± 2.0 0 0 0 1.25 ± 0.03 0 89M1 pseudomorphic Fe monolayer; Fe-Cu and
(1x1)-Fe Cu(1)-Cu(2) interlayer spacings are (within
error bar) equal to Cu-Cu bulk interlayer
spacing
Pd(110)+ LEED no no 6.1 ± 2.2 0 0 0 1.22 ± 0.03 0 93W4 Pt filling troughs of unreconstructed; relaxed
(1x1)-Pt substrate; extending bulk Pd fcc structure
Ni(110)+ LEED no no 10.2 ± 1.6 0 0 0 0.84 ± 0.03 0 85B2 atomic adsorption in hollow (center) site
c(2x2)-S
Ni(110)+ ICISS no no 5.0 ± 3.2 0 0 0 0.89 ± 0.05 0 86F1 atomic adsorption in bulk continuation site
c(2x2)-S (center of rectangle)
Ni(110)+ AR- no no 10.4 ± 1.6 0 0 0 0.82 ± 0.02 0 87R2 atomic adsorption in bulk continuation site
c(2x2)-S PEFS 0 0; 0; 0; (center of rectangle) with buckling in 2nd Ni
10.4 ± 1.6 0 0 layer
Ni(110)+ SE- no no 12.5 ± 3.2 0 0 0 0.83 ± 0.04 0 87W3 atomic adsorption in bulk continuation site
c(2x2)-S XAFS (center of rectangle)
Ni(110)+ MEIS no no 5.2 ± 3.2 0 0 0 0.87 ± 0.03 0 79v2 atomic adsorption in hollow (center) site
c(2x2)-S
Ni(110)+ SE- no no 14.0 ± 2.4 0 0 0 0.77 ± 0.02 0 94Y atomic overlayer in hollow sites of
c(2x2)-S XAFS unreconstructed substrate; with expansion of
top Ni-Ni spacing
Rh(110)+ LEED no no 7.5 0 0 0 0.82 0 94W4 atomic adsorption on relaxed; unreconstructed
c(2x2)-S -3.8 0; -8.3 0; 0; substrate: S on the center hollow site; 2nd
0 0 layer Rh buckled
4.1-68
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
adsorption at 3-fold coordinated sites of unreconstructed substrate (see Fig. 21)
Rh(110)+ LEED no no -1.3 ± 3.7 0 0 0 0.78 ± 0.05 0.92 ± 0.05 91H1 atomic adsorption of hydrogen in 3-fold
(1x1)-2H hollows on either side of Rh ridges; reducing
clean-surface relaxation
Ni(110)+ LEED no no -4.4 ± 1.6 0 0 0 0.41 ± 0.10 0.66 87R1 atomic adsorption in fcc 3-fold hollows on
(2x1)-2H 5.2 ± 1.6 0 0 0 (111) facets of unreconstructed substrate with
multilayer relaxations perp. to surface
Pd(110)+ LEED no no -2.2 ± 1.5 0 0 0 0.60 ± 0.10 0.46 ± 0.30 87S1 atomic adsorption over outermost 3-fold
(2x1)-2H 2.9 ± 1.5 0 0 0 coord. hollow sites over (111) facets of bulk-
like substrate with interlayer spacing
relaxations
Rh(110)+ LEED no no 1.1 ± 4.5 0 0 0 0.60 ± 0.05 0.58 ± 0.10 93G1 atomic O (2 per (2x1) unit cell) in
(2x1)-2O 2.6 ± 5.2 0 0 0 asymmetrical 3-fold coordinated sites;
forming zigzag chains within troughs of
slightly relaxed substrate
Rh(110)+ LEED no no -1.1 ± 3.0 0 0 0 0.60 ± 0.04 0.77 ± 0.10 95B2 O in fcc 3-fold hollow site on facets of
(2x1)-2O 2.6 ± 5.2 0; 0; 0; unreconstructed substrate; with multilayer
0 ± 0.05; 0 relaxation; incl. lateral relaxation in 2nd Rh
± 0.07 layer
Rh(110)+ LEED no no -2.5 ± 2.0 3.0 ± 0.7 0.007 ± 0 0.80 ± 0.10 1.04 ± 0.10 89P3 atomic adsorption in nearly 3-fold sites on
(1x2)-H 0.03 (111) facets on side of troughs (with long H-
Rh distance to 2nd-Rh-layer atoms); top-Rh-
rows to which H is bonded are buckled out
and laterally shifted towards H ('shift-
buckling')
4.1-69
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Rh(110)+ LEED no no -1.6 ± 1.0 2.2 ± 1.5 0 0 0.71 ± 0.10; 0.55 ± 0.20; 89M2 atomic adsorption of hydrogen with top layer
(1x2)-3H 1.00 ± 0.10; 1.22 ± 0.20; relaxation (slight buckling of doubly occupied
1.15 ± 0.10 1.66 ± 0.20 Rh atoms); all H in 3 inequivalent quasi-3-fold
sites in sides of troughs of unreconstructed
substrate
Rh(110)+ LEED no no -4.1 ± 1.5 2.2 ± 1.5 0.04 ± 0.03 0 0.51 ± 0.10 0.70 ± 0.20 89L2 atomic adsorption of H in 3-fold sites on side
(1x3)-H 1.1 ± 1.5 0 0 0 of troughs; slight buckling of top layer
adsorption at outermost 3-fold sites and bottom long-bridge sites in trough (see Fig. 21 and 22)
Rh(110)+ LEED no no 0.7 ± 3.7 0 0 0 0.57 ± 0.04 -0.57 ± 0.10 95G1 substrate reconstruction with missing rows
c(4x2)-N+2O: parallel to ridges; atomic adsorption in
O at 3-fold outermost 3-fold coordinated fcc-hollow sites
sites on the flanks of the ridges; N in long-bridge
sites at bottom of troughs; buckling in 3rd
substrate layer
Rh(110)+ LEED no no 0.7 ± 3.7 0 0 0 -1.23 ± 0.05 0 95G1 substrate reconstruction with missing rows
c(4x2)-N+2O: parallel to ridges; atomic adsorption in
N at long- outermost 3-fold coordinated fcc-hollow sites
bridge site on the flanks of the ridges; N in long-bridge
sites at bottom of troughs; buckling in 3rd
substrate layer
adsorption at short-bridge sites of unreconstructed substrate (see Fig. 23)
Ir(110)+ LEED yes no -2.2 ± 5.1 0 0 0 1.37 ± 0.05 0 78C atomic adsorption in short-bridge site on
c(2x2)-O unreconstructed substrate with top Ir-Ir layer
spacing contraction
4.1-70
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
adsorption at multiple sites
Rh(110)+ LEED no no 95W2 atomic adsorption on relaxed; unreconstructed

(3x2)-4S substrate: 1 S at center,1 S at long-bridge; 2 S
at off-center sites; off-center site S shift by
0.39Å from center; 1st-layer Rh atoms
forming the long-bridge site are buckled
outward by 0.20Å and laterally shift by 0.27Å
to open up the site
admolecules near top or short-bridge sites over ridges of unreconstructed substrate (see Figs. 23 and 24)
Cu(110)+ PED no no -11.0 ± 4.7 0; 0; 0; 1.87 ± 0.02 0 95H3 CO occupies atop sites on unreconstructed
(2x1)-CO -11.0 ± 4.7 0 0 substrate; small buckling of top Cu layer
Ni(110)+ AR- no no 1.9 ± 1.6 0 0 0 1.43 ± 0.02 0 93H4 molecular CO adsorption near bridge site of
(2x1)-2CO PEFS unreconstructed; perhaps slightly relaxed;
substrate; with C-O axis tilted 19° from surface
normal
Ni(110)+ LEED no no 0.0 ± 4.0 0 0 0 1.29 ± 0.06 0 94Z CO molecules tilted in alternate directions
(2x1)-2CO along the short bridge rows; 20° tilt of whole
molecule
Rh(110)+ LEED no no 1.9 ± 3.7 0 0 0 1.41 ± 0.05 0 94B6 CO near bridge site adsorption on ridges of
(2x1)-2CO unreconstructed substrate; C-O axis tilted 24°
from surface normal in zigzag fashion;
multilayer relaxation in substrate
Cu(110)+ PED no no -2.3 ± 3.1 0 0 0 1.90 ± 0.04 0 92W2 CH3COO (acetate) adsorption; with both O
(disordered)- down; O are approx. atop so molecule bridges
CH3COO 2 Cu atoms; C-C axis and molecular plane
perp. to surface; H atom sites in methyl group
not determined
4.1-71
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Cu(110)+ PED no no -2.3 ± 3.1 0 0 0 1.90 ± 0.04 0 92W2 CF3COO (trifluoro-acetate) adsorption; both O
(disordered)- down; O approx. atop so molecule bridges
CF3COO 2 Cu atoms; C-C axis and molecular plane
perp. to surface; F atom sites in fluoro-methyl
group not determined
Cu(110)+ PED no no 0.0 ± 5.5 0; 0; 0; 1.33 ± 0.02 0 96H3 disordered overlayer of NH2 or NH in short
(disordered)- -5.5 ± 5.5 0 0 bridge sites of unreconstructed relaxed
NHx substrate
(x=2 or 1)
admolecules at center sites (see Fig. 20)
Ni(110)+ NE- no no 98B1 unreconstructed; relaxed substrate with CN

c(2x2)-CN XAFS lying perpendicular to troughs across center site
PD of rectangular hollow; N higher than C
adsorption at long-bridge sites on cross-ridge missing/added-rows substrate
Ag(110)+ ICISS no yes 14.9 ± 3.5 0 0.08 ± 0.05 0 -0.03 ± 0.05 0 93C1 added row reconstruction with multilayer
(2x1)-O relaxation; O in long bridge site
Cu(110)+ ICISS no yes 25.2 ± 15.6 0 0 0 -0.60 0 86Y2 atomic adsorption in long-bridge sites (O
(2x1)-O below top Cu layer); with missing Cu [001]
rows
Cu(110)+ XRD no yes 29.0 ± 3.9 0 0.03 ± 0.05 0 -0.34 ± 0.20 0 90F1 atomic adsorption in long bridge sites with
(2x1)-O missing-row reconstruction and slight second-
row pairing away from O sites
Cu(110)+ LEED no yes 16.6 ± 3.9 0 0.03 ± 0.05 0 0.04 ± 0.05 0 90P1 atomic adsorption in long bridge sites with
(2x1)-O missing-row reconstruction and slight second-
row pairing away from O sites
4.1-72
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Cu(110)+ ICISS no yes 18.2 ± 11.7 0 0.12 ± 0.07 0 -0.08 ± 0.20 0 91D2 O in long bridge sites with missing row
(2x1)-O reconstruction; row pairing (away from O) of
second Cu layer
Cu(110)+ LEIS no yes 0 0 0 0 -0.05 ± 0.06 0 93D2 added-row reconstruction with O in long
(2x1)-O bridge site
Ni(110)+ LEED no yes 20.4 0 0 0 0.2 0.1 ± 0.1 90K missing-row structure in which the O atoms
(2x1)-O are above long bridge sites in [001] direction
with slight asymmetry; top 2 Ni layers have an
expanded separation while the 2nd and 3rd
have a contracted separation; the 3rd layer is
slightly buckled
Rh(110)+ LEED no yes -1.5 ± 5.9 0 0.0 ± 0.14 0 0.0 ± 0.08 0 95D2 missing/added row reconstruction; with N
(2x1)-N atoms in long bridge sites
Rh(110)+ LEED no yes -3.7 ± 3.7 0 0.0 ± 0.05 0 0.09 ± 0.04 0 95G1 added-row reconstruction across ridges; N in
(2x1)-N long-bridge positions forming Rh-N-Rh
chains; buckling in 3rd substrate layer
adsorption on missing-row/added-rows substrate along ridge; at outermost 3-fold sites
Ir(110)-(1x2)+ LEED yes yes -3.3 ± 7.4 0 0 0 0.94 ± 0.10 -0.20 87C1 missing-row structure of substrate; atomic S
(2x2)-2S over outermost 3-fold fcc-hollow sites in zig-
zag arrangement (2 per cell); bonding to two
top-layer Ir atoms and one second-layer Ir
atom
adsorption on missing-row/added-rows substrate along ridge; at middle 3-fold sites
Ni(110)+ TOF- no yes 0 0 0 0 0.21 -0.40 ± 0.12 92B2 atomic H resides at the pseudo-three-fold sites;
(1x2)-2H SARS Ni substrate is (1x2) missing-row reconstructed
4.1-73
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
adsorption on missing-row/added-rows substrate at in-trough hollow site
Cu(110)- PED no yes 2.4 ± 6.3 0 0 0 1.02 ± 0.04 0 94H4 (1x2) missing row reconstruction induced by K
(1x2)+ adsorption; K coverage < 0.5; so not ordered
(disordered)- overlayer; K atoms occupy 4-fold coordinated
K hollows at bottom of missing-row troughs
adsorption at substitutional sites in top layer (see Fig. 25)
Au(110)+ MEIS yes yes -13.0 ± 3.0 0 0 0 1.05 ± 0.20 0 89H1 mixed Au/K top layer; inducing spacing
c(2x2)-K relaxations and buckling in deeper Au layers
Cu(110)+ LEED no yes -5.7 ± 1.6 0 0 0 0.22 ± 0.05 0 98R almost perfectly ordered mixed Mn-Cu top
c(2x2)-Mn layer: 87% Mn on site 1; 94% Cu on site 2; no
Mn diffusion into 2nd and deeper layers;
buckling in top layer; relaxation of top 3 layers
row-pairing reconstruction in top substrate layer
Pd(110)+ LEED no yes -11.0 ± 2.2 0 ± 0.20 0 0 0 87K H-induced row pairing reconstruction (H
(1x2)-H ± 0.02 positions not determined)
Cu(110)+ XRD no yes 93B1 N-induced reconstruction of top Cu layer to

(2x3)-4N form nearly square buckled lattice of higher
density; N deep in 4-fold hollow sites of this
layer; forming 'c(2x2)' superlattice wrt it; 2nd
through 4th Cu layers slightly buckled
4.1-74
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Cu(110)+ LEED no yes 94V1 N-induced reconstruction of top Cu layer to
(2x3)-4N form nearly square buckled lattice of higher
density; N deep in 4-fold hollow sites of this
layer; forming 'c(2x2)' superlattice wrt it; 2nd
Cu layer slightly buckled
Cu(110)+ LEED no yes 97M4 buckled pseudo-(100) surface reconstruction of
(2x3)-3N topmost layer; which has 3 N and 6 Cu atoms
per (3x2) unit cell; N atoms occupy 4-fold
coordinated hollows; outermost N site
occupation only 30%; the following 4
substrate layers are also buckled
Ni(110)+ SE- no yes 94W2 reconstruction with inserted Ni row in [1-10]
(2x3)-3N XAFS direction; forming buckled top Ni layer with
quasi-square lattice; 1 N atom in hollow sites
slightly above deepest buckled Ni atoms and 2
N atoms below hollow site of inclined Ni
square (interstitial site between top 2 Ni layers)
Ni(110)+ XRD no yes 93F2 missing-row-pair reconstruction; S adsorbed at
(4x1)-3S hollow sites on remaining-Ni-row pairs; and
near hollow sites substituting for missing Ni
rows; buckling of top Ni layers
Ag(110)+ LEIS no yes 93D1 substrate reconstruction with missing rows and
c(6x2)-4O overlayer Ni atoms; O adatoms between
overlayer-Ni and next-layer Ni; and within
next inter-Ni spacing
Cu(110)+ LEIS no yes 93D2 substrate reconstruction with missing rows and
c(6x2)-4O overlayer Cu atoms; O adatoms between
overlayer-Cu and next-layer Cu; and within
next inter-Cu spacing
4.1-75
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Cu(110)+ LEED no yes 95L2 atomic adsorption on reconstructed substrate:
c(6x2)-4O two types of O; each bonded with 4 Cu; this
structure is composed of double-stranded Cu-O
chains and is similar to a modified (211) plane
of bulk Cu2O; the basic building blocks are O-
Cu-O 3-atom rods
Cu(110)+ LEED no yes 96L2 each P occupies an identical 6-coordinate site
(2,2|-1,1)-2P created by the reconstructed Cu(110); which
itself corresponds to a quarter ML of added Cu
atoms at hollow sites; each bonding to 2 P
atoms and 5 other bulk-like Cu atoms
Cu(110)+ GIXD no yes 96L3 combination of Bi overlayer in troughs and
(4x1)-3Bi substitution of every fourth Cu row in the [001]
direction of the topmost Cu layer by Bi atoms
Cu(110)- LEED no yes 97M3 every 4th Cu row in the [001] direction (perp.
(4x1)-3Li to troughs) is substituted by Li atoms;
remaining Cu rows are covered by 2 Li
adatoms per unit cell
Table 16. Structures of clean hcp(10-10) surfaces.
nique rec. [Å] [%] [%] [%] [%] [%]
Be(10-10) LEED no 1.319; -25.0 5.1 -11.0 2.0 0 96H4 relaxed bulk with lower-corrugation termination (of
2.637 two possible terminations for a (10-10) hcp surface)
Co(10-10) LEED no 1.45; -6.5 ± 2.0 1.0 ± 2.0 0.0 ± 4.0 0 0 90L2 relaxed bulk with lower-corrugation termination (of
2.9 two possible terminations for a (10-10) hcp surface) and
multilayer relaxations
Co(10-10) LEED no 1.436; -13.0 ± 0.4 3.0 ± 0.2 0.5 ± 0.6 0 0 91O2 relaxed bulk with lower-corrugation termination (of
2.872 two possible terminations for a (10-10) hcp surface) and
multilayer relaxations
4.1-76
nique rec. [Å] [%] [%] [%] [%] [%]
Re(10-10) LEED no 2.4; -16.2 ± 12.6 2.0 ± 4.2 0 0 0 80D bulk termination with top interlayer spacing
4.8 contraction; second interlayer spacing may be
expanded; termination between widely spaced layers
Ti(10-10) LEED no 2.555; -4.3 ± 6.0 4.7 ± 3.0 0 0 0 90W1 70% of surface bulk terminated with narrow top
5.11 interlayer spacing (d12) contracted about 5%; second
interlayer spacing (d23) expanded about 1-2%; 30%
of surface bulk terminated with expanded (+6%) large
(d23) interlayer spacing
Table 17. Adsorbate-induced structures on hcp(10-10) surfaces.
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
adsorption at center site (see Fig. 26)
Co(10-10)+ LEED no no -5.3 ± 14.0 0 0 0 2.44 ± 0.10 0 91B atomic adsorption at 4-fold hollow of bulk terminated
c(2x2)-K structure of lower corrugation
adsorption in 3-fold hollow sites on sides of troughs; relaxations given relative to center sites (see Fig. 27)
Co(10-10)+ LEED no no 25.4 ± 4.2 0 0 0 0.74 ± 0.05 0.97 ± 0.41 97G4 relaxed bulk with lower-corrugation termination (of
(2x1)-2O -3.2 ± 3.5 0 0 0 two possible terminations for a (10-10) hcp surface);
oxygen forms zigzag chains; in hcp-hollow sites on
sides of Co ridges
Ru(10-10)+ LEED no no 3.7 ± 1.3 0 0 0 0.96 ± 0.02 1.13 ± 0.05 98S1 relaxed bulk with lower-corrugation termination (of
(2x1)-2O -2.1 ± 1.3 0 0 0 two possible terminations for a (10-10) hcp surface);
oxygen forms zigzag chains; in hcp-hollow sites on
sides of Ru ridges
4.1-77
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
Ru(10-10)+ LEED no no -4.0 ± 5.0; 0; 2.0 ± 3.0; complex 1.02 ± 0.03 0.95 ± 0.06 98S1 relaxed bulk with lower-corrugation termination (of
c(2x4)-2O -7.8 ± 5.0; 0; 0; two possible terminations for a (10-10) hcp surface);
-1.4 ± 5.0 0 0 oxygen forms zigzag chains; in hcp-hollow sites on
-1.4 ± 1.3 -3.8 ± 5.0; 0; 0.01 ± 0.03; sides of alternate Ru ridges
2.6 ± 5.0 0 0
adsorption at short-bridge sites and 3-fold hollow sites in sides of troughs (see Fig.s 27 and 28)
Re(10-10)+ LEED no no 98D1 little change in top two Ru-Ru interlayer spacings;
c(2x2)-3H but contraction by 0.09 Å of third spacing; Re atoms
of short-bridge site are possibly displaced laterally
toward site by 0.02 Å
Ru(10-10)+ LEED no no 98D1 little change in top two Re-Re interlayer spacings; but
c(2x2)-3H contraction by 0.05 Å of third spacing; Re atoms of
short-bridge site are possibly displaced laterally
toward site by 0.02 Å
nique rec. [Å] [%] [%] [%] [%] [%]
Fe(211) LEED no 1.17 -10.4 ± 2.6 5.0 ± 2.6 -1.8 ± 3.4 0 0 84S bulk termination with multilayer relaxation
perpendicular and parallel to surface
W(211) TOF- no 1.29 -9.4 ± 5.4 -0.2 ± 5.4 0 0 0 89R bulk termination with registry shift by 6.0%; relative to
SARS bulk
4.1-78
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
adsorption at 3-fold coordinated sites of unreconstructed substrate
W(211)+ TOF- no no 89B3 atomic O in three out of four 3-fold coordinated sites
(1x2)-3O SARS on an unrelaxed and unreconstructed W substrate; as
found consistent with experimental data
adsorption on close-packed missing-row reconstruction
Fe(211)+ LEED no yes 95H3 hydrogen induced missing row reconstruction of

(1x2)-2H Fe(211); removal of close-packed rows in top layer;
row pairing in 2nd layer and buckling in 3rd layer;
adsorption site of H not determined
adsorption on non-close-packed missing-row reconstruction
Fe(211)+ LEED no yes 86S1 atomic adsorption in long-bridge sites; forming -Fe-
(2x1)-O O-Fe-O- strings perpendicular to clean-surface
ridges; in which half the Fe atoms are missing
('missing-row' model)
4.1-79
nique rec. [Å] [%] [%] [%] [%] [%]
Fe(111) LEED no 0.827 -15.4 ± 3.6 0 0 0 0 81S2 bulk termination with top spacing contraction
Fe(111) LEED no 0.827 -16.6 ± 3.0 -9.3 ± 3.0 4.0 ± 3.6 -2.1 ± 3.6 0 86S2 bulk termination with multilayer relaxation
perpendicular to surface
Mo(111) LEIS no 0.909 -18.0 ± 2.0 4.0 ± 4.0 0 0 0 86O bulk termination with multilayer relaxation
perpendicular. to surface
Mo(111) LEED no 0.907 -18.8 ± 2.0 -18.9 6.4 2.2 0 99A bulk termination with multilayer relaxation
perpendicular to surface
nique rec. ind [%] [%] [%] [°] [Å] [Å]
rec.
adsorption at asymmetrical sites
Mo(111)+ LEED no no -17.4 ± 1.5 0 0 0 0.03 ± 0.51 0 99A H adsorbs in triplets around each deep hollow site;
(1x1)-3H inducing little change in 1st Mo-Mo spacing; but
large derelaxation of 2nd Mo-Mo spacing to near
bulk value
4.1-80
Table 22. Structures of clean Si; Ge and C(111) surfaces. Here; dbulk gives the spacing between the pairs of bilayers in the bulk.
Surface Tech- Clean dbulk d12 ω Ref. description

nique rec. [Å] [%] (°)
Si(111)-(1x1) LEED no 2.35 - - 86J unreconstructed bulk termination with multilayer relaxations perpendicular to surface
(laser
annealed)
Si(111)-(2x1) LEED yes 2.35 - - 84H1 tilted π-bonded chain model with overall compression
Si(111)-(2x1) MEIS yes 2.35 - - 85S tilted π-bonded chain model; with tilt in lower chain in same direction as tilt in upper chain
Si(111)-(2x1) LEED yes 2.35 - - 86S3 tilted π-bonded chain model with relaxations down to 4th bilayer
Si(111)-(7x7) LEED yes 2.35 - - 88T2 optimized DAS (dimer-adatom-stacking fault) model
Ge(111)- LEED yes 2.45 - - 90T3 2 adatoms A and B in the top layer in T4 sites with identical local environments; relaxations
c(8x2) found in the top 5 Ge layers (adatoms + 2 bilayers)
Table 23. Adsorbate-induced structures on Si; Ge and C (111) surfaces. Here; d01 is the local adsorbate height; while ∆d12 is the relative first bilayer spacing change.
Surface Tech- Clean Ads- d01 ∆d12 ω Ref. Description

nique rec. ind [Å] [%] [°]
rec.
adsorption at unknown sites
Ge(111)+ LEED yes no - 0 87I atomic adsorption stabilizing unreconstructed substrate with relaxed top two interlayer
(1x1)-H spacings (H position not determined)
Si(111)+ MEIS yes no - -2 ± 2 94N4 unreconstructed; nearly unrelaxed ideal bulk Si termination (H position not determined)
(1x1)-H
adsorption at T4 sites (see Fig. 29)
Ge(111)+ LEED yes no 1.32 1 91W2 atomic adsorption of Bi in T4 site (3-fold hollow above 2nd Ge layer) on
(√3x√3) unreconstructed; relaxed substrate
R30°-Bi
4.1-81
rec.
Ge(111)+ LEED yes no 1.7 1 89H3 α structure: atomic adsorption of Pb in T4 sites on unreconstructed; relaxed substrate:
(√3x√3) buckling of second and third Ge monolayers (first is planar)
R30°-Pb
(1/3ML)
Si(111)+ LEED yes no 1.39 -22 90H2 Al adsorbed at T4 site; the three 1st-layer Si atoms are moved radially inwards and up;
(√3x√3) the Si below the T4 site is moved down; pushing the Si right below it downwards; other
R30°-Al 2nd- and 3rd-layer Si atoms below them are moved upwards
Si(111)+ LEED yes no 1.38 -22 92N Al at T4 site on unreconstructed; relaxed substrate; 1st-layer Si atoms are moved
(√3x√3) radially inwards and up; the Si below the T4 site is moved down; pushing the Si right
R30°-Al below it downwards; other 2nd- and 3rd-layer Si atoms below them are moved upwards
Si(111)+ RH- yes no 1.42 ± 0.06 -15 95H2 atomic adsorption in 4-fold coordinated T4 site; large rumpling in 2nd and 3rd layers of
(√3x√3) EED substrate
R30°-Al
Si(111)+ PD yes no 1.30 ± 0.20 - 99S2 Al at T4 site on unreconstructed; relaxed substrate; 1st-layer Si atoms are moved
(√3x√3) radially inwards
R30°-Al
Si(111)+ LEED yes no 1.11 -14 92W1 Bi centered at T4 site; nearest Si neighbors squeezed together; Si atom directly below
(√3x√3) Bi and third layer Si atom directly below pushed downwards; second-layer Si atoms
R30°-Bi surrounding the hollow H3 site are moved upwards
Si(111)+ MEIS yes no 1.45 -23 92C Ga centered at T4 site on unreconstructed; relaxed substrate; nearest Si atoms squeezed
(√3x√3) together; two Si atoms directly below Ga pushed downwards; 2nd-layer Si atoms
R30°-Ga surrounding the hollow H3 site are moved upwards
Si(111)+ RH- yes no 1.51 ± 0.06 3±2 95H2 atomic adsorption in 4-fold coordinated T4 site; large rumpling in 2nd and 3rd layers of
R30°-Ga
Si(111)+ LEED yes no 1.35 -24 88K atomic adsorption in 4-fold coordinated T4 'top' site over top bilayer; with relaxations
(√3x√3) down into 2nd bilayer
R30°-Ga
Si(111)+ XRD yes no 1.85 ± 0.05 -15 ± 3 93F1 Ga centered at T4 site on unreconstructed; relaxed substrate; nearest Si atoms squeezed
(√3x√3) together; two Si atoms directly below Ga pushed downwards; 2nd-layer Si atoms
R30°-In surrounding the hollow H3 site are moved upwards
4.1-82
rec.
Si(111)+ SE- yes no 2.10 ± 0.06 0±2 93W6 In at T4 site on unreconstructed substrate with no appreciable surface relaxations within
(√3x√3) XAFS about 0.25Å
R30°-In XSW
Si(111)+ RH- yes no 1.83 ± 0.06 -13 ± 3 95H2 atomic adsorption in 4-fold coordinated T4 site; large rumpling in 2nd and 3rd layers of
R30°-In
Si(111)+ PD yes no 1.70 ± 0.10 - 99S2 In at T4 site on unreconstructed; relaxed substrate; 1st-layer Si atoms are moved radially
(√3x√3) inwards
R30°-In
Si(111)+ LEED yes no 1.43 ± 0.05 -6 ± 2 91D1 atomic adsorption above T4 site; the three first-layer Si atoms are moved in as well as
(√3x√3) up; the Si right below Pb is moved down together with the Si atom below it; all the
R30°-Pb (β other Si's in the 2nd; 3rd; and 4th Si layers are moved upwards; the 5th Si layer and
phase) below are in bulk positions
Si(111)+ XRD yes no 1.59 ± 0.3 -25 89C atomic adsorption at T4 site; the three first-layer Si's are moved radially inwards; the Si
(√3x√3) below the T4 site is moved down; pushing the Si right below it downwards; other
R30°-Sn second-layer Si's and third-layer Si's below them are moved upwards; layers 4; 5; and 6
are laterally moved
Ge(111)+ XRD yes no 2.62 ± 0.03 3±3 92V Sb forms 6° tilted zig-zag chains; saturating the dangling bonds of the unreconstructed;
(2x1)-2Sb relaxed; full-bilayer-terminated substrate by slightly off-top adsorption
C(111)+ MEIS yes no - 0 86D unreconstructed bulk diamond termination between bilayers; probably stabilized by H;
(1x1)-H with minor C-C spacing contraction in top bilayer (H positions not determined; but
(diamond) probably terminate dangling bonds)
Ge(111)+ SE- yes no 2.07 ± 0.03 0 83C atomic adsorption in top sites on unrelaxed unreconstructed substrate
(1x1)-Cl XAFS
Ge(111)+ SE- yes no 2.50 ± 0.04 0 89B2 atomic adsorption of I in top sites on unreconstructed; relaxed substrate: first substrate
(1x1)-I XAFS interlayer spacing contracted by 10%
XSW
Ge(111)+ AR- yes no 2.26 ± 0.04 8 90T1 adsorption of partially dissociated PH3 in tilted top sites on unreconstructed; relaxed
(1x1)-PHx PEFS substrate; first Ge-Ge interlayer spacing contracted by 16%
4.1-83
rec.
Si(111)+ XSW yes no 2.56 0 87D2 atomic adsorption in 1-fold coordinated top sites over unreconstructed; unrelaxed
(√3x√3) substrate terminated between bilayers
R30°-Pb
adsorption at bridge sites (see Fig. 31)
Ge(111)+ AR- yes no 1.03 ± 0.05 8±2 87R3 atomic adsorption in bridge sites with shorter bond to 3rd Ge atom; with unreconstructed
(2x2)-S PEFS substrate relaxed perpendicular to surface
adclusters at T4 site (see Fig. 29)
Si(111)+ LEED yes no 2.21 -21 92W1 Bi trimers centered at T4 site; nearest Si neighbors squeezed together; Si atom directly
(√3x√3) below Bi and third layer Si atom directly below pushed downwards; second-layer Si
R30°-3Bi atoms surrounding the hollow H3 site are moved upwards
substitution below T4 site
Si(111)+ LEED yes yes -2.32 -25 90H1 B atom replaces a second layer Si atom; which becomes an adatom at the T4 site over
(√3x√3) the B atom; this B position is the B5 site
R30°-B
Si(111)+ PD yes yes -2.21 -20 99B1 B atom replaces a second layer Si atom; which becomes an adatom at the T4 site over
(√3x√3) the B atom; this B position is the B5 site
R30°-B
substitution of top half of top bilayer (see Fig. 32)
Ge(111)+ HEIS yes no 1.19 0 94G3 atomic substitutional replacement of top half of top Si bilayer: otherwise
(1x1)-Sb unreconstructed; but relaxed substrate
Si(111)+ MEIS yes no 0.99 0 87C2 atomic substitutional replacement of top half of top Si bilayer: otherwise
(1x1)-As unreconstructed; unrelaxed substrate
4.1-84
rec.
Si(111)+ XSW yes no 0.99 ± 0.03 0 87P atomic substitutional replacement of top half of top Si bilayer: otherwise
Si(111)+ MEIS yes no 1.02 ± 0.06 0 87H1 atomic substitutional replacement of top half of top Si bilayer: otherwise
partial substitution of top half of top bilayer (see Fig. 32)
Si(111)+ XRD yes yes -0.8 14 ± 1 87T triangles of 3 Bi replace every third Si in top layer; which is lower half of a bilayer
(√3x√3)
R30°-3Bi
Si(111)+ LEED yes yes 2.21 41 91W1 triangles of 3 Bi replace every third Si in top layer; which is lower half of a bilayer
(√3x√3)
R30°-3Bi
honeycomb-chained-trimer (HCT) structure
Ge(111)+ LEED yes yes 0.70 ± 0.03 -1 94H5 honey-comb chained trimer (HCT) model: top Ge half bilayer replaced by Ag; 2nd
(√3x√3) layer Ge atoms form trimers
R30°-3Ag
Si(111)+ LEED yes yes 0.45 -2 93O1 top Si half-bilayer substituted by Li (missing top layer); 2nd half-bilayer Si atoms form
(√3x√3) trimers
R30°-3Li
Si(111)+ XRD yes yes 0.80 ± 0.02 -4 93T top Si half-bilayer substituted by Ag (missing top layer); 2nd half-bilayer Si atoms form
(√3x√3) trimers; deep relaxations
R30°-3Ag
Si(111)+ LEED yes yes 0.69 -2 93O1 top Si half-bilayer substituted by Ag (missing top layer); 2nd half-bilayer Si atoms form
(√3x√3) trimers
R30°-3Ag
Si(111)+ QK- yes yes 0.79 0 93J top Si half-bilayer substituted by Ag (missing top layer); 2nd half-bilayer Si atoms form
(√3x√3) LEED/ trimers; deep relaxations
R30°-3Ag CMTA
4.1-85
rec.
Si(111)+ LEED yes yes 0.78 ± 0.05 -2 95O3 top Si half-bilayer substituted by Ag (missing top layer); 2nd half-bilayer Si atoms form
(√3x√3) trimers
R30°-3Ag
conjugate HCT structure
Ge(111)+ XRD yes no 0.42 ± 0.02 6 93H3 conjugate honeycomb-chained-trimer (CHCT) model: Au trimers centered at T4 sites;
(√3x√3) replacing top half of top Ge bilayer; nearest Ge neighbors squeezed apart
R30°-3Au
Ge(111)+ LEED yes no 0.51 0 95O4 conjugate honeycomb-chained-trimer (CHCT) model: Au trimers centered at T4 sites;
(√3x√3) replacing top half of top Ge bilayer; nearest Ge neighbors squeezed apart
R30°-3Au
Si(111)+ LEED yes no 0.56 0 92Q1 conjugate honeycomb-chained-trimer (CHCT) model: Au trimers centered at T4 sites;
(√3x√3) nearest Si neighbors in the missing-top-layer are squeezed apart
R30°-3Au
Si(111)+ LEED yes no 0.56 0 93O1 top Si half-bilayer substituted by Au (missing top layer); Au atoms form trimers
(√3x√3)
R30°-3Au
Si(111)+ XRD yes no 0.93 -8 94K conjugate honeycomb-chained trimer (CHCT) model: Au trimers centered at T4 sites
(√3x√3)
R30°-3Au
Si(111)+ XRD yes yes 1 -58 94W3 reconstruction with zigzag Si chains separated by CaF2 chains filling missing Si rows; Si
(1x3)-CaF2 chains oriented along [1-10]; obtained by mainly lateral displacements by <1Å; Ca on
top of Si near missing Si position; F bonding to two Ca and weakly to one Si of a Si
chain
Si(111)+ XRD yes yes - - 98G1 complex reconstruction; with 14 independent Au positions in a tiling of incomplete
(6x6)-14Au pentagonal and trimer units; coordinates normal to surface not determined
4.1-86
rec.
Ge(111)+ XRD yes yes - - 98C missing-top-layer reconstruction; with 6 Ag atoms placed on Ge substitutional sites in
(4x4)-6Ag one triangular subunit of the 2D unit cell; and 9 Ge atoms forming a ring-like assembly
in the other triangular subunit; coordinates normal to surface not determined
Si(111)+ XRD yes yes 0.10; - 99B2 chains of Si atoms alternating with zig-zag chains of In atoms on an essentially
(4x1)-4In 0.21 unperturbed Si lattice
Si(111)+ XRD yes yes 2.24 ± 0.04 - 98L reconstruction into consecutive 5- and 6-fold Si rings separated by channels containing
(3x1)-Li LEED the Li atoms
Table 24. Structures of clean Si and Ge (100) surfaces. Here; dbulk is the bulk interlayer spacing; d12 is the spacing between the Group IV dimer atoms; and ω is the Group IV
dimer rotation angle.
Surface Tech- Clean dbulk d12 ω Ref. Description

nique rec. [Å] [Å] (°)
Ge(100)- XRD yes 1.41 1.28 ± 0.04 31 81E tilted dimer reconstruction with lateral relaxation in 2nd layer
(2x1)
Ge(100)- XRD yes 1.412 0 0 88G symmetric dimer reconstruction
(2x1)
Ge(100)- XRD yes 1.414 0.74 17 92R asymmetric dimer reconstruction with multilayer relaxations; lateral and perpendicular; in top
(2x1) 10 layers
Ge(100)- XRD yes 1.415 0.69 ± 0.04 16 96T2 disordered reconstruction with asymmetric Ge dimers; 2 equivalent and random orientations
(2x1)
(disordered)
Si(100)-(2x1) LEED yes 1.358 0.36 ± 0.2 8 84H2 buckled dimer with multilayer relaxations
Si(100)-(2x1) GIXD yes 1.358 0.31 7 90J1 clean surface with buckled dimers
Si(100)-(2x1) LEED yes 1.358 0.14 3 91Z 2 coexisting phases: 75% (2x1) and 25% c(4x2); (2x1) has weakly buckled dimers
Si(100)-(2x1) LEED yes 1.358 0.73 ± 0.04 19 97O2 asymmetrical buckled dimer structure; with multilayer relaxation to 5th layer
Ge(100)- XRD yes 1.415 0.83 - 95F2 ordered reconstruction based on dimers in 'antiferromagnetic' arrangement
c(4x2)
Si(100)- LEED yes 1.358 0.56 14 91Z 2 coexisting phases; 75% (2x1) and 25% c(4x2); c(4x2) has strongly buckled dimers
c(4x2)
4.1-87
Table 25. Adsorbate-induced structures on Si and Ge (100) surfaces. Here; d01 is the local adsorbate height; d12 is the spacing between the Group IV dimer atoms; and ω
is the Group IV dimer rotation angle.
Surface Tech- Clean Ads- d01 d12 ω Ref. Description

nique rec. ind [Å] [Å] [°]
rec.
adsorption at center sites of unreconstructed substrate (see Fig. 33)
Si(100)+0.4 SE- yes no 0.00 ± 0.02 0.00 ± 0.02 - 91M3 atomic adsorption in-plane with top layer of bulk-like Si(100); at center of square
ML-Co XAFS of top-layer Si atoms
adsorption at continuation bridge sites of unreconstructed substrate (see Fig. 34)
Ge(100)+ AR- yes no 1.08 - - 88L atomic adsorption in bridge (i.e. bulk continuation) sites of unreconstructed but
(2x1)-S PEFS relaxed substrate
adsorption at dangling-bond sites of unreconstructed substrate
Si(100)+ TOF- yes no 0.81 - - 93S2 atomic H saturates the Si dangling bonds; forming unreconstructed substrate
(1x1)-2H SARS
adsorption at dangling bond sites of dimers
Ge(100)+ LEED yes yes 1.35 0 0 96P H (D) atoms cap non-tilted Ge dimer atoms; symmetric dimers; relaxations
(2x1)-H (D) down to fifth layer
Si(100)+ HEIS yes yes 1.017 (Ge) 0 - 94G3 Sb forms asymmetrical dimers on Ge monolayer on unrelaxed substrate; Ge
(disordered)- 1.428 (Ge) resides near continuation sites of substrate; so that whole structure is similar to
Ge+ 2.847 (Sb) clean dimerized Si(100); but considerably disordered
(disordered)- 3.183 (Sb)
Sb
Si(100)+ TOF- yes yes 0.89 0.0 0.0 93S2 atomic H resides at the Si dangling bond position of symmetrical dimers
(2x1)-2H SARS
4.1-88
rec.
Si(100)- PED yes yes 1.62 ± 0.4 0.3 ± 0.4 8±8 97F3 NH2 adsorbed on one end of Si dimers; buckling of dimers probably lifted
(2x1)+
(disordered)-
NH2
Si(100)- PED yes yes - - - 98F OH and H adsorbed at dangling-bond sites of relatively symmetric Si dimers
(2x1)+
(disordered)-
OH+H
Si(100)+ XSW yes yes 3.06 ± 0.03 0.83 ± 0.03 20 ± 2 95C1 Rb adsorbed on top of the highest of the two Si atoms forming an asymmetric
(2x1)-Rb surface dimer
(top;
disordered)
adsorption at pedestal sites on dimers
Si(100)+ LEED yes yes 1.85 0 0 90W2 atomic adsorption in 'pedestal site'; bridging pairs of adjacent Si dimers; which
(2x1)-Na are stretched wrt clean Si(100)-(2x1)
Si(100)+ XSW yes yes 1.44 ± 0.03 0.00 ± 0.02 0±2 95C1 Rb adsorbed at pedestal site; at center between two adjacent symmetrical Si
(2x1)-Rb dimers
(pedestal;
disordered)
adsorption at bridge sites on dimers
Si(100)+ XSW yes yes 2.40 ± 0.03 0.00 ± 0.02 0±2 95C1 Rb adsorbed at bridge site; over midpoint of symmetrical dimer
(2x1)-Rb
(bridge;
disordered)
4.1-89
rec.
adsorption at valley sites on dimers
Si(100)+ XSW yes yes 1.38 ± 0.03 0.00 ± 0.02 0±2 95C1 Rb adsorbed at valley site; at center between 4 symmetrical dimers
(2x1)-Rb
(valley;
disordered)
adsorption at cave+pedestal sites on dimers
Si(100)+ LEED yes yes 1.75 1.15 ± 0.1 29 91U atomic adsorption as 'double layer' model; with K at both the pedestal and cave
(2x1)-2K sites on a dimerized Si(100)-(2x1) substrate
Si(100)+ LEED yes yes 1.03; 0 0 93U atomic adsorption as 'double layer' model; with K at both the pedestal and cave
(2x1)-2K 1.58 sites on a dimerized Si(100)-(2x1) substrate
Si(100)+ LEED yes yes 2.46 0 0 93U atomic adsorption as 'double layer' model; with Cs at both the pedestal and cave
(2x1)-2Cs sites on a dimerized Si(100)-(2x1) substrate
2.95 0 0
adsorption at cave+bridge sites on dimer
Si(100)+ XRD yes yes 2.72 0 0 98M2 partial lifting of clean-surface dimerization; with adsorption on both dimer-bridge
(2x1)-2K 2.17 site and valley-bridge site
Si(100)+ XRD yes yes 2.66 0 0 98M2 partial lifting of clean-surface dimerization; with adsorption on both dimer-bridge
(2x1)-2Cs site and valley-bridge site
dimers on unreconstructed substrate
Ge(100)+ XRD yes no 1.39 ± 0.06 - 0 92L asymmetric Sb-Sb dimers replace Ge-Ge dimers of clean Ge(100); dimers are
(2x1)-2Sb 1.43 ± 0.06 laterally shifted from symmetry axis by 0.16 Å; and perhaps slightly tilted;
substrate relaxes to 4th Ge layer (laterally in 1st; 4th layers; buckling in 2nd; 3rd
layers)
4.1-90
rec.
Ge(100)+ XSW yes no 2.01 ± 0.07 - 0 95L1 symmetrical Sb dimer overlayer on unreconstructed; relaxed substrate: topmost
(2x1)-2Sb Ge-Ge interlayer spacing contracted (this contraction could be spread more
uniformly over more spacings)
Si(100)+ XSW yes no 1.64 ± 0.02 - 0 95L3 Sb dimer on unreconstructed substrate (dimer orientation perp. to that of the Si
(2x1)-2Sb dimer formed after removal of the Sb layer; i.e. parallel to Si dimer formed by
substitution of Si for Sb)
Si(100)+ SE- yes no 1.74 ± 0.06 - 0 91R Sb dimer on unreconstructed substrate (dimer orientation perp. to that of the Si
(2x1)-2Sb XAFS dimer formed after removal of the Sb layer; i.e. parallel to Si dimer formed by
substitution of Si for Sb)
dimers on dimers (parallel)
Si(100)+ LEED yes yes 1.08 ± 0.05 0.00 ± 0.05 0 ± 1 93S1 non-buckled Al dimer between and parallel to Si dimers (like clean-surface
(2x2)-2Al dimers but without buckling); with multilayer relaxations
Si(100)+ LEED yes yes 1.07 ± 0.05 0.00 ± 0.05 0 ± 1 94S1 non-buckled Ga dimer between and parallel to Si dimers (like clean-surface
(2x2)-2Ga dimers but without buckling); with multilayer relaxations
Si(100)+ XSW yes yes 1.03 ± 0.02 - - 95T non-buckled Ga dimers are centered at valley bridge sites with the Ga-dimer
(2x2)-2Ga bond oriented parallel to the underlying Si-dimer bonds
complex reconstructions
Si(100)+ TOF- yes yes - 0 0 93W2 for Si substrate; the crosswise linked dimer (CLD) model is consistent with
c(4x4)-12H SARS experimental data
Ge(100)- XRD yes yes 0.057 0.792 19 94M3 disordered overlayer on reconstructed relaxed substrate; adatoms occupy T3 site
(2x1)+Cs (on top of 3rd layer Ge); asymmetric Ge-dimer remain; with 2 equivalent
(disordered) random orientations
Ge(100)- XRD yes yes 0.51 ± 0.2 0.57 ± 0.06 12 ± 2 95M2 disordered overlayer on reconstructed relaxed substrate; Na occupies two sites:
(2x1)+Na near T3 (on top of 3rd layer Ge) and near T4 site; asymmetric Ge dimers remain;
(disordered) with 2 equivalent random orientations
Ge(100)- XRD yes yes 0.79 ± 0.2 0.57 ± 0.06 12 ± 2 95M2 disordered overlayer on reconstructed relaxed substrate; adatoms occupy T3 site
(2x1)+K (on top of 3rd layer Ge); asymmetric Ge-dimers remain; with 2 equivalent
(disordered) random orientations
4.1-91
rec.
Si(100)+ GIXD yes yes 0.866 (Si) 0 0 98B2 dimer rows with a sequence of two In-Si dimers followed by a Si vacancy
(3x4)-6In STM 0.996(In) allowing stress relief; In-Si-In 'trimers' between the dimer rows saturating
2.396(In) dangling bonds of Si atoms; relaxations down to the sixth layer
2.566 (Si)
Table 26. Structures of clean Si(311) surfaces.

Ge(311)- GIXD yes 1.706 98V3 reconstructed dimer-adatom-interstitial model (interstitial site half occupied); relaxation around
(3x1) the interstitial sites amounts up to about 1 Å
Table 27. Adsorbate-induced structures on Si(311) surfaces.

rec.
overlayer in 2-fold coordinated continuation site
Si(311)+ QK- yes no 1.37 95Z adatom on bridging continuation site on unreconstructed substrate relaxed down to 9th
(1x1)-Pb LEED Si monolayer
dimerization of substrate
Si(311)+ LEED yes yes - 94H6 2 top layer (100)-like Si atoms form dimers; 3rd (100)-like Si atom absent; 2 Si atoms;
(3x1)-H previously bonded to it; form another dimer; surface relaxations extend down to six
layers from the surface; H positions not determined
4.1-92
Table 28. Structures of clean zincblende(110) surfaces. Here; dbulk is the bulk interlayer spacing; d12 is the outermost spacing (buckling) between the tilted Group III-V
(or II-VI) atom chains; and ω is the tilt angle of these chains.

AlP(110)- LEED no 1.925 0.63 25 83D3 top layer composed of tilted zigzag chain
(1x1)
CdTe(110)- LEED no 2.291 0.73 30 97D top layer composed of tilted zigzag chain
(1x1)
CuBr(110)- LEED no 2.012 0.76 35 96D3 top layer composed of tilted zigzag chain
(1x1)
CuCl(110)- LEED no 1.911 0.78 53 96D3 top layer composed of tilted zigzag chain
(1x1)
GaAs(110)- LEED no 1.999 0.69 28 84T1 top layer composed of tilted zigzag chain
(1x1)
GaAs(110)- LEED no 1.999 0.40 16 84G2 top layer composed of tilted zigzag chain
(1x1)
GaAs(110)- LEED no 1.999 0.67 29 93C2 top layer composed of tilted zigzag chain
(1x1)
GaP(110)- LEED no 1.927 0.61 28 93L3 top layer composed of tilted zigzag chain
(1x1)
GaSb(110)- LEED no 2.163 0.77 30 83D4 top layer composed of tilted zigzag chain
(1x1)
GaSb(110)- MEIS no 2.163 0.73 29 86S4 top layer composed of tilted zigzag chain
(1x1)
InP(110)- LEED no 2.075 0.64 26 80T top layer composed of tilted zigzag chain
(1x1)
InP(110)- SE- no 2.074 0.66 27 92W3 top layer composed of tilted zigzag chain
(1x1) XAFS
InP(110)- LEPD no 2.075 0.61 25 93C2 top layer composed of tilted zigzag chain
(1x1)
InP(110)- PED no 2.074 0.57 23 93G2 top layer composed of tilted zigzag chain
(1x1)
InSb(110)- LEED no 2.29 0.78 29 80M2 top layer composed of tilted zigzag chain
(1x1)
4.1-93
InSb(110)- LEED no 2.29 0.81 41 87D1 top layer composed of tilted zigzag chain
(1x1)
ZnS(110)- LEED no 1.913 0.55 30 93L3 top layer composed of tilted zigzag chain
(1x1)
ZnSe(110)- LEED no 2.004 0.68 29 84D top layer composed of tilted zigzag chain
(1x1)
ZnTe(110)- LEED no 2.153 0.71 28 83D5 top layer composed of tilted zigzag chain
(1x1)
Table 29. Adsorbate-induced structures on zincblende(110) surfaces. Here; d01 is the local adsorbate height; d12 is the outermost spacing (buckling) between the tilted Group III-
V atom chains; and ω is the tilt angle of these chains.

rec.
adsorption at dangling-bond sites
GaAs(110)+ PD no no - 0.15 6 ±1.5 95R surface derelaxes towards ideal termination; H atom positions unknown
H (0.25 ML)
GaAs(110)+ GIXD no no - -0.115 -5 ± 1 94R small counter-relaxation; H atom positions unknown
H (0.8 ML)
GaAs(110)+ TOF- no no - 0.0 ± 0.08 0±3 97G2 surface derelaxes towards ideal termination; H atom positions unknown
H (low SARS
coverage)
GaAs(110)+ TOF- no no - -0.08 ± 0.08 -3 ± 3 97G2 small counter-relaxation; H atom positions unknown
H (high SARS
coverage)
GaAs(110)+ LEED no no 2.39 -0.100 -4 82D Sb forms zigzag chains continuing GaAs lattice outward; but with expanded Sb-Sb
(1x1)-2Sb 2.29 and Sb-substrate distances; and with slight tilting of topmost GaAs chains
4.1-94
rec.
GaAs(110)+ LEED no no 2.36 -0.111 -5 90F2 Sb forms slightly tilted zigzag chains continuing GaAs lattice outward but with
(1x1)-2Sb 2.29 expanded Sb-Sb and Sb-substrate distances and with slight tilting of topmost GaAs
chains
GaAs(110)+ LEED no no 2.51 -0.106 -4 90F2 Bi forms slightly tilted zigzag chains continuing GaAs lattice outward but with
(1x1)-2Bi 2.42 expanded Bi-Bi and Bi-substrate distances and with slight tilting of topmost GaAs
chains
GaSb(110)+ XRD no no - - 34 (Bi-Bi) 98V1 Bi forms almost untilted zigzag chains bonded alternately to Ga and Sb atoms of
(1x1)-2Bi bulk-terminated unrelaxed surface
InP(110)+ LEED no no 2.39 -0.027 -1 92F adatoms forming (slightly tilted) zigzag chains; continuing relaxed substrate lattice
(1x1)-2Sb 2.26
InP(110)+ LEED no no 2.6 0.038 1 92F adatoms forming (slightly tilted) zigzag chains; continuing relaxed substrate lattice
(1x1)-2Bi 2.4
InP(110)+ XSW no no 1.97 ± 0.06 0.0 0 96D2 S atoms bonded to surface In and occupying sites near P sites of continuation of
(1x1)-SH+H bulk structure into vacuum; outer InP layer is 'unrelaxed' to bulk-terminated
structure
substitution in 1st layer
GaSb(110)+ XRD no yes - - - 98V2 2 strongly tilted (34°) Bi-Bi zig-zag rows replace every other Ga-Sb zig-zag row of
(2x1)-4Bi clean surface; inducing subsurface relaxations
substitution in 2nd layer
GaAs(110)+ LEED no yes - 0.69 31 81K substitution of Al in 2nd-layer Ga positions; otherwise same structure as
(1x1)-1Al GaAs(110) (class. no. 31.33.26); except for 0.1Å reduction of 1st-2nd layer
(low spacing
coverage)
4.1-95
rec.
substitution in deeper layer
GaAs(110)+ LEED no yes - 0.69 31 81K substitution of Al in 2nd- and 3rd-layer Ga positions; otherwise same structure as
(1x1)-2Al GaAs(110) (class. no. 31.33.26); except for 0.1Å reduction of 1st-2nd layer
(medium spacing
coverage)
GaAs(110)+ LEED no yes - 0.69 31 81K substitution of Al in 1st; 2nd- and 3rd-layer Ga positions; otherwise same structure
(1x1)-3Al as GaAs(110)-2Al; except for 0.1Å reduction of 1st-2nd layer spacing; higher
(high coverages cause Al substitution in deeper layers; e.g. at 8.5ML substitution down
coverage) to at least 6th layer
Table 30. Structures of clean zincblende(111) surfaces. Here; dbulk is the bulk interlayer spacing; d12 is the outermost spacing between Group III-V atoms; and ω is the tilt angle
of these III-V bonds; relative to the surface plane.

GaAs(111)- LEED yes 0.816; 0.2 5 84T2 one missing Ga per (2x2) unit cell in heavily relaxed top bilayer; top bilayer almost planar
(2x2) 2.448
GaP(111)- LEED yes 0.787; 0.1 2 85X2 one missing Ga per (2x2) unit cell in heavily relaxed top bilayer; top bilayer almost planar
(2x2) 2.360
GaSb(111)- XRD yes 0.88; 0 0 87F one missing Ga per (2x2) unit cell in heavily relaxed top bilayer; top bilayer almost planar
(2x2) 2.64
4.1-96
Table 31. Adsorbate-induced structures on zincblende(111) surfaces. Here; d01 is the local adsorbate height; d12 is the outermost spacing between Group III-V atoms;
and ω is the tilt angle of these III-V bonds; relative to the surface plane.

rec.
GaAs(111)+ XSW yes no 2.17 ± 0.04 -0.816 19 93S5 S adatoms at top sites (bonding to Ga) on unreconstructed full-bilayer
(1x1)-S termination; substrate assumed unrelaxed
3C- LEED no no 1.61 -0.63 19 97S1 adsorption at top sites; inducing multilayer subsurface relaxations
SiC(111)+
(disordered)-O
Table 32. Structures of clean zincblende(-1-1-1) surfaces. Here; dbulk is the bulk interlayer spacing; d12 is the outermost spacing between Group III-V atoms; and ω is the tilt
angle of these III-V bonds; relative to the surface plane.

InSb XRD yes 0.935; 94W1 complex reconstruction composed of two types of rings of 6 atoms each; partly disordered
(-1-1-1)-(3x3) 2.806
(disordered)
Table 33. Adsorbate-induced structures on zincblende(-1-1-1) surfaces. Here; d01 is the local adsorbate height; d12 is the outermost spacing between Group III-V atoms; and ω
is the tilt angle of these III-V bonds; relative to the surface plane.

rec.
GaAs XSW yes no 0.69 ± 0.04 0.816 - 93S5 S adatoms substituting for top half of top bilayer; i.e. bonding to 3 Ga atoms;
(-1-1-1)+ substrate assumed unrelaxed
(1x1)-S
4.1-97
Table 34. Structures of clean zincblende(100) surfaces. Here; dbulk is the bulk interlayer spacing; d12 is the outermost spacing between Group IV-IV or III-V atoms; and
ω is the tilt angle of their bonds; relative to the surface plane.

SiC(100)- LEED yes 1.093 0.20 (Si-Si) 95S1 Si-rich Si-terminated reconstruction with asymmetric buckled Si dimers; small
(2x1) 1.21 (Si-C) relaxations in deeper layers
SiC(100)- LEED yes 1.093 0.0 (Si-Si) 91P C-rich C-terminated reconstruction with symmetric C pairs bridging Si pairs;
c(2x2) (C2H4 1.62 (Si-C) slight relaxations in second layer; this structure possibly contains hydrogen
exposed)
SiC(100)- LEED yes 1.093 0.0 (Si-Si) 91P C-rich C-terminated reconstruction with symmetric C pairs bridging Si pairs;
c(2x2) (Si 1.60 (Si-C) marked relaxations in second layer; this structure is presumably hydrogen-free
sublimation)
GaAs(100)- RH- yes 1.413 1.52 35 90F2 reconstruction with As termination as three As2 dimers; with substrate assumed
(4x2) EED unrelaxed
GaAs(100)- GIXD yes 1.413 1.77 41 96G1 reconstruction with As termination as two As dimers; missing Ga row in second
(4x2) layer; As dimers in third layer
InP(100)- TOF- yes 1.47 0.15 (In-In) 96D2 reconstruction with In termination as three In2 dimers; with a 2nd-layer P2 dimer
(4x2) SARS 1.32 (In-P) 32 exposed in the trough
GaAs(100)- LEED yes 1.414 0.86; 27 95C2 three Ga dimers and a dimer vacancy in top layer; the middle Ga dimer is fully
c(8x2) (Ga- 1.05 dimerized; while dimerization of the other two dimers is subtle; second (As) layer
terminated) and deeper layers have no vacancies; strong relaxations down to the third layer
Table 35. Adsorbate-induced structures on zincblende(100) surfaces. Here; d01 is the local adsorbate height; d12 is the outermost spacing between Group III-V atoms; and ω is
the tilt angle of these III-V bonds; relative to the surface plane.

rec.
GaAs(100)+ XSW yes no 1.1 0 - 94S7 S atoms at bridge sites on Ga-terminated surface; which is assumed non-reconstructed
(1x1)-S
4.1-98
Table 36. Structures of clean 6H-SiC(0001) surfaces. Here; dbulk is the bulk interlayer spacing; d12 is the outermost spacing between Group IV-IV atoms; and ω is the tilt
angle of their bonds; relative to the surface plane.

6H- LEED no 1.9 0.64 20 97S1 small relaxations of interlayer spacings
SiC(0001)-
(1x1)
Table 37. Adsorbate-induced structures on 6H-SiC(0001) surfaces. Here; d01 is the local adsorbate height; d12 is the outermost spacing between Group IV-IV atoms; and ω is
the tilt angle of these IV-IV bonds; relative to the surface plane.

rec.
6H- LEED no no 1.02 0.60 18 97S1 adsorption at top sites; inducing multilayer subsurface relaxations
SiC(0001)+H
6H- LEED no no 1.66 0.55 17 97S1 adsorption at top sites; inducing multilayer subsurface relaxations
SiC(0001)+O
6H- LEED no no 1.65± 0.03 0.58 ± 0.02 18 95S1 unreconstructed relaxed substrate; with OH groups saturating the dangling bonds of
SiC(0001)+ top Si layer; adatom site: top position on Si (T1-site) (H ignored) O-Si bond length:
(1x1)-OH 1.65Å; first bilayer spacing 7.5% contracted; interbilayer spacings are bulklike
Figures for 4.1
Fig. 1. Generic labeling scheme for

relaxations in a surface - top view. This
Fig. shows only one shell (labeled s) of
symmetrically equivalent atoms in one
particular layer (labeled l), surrounding
the adsorbate site. The relaxed atomic
positions are shown as black balls,
displaced relative to the ideal bulk-like
positions (gray balls). The relaxed radial
position is labeled as rls(1+∆rls), with an
in-plane rotation angle of αls.
Fig. 2. Generic labeling scheme for

relaxations in a surface - side view. An
adsorbate defines layer 0 and the
adsorbate site (or adsorption axis, which
is usually a symmetry axis); the adsorbate
may be displaced away from the
symmetry axis by an amount ∆r0, and it
may contain more atoms (not shown
here). Substrate layers are labeled l = 1,
2, 3, …, and shown here as gray bars,
with a non-zero thickness due to buckling
from a planar layer in the bulk. The
spacings between layers are labeled
dbulk(1+∆dl,l+1), where dbulk is given in
the tables for clean surfaces; these
spacings are measured between the thick
lines defined as the height of those atoms
which are nearest to the dashed
adsorption axis (these atoms are labeled
a). In a given layer l = 1, 2, 3, …, the
radial distance of atoms in shells s = a, b,
c, … (centered on the adsorption axis) is
given by rls(1+∆rls), where rls is the ideal
unrelaxed distance. Similarly, the
buckling of an atom within layer l is
given as bls/dbulk, relative to its ideal non-
buckled position on the thick line.

(a) 3c (a) 2c
1c 1c 1c 1c
2c 2b 2c 3c 3b 3c
3c 3b 3b 3c 2b 2b
1b 1a 1b
1b 1a 1b
2c 2a 2a 2c
3c 3a 3a 3c
3b 3a 3b 2a
2b 2b
1c 1a 1a 1c
1c 1a 1a 1c
2b 2a 2b
3c 3b 3b 3c 3b 3a 3b
1c 1b 1c 2c 2b 2b 2c
2c 2c 1c 1b 1c
3c 3c 3c
(b) (b)
1c 1b 1a 1a 1a 1b 1c 1c 1b 1a 1a 1a 1b 1c
2c 2b 2a 2a 2a 2b 2c 2c 2b 2b 2a 2b 2b 2c
3c 3b 3b 3a 3b 3b 3c 3c 3b 3a 3a 3a 3b 3c
Fig. 3. Sketch of fcc(111) fcc-hollow site. Fig. 4. Sketch of fcc(111) hcp-hollow site.
Views are (a) along the surface normal and (b) parallel to surface. The dashed line in (a) denotes the cutting plane
used for the view in (b). The digits 1, 2, 3, … label atomic layers of the substrate (index l), while the letters a, b, c, …
label atomic shells around the adsorption site axis (index s). These views and conventions are used in
Figs. 3 - 35.
(a) (a)
1c 1c 1b 1c
3c 3c 3c 3c
2c 2b 2c 2c 2b 2c
1c 1b 1b 1c 1b 1a 1a 1b
3b 3a 3b 3b 3a 3b
2c 2a 1a 2a 2c 2c 2a 2a 2c
1b 1b 1c 1a 1a 1c
3c 3a 3a 3c 3c 3a 3a 3c
2b 2a 2b 2b 2a 2b
1c 1b 1b 1c 1b 1a 1a 1b
3c 3b 3c 3c 3b 3c
2c 2c 2c 2c
1c 1c 1b 1c
(b)
1c 1b 1a 1a 1a 1a 1b 1c
(b)
1c 1b 1b 1a 1b 1b 1c
2c 2b 2a 2a 2a 2b 2c
2c 2b 2a 2a 2a 2b 2c
3c 3b 3a 3a 3a 3b 3c
3c 3b 3a 3a 3a 3b 3c
Fig. 5. Sketch of fcc(111) top site. Fig. 6. Sketch of fcc(111) substitutional site.

(a) 1c 1c (a) 2c
2c 2b 2c 1c 1c
1b 1a 1b 2b 2b
2c 2a 2a 2c 1b 1a 1b
2a
1c 1a 1a 1c 2b 2b
2b 2a 2b 1c 1a 1a 1c
1c 1b 1c 2c 2b 2b 2c
2c 2c 1c 1b 1c
(b) (b)
1c 1b 1a 1a 1a 1b 1c 1c 1b 1a 1a 1a 1b 1c
2c 2b 2a 2a 2a 2b 2c 2c 2b 2b 2a 2b 2b 2c
3c 3b 3a 3a 3a 3b 3c 3c 3b 3a 3a 3a 3b 3c
Fig. 7. Sketch of hcp(0001) fcc-hollow site. Fig. 8. Sketch of hcp(0001) hcp-hollow site.
(a) (a) 1c 1c
1c 2c 2b 2c
2c 2b 2c
1c 1b 1b 1c 1b 1a 1b
2c 2a 2a 2c
2c 2a 1a 2a 2c
1b 1b
1c 1a 1a 1c
2b 2a 2b 2b 2a 2b
1c 1b 1b 1c
2c 2c 1c 1b 1c
1c 2c 2c
1a
(b)
1c 1b 1a 1a 1b 1c
(b)
1c 1b 1b 1a 1b 1b 1c
2c 2b 2a 2a 2a 2b 2c
2c 2b 2a 2a 2a 2b 2c
3c 3b 3a 3a 3a 3b 3c
3c 3b 3b 3a 3b 3b 3c
Fig. 9. Sketch of hcp(0001) top site. Fig. 10. Sketch of hcp(0001) octahedral interstitial site.

(a) 2c (a)
1c 1c
1c 2b 1b 2b 1c
2b 2b
1b 1a 1b 2a
2c 1a 1a 2c
2a
2b 2b
1c 1a 1a 1c
1c 2b 1b 2b 1c
2c 2b 2b 2c
1c 1b 1c
1a
(b)
1c 1b 1a 1a 1b 1c
(b)
1c 1a 1b 1a 1c
2c 2b 2b 2a 2b 2b 2c
2c 2b 2a 2b 2c
3c 3b 3a 3a 3a 3b 3c
3c 3a 3b 3a 3c
Fig. 11. Sketch of hcp(0001) tetrahedral interstitial site. Fig. 12. Sketch of bcc(110) center site.
(a) (a) 1c 1b 1b 1c
2c 2b 2c
1d 2b 1a 2b 1d
1b 1a 1a 1b
2a
2d 1b 1b 2d 2b 2b
2a
1b 1a 1a 1b
1e 2c 1c 2c 1e
2c 2b 2c
1c 1b 1b 1c
(b)
1d 1b 1a 1b 1d (b) 1b 1a 1a 1b
2d 2b 2a 2b 2d 2b 2a 2b
3d 3b 3a 3b 3d 3b 3a 3a 3b
Fig. 13. Sketch of bcc(110) 3-fold coordinated hollow site. Fig. 14. Sketch of fcc(100) hollow site.

(a) (a) 1c
2c 2b 2b 2c 2c 2b 2b 2c
1c 1b 1c 1b 1a 1b
2b 2a 2a 2b 2b 2a 2a 2b
1a 3a
1b 1b 1c 1a 1a 1c
2b 2a 2a 2b 2b 2a 2a 2b
1c 1b 1c 1b 1a 1b
2c 2b 2b 2c 2c 2b 2b 2c
1c
(b) 1c 1a 1a 1c
(b) 1b 1a 1b 2b 2a 2a 2b
2b 2a 2a 2b
3d 3b 3a 3b 3d
3b 3a 3b
Fig. 15. Sketch of fcc(100) top site. Fig. 16. Sketch of fcc(100) substitutional site.
(a) 1c 1b 1b 1c (a) 2c
2c 2b 2c 1b 1b
1b 1a 1a 1b 2b 2a 2b
2a
2b 2b 1c 1a 1a 1c
1b 1a 1a 1b 2b 2a 2b
2c 2b 2c 1b 1b
1c 1b 1b 1c 2c
(b) 1b 1a 1a 1b (b) 1c 1a 1a 1c
2b 2a 2b 2b 2a 2b
3b 3a 3a 3b 3c 3a 3a 3c
Fig. 17. Sketch of bcc(100) hollow site. Fig. 18. Sketch of bcc(100) bridge site.

(a) 2c
(a) 1b 1b
1b 1b
2d 2b 2d
2b 2a 2b 1c 1a 1a 1c
2a
1c 1a 1a 1c 2c 2c
2b 2a 2b 1c 1a 1a 1c
2d 2b 2d
1b 1b
1b 1b
2c
(b) 1c 1a 1a 1c (b) 1c 1a 1a 1c
2b 2a 2b 2c 2a 2c
3c 3a 3a 3c 3c 3a 3a 3c
Fig. 19. Sketch of bcc(100) 4-fold coordinated Fig. 20. Sketch of fcc(110) center site.
interstitial site.
(a) (a) 1c 1c
1c 2d 2c 2d
2b 1b 1b
1b 1a 2b 2a 2b
2a 2c 1c 1a 1a 1c
1b 1a 2b 2a 2b
2b 1b 1b
1c 2d 2c 2d
1c 1c
(b) 1b 1a
(b) 1c 1a 1a 1c
2a 2c
2b 2a 2b
3b 3a
3c 3a 3a 3c
Fig. 21. Sketch of fcc(110) 3-fold coordinated hollow Fig. 22. Sketch of fcc(110) long-bridge site.
site.

(a) 2d (a)
2b 2b
1c 1b 1b 1c
1d 1b 1d
2c 2b 2a 2b 2c
2c 2a 2a 2c
1a
1b 1a 1a 1b 1c 1c
2c 2a 2a 2c
2c 2b 2a 2b 2c
1d 1b 1d
1c 1b 1b 1c
2b 2b
2d
(b) 1b 1a 1a 1b
(b) 1c 1a 1c
2c 2b 2a 2b 2c
2c 2a 2a 2c
3b 3a 3a 3b
3c 3a 3c
Fig. 23. Sketch of fcc(110) short-bridge site. Fig. 24. Sketch of fcc(110) upper top site.
(a) 2c 2c
(a) 1b 4b 1b
1c 1b 1c
3b 2b 3b
2b 2a 2a 2b 4c 1a 4a 1a 4c
3a 2a
1a 1a 2c 3a 3a 2c
2b 2a 2a 2b 4c 1a 4a 1a 4c
3b 2b 3b
1c 1b 1c
1b 4b 1b
2c 2c
(b) 1a 1b 1a
2b 2a 2a 2b (b) 1a 1a
3b 3a 3b 2c 2a 2c
3a 3a
4c 4a 4c
Fig. 25. Sketch of fcc(110) upper substitutional site. Fig. 26. Sketch of hcp(10-10) center site.

(a) 1c 1c
(a) 4c 1c 3c
2b 3b 2b 2a 2b
1b 4a 1a 4b 4b 4a 4a 4b
3c 2a 3a 2c 1b 1a 1a 1b
3b 3a 3b
1b 4a 1a 4b
2b 3b 2b 2a 2b
4b 4a 4a 4b
4c 1c
1c 1c
3c
(b) 1b 1a
2a 2c
(b) 1b 1a 1a 1b
3c 3a
2b 2a 2b
4a 4b
3b 3a 3b
4b 4a 4a 4b
Fig. 27. Sketch of hcp(10-10) 3-fold coordinated Fig. 28. Sketch of hcp(10-10) short-bridge site.
hollow site.
(a) 1c 2c 4c 1c
(a) 1b 2b 4b 1c
2c 4b 1b 2b 4c
1c 2b 4a 1a 2b 4c 1b 2a 4a 1b 2c
2a 1a
4b 1a 4a 1b 1c 2b 4a 2a 4b 1c
1c 2b 4a 1a 2b 4c 1b 2a 4a 1b 2c
2c 4b 1b 2b 4c
1b 2b 4b 1c
1c 2c 4c 1c
(b) 1c 1a 1a 1b
2b 2a 2b
(b) 1c 1b 1a 1b 1c
2b 4c
2a 2a 2c
3b 3a 3b
4b 4a 4a 3b 3a 3a 3c
4a 4a 4b
Fig. 29. Sketch of diamond(111) T4 site. Fig. 30. Sketch of diamond(111) top site.

(a) 1b 2c 4c 1b
(a) 1d 4c 2c 1e
2c 4b 1a 2b 4c
2b 1a 4b 4c 1a 2a 4a 1a 2c
1b 4a 2a 1c 1b 2b 4a 2a 4b 1b
2b 1a 4b 4c 1a 2a 4a 1a 2c
2c 4b 1a 2b 4c
1d 4c 2c 1e
1b 2c 4c 1b
(b) 1b 1a 1c (b) 1b 1a 1a 1b
2b 2a 2b 2a 2a 2c
3b 3a 3b 3a 3a 3c
4a 4b 4c 4a 4a 4b
Fig. 31. Sketch of diamond(111) bridge site. Fig. 32. Sketch of diamond(111) substitutional top site.
(a) 1c 2c 1c
(a) 4d 1b 4b 1b 4d
3d 4b 3c 4b 3d
1b 2b 1a 2a 1a 2b 1b 2b 3b 2a 3a 2a 3b 2b
4a
4c 3b 4a 3a 4a 3b 4c 1c 4c 1a 1a 4c 1c
1b 2b 1a 2a 1a 2b 1b 2b 3b 2a 3a 2a 3b 2b
3d 4b 3c 4b 3d
4d 1b 4b 1b 4d
1c 2c 1c
(b) 1c 1a 1a 1c
(b) 1b 1a 1a 1b
2b 2a 2a 2b
2b 2a 2b
3b 3a 3b
3b 3a 3b
4c 4a 4c
4c 4a 4a 4c
Fig. 33. Sketch of diamond(100) center site. Fig. 34. Sketch of diamond(100) continuation bridge
site.

(a) 1c 2c 4c 1c
2c 4b 1b 2b 4c
4c 1b 2a 4a 1b 2c
1a
1c 2b 4a 2a 4b 1c
4c 1b 2a 4a 1b 2c
2c 4b 1b 2b 4c
1c 2c 4c 1c
(b) 1c 1b 1a 1b 1c
2b 2a 2a 2c
3b 3a 3a 3c
4c 4a 4a 4b
Fig. 35. Sketch of zincblende(111) top site.

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94X Xu, C., Burnham, J.S., Goss, S.H., Caffey, K., Winograd, N.: Phys. Rev. B49 (1994) 4842.
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4.2 Electron work function of metals and semiconductors
K. JACOBI
4.2.1 Introduction
4.2.1.1 List of abbreviations
AES Auger Electron Spectroscopy

ARUPS Angle-Resolved UV Photoelectron Spectroscopy
∆Φ work-function change
ELS Energy Loss Spectroscopy
FEM Field Emission Microscopy
HAS He Atom Scattering
HREELS High-Resolution Electron Energy Loss Spectroscopy
INS Ion Neutralization Spectroscopy
IPES Inverse Photoelectron Spectroscopy
IRAS IR Reflection Absorption Spectroscopy
LEED Low-Energy Electron Diffraction
MDS Metastable Deexcitation Spectroscopy
min minimum
ML monolayer
NMR Nuclear Magnetic Resonance
NRA Nuclear Reaction Analysis
PYS Photoelectron Yield Spectroscopy
RBS Rutherford Backscattering Spectroscopy
SE Secondary Electron
TDS Thermal Desorption Spectroscopy
SIMS Secondary Ion Mass Spectroscopy
4.2.1.2 Definition of work function
At the solid-state vacuum interface, the electron density drops to zero within less than an atomic distance
normal to the surface (z-direction). This drop in electron density is typically characterized by some spill-
out of the most weakly bound electrons, i.e., the electrons in the valence or conduction band, into the
vacuum leaving behind some positively charged volume in the first atomic layer. Thus, at the surface a
dipole is established with its negative end pointing out of the surface. If the electrostatic potentials energy
of an electron is given by v(z), this surface dipole can be described by a potential step
D = v() – v(- ) (1)
So, the potential of an electron at rest in a macroscopic distance away from the surface v() is larger than
the average potential deep in the crystal v(- ). This potential step serves, in part, to keep the electrons
within the crystal. v() often is called the “vacuum level”. The second part of the surface barrier keeping
the electrons within the solid matter (at low temperature) is due to short range Coulomb interactions
– exchange and correlation – which is a pure bulk effect.
On this background the work function Φ is defined as the minimum energy needed to transfer an
electron from the bulk to a point in a macroscopic distance outside the surface leaving it there a rest, i.e.,
at zero kinetic energy. With EN, the total energy of N electrons in the bulk, Φ is given by:

4.2-2 4.2 Electron work function of metals and semiconductors [Ref. p 4.2-118
Φ = v() + EN–1 – EN (2)

= v() – µ ,
where
 ∂F 
µ=   = EN – EN–1 (3)
 ∂N  T, V
is the electrochemical potential of the electron as derived from the free Helmholtz energy F at constant
temperature T and constant volume V of the system. By this equation the work function is defined as the
energy difference of an electron at the Fermi level EF Łµ and at an infinite distance at rest v(). Choosing
v(– ) as a reference level, Eq. (2) transforms into
Φ=D– µ (4)
where µ is the bulk chemical potential referred to the mean electrostatic potential in bulk v(- ). Formula
(4) clearly separates the surface component D and the bulk component µ of the work function.
At this point, it becomes also evident how adsorbates can influence Φ. Adsorbates at a condensed-matter
surface do certainly not influence µ but may influence the dipole layer at the surface. As it was outlined
already by Bonzel in the introduction, adsorbed species may develop a dipole moment during bond
formation with the surface atoms or its permanent dipole may get oriented in the electric field at the
surface. The work function change ∆Φ is given by the classic Helmholtz equation
∞
∆Φ = 4πe ∫ zδn (z)dz .
−∞
(5)
δn ( z ) denotes the redistribution of valence charge density that accompanies adsorption.
A compilation of work function data for clean metal surfaces (mostly single cristalline) are published in
[94J3].
4.2.1.3 Work function versus local potential
It is well known that the work function of a single-crystalline sample depends on the crystallographic
surface plane for which it is measured. Generally, Φ increases with the surface atomic density. On the
other hand, according to the definition given above Φ is a macroscopic thermodynamic quantity
independent of surface crystallography. If the work function would simply depend on the path way
normal to the surface, along which the electron is transferred into vacuum, the construction of a
perpetuum mobile would be possible. Since the latter cannot be the case, a paradoxical situation arises.
The answer to this paradoxon has been found in the consideration of the inhomogeneous field at the edges
between the differently oriented surfaces. Moving the electron from in front of one surface to another the
electron looses or gains energy in crossing the edge fields. At infinity there is only one value of Φ and the
face-specific values have to be lowered or raised approaching the material-specific value at infinity. From
this argument it is much more reasonable to talk about the local potential in front of a surface instead of
the work function of this surface. This point was stressed by Wandelt who introduced photoemission from
adsorbed Xe as a method to probe the local potential in front of a surface [87W].
The question remains how far the probe has to be above the surface to measure the local potential.
From our remarks up to this point, an atomic distance would be enough as we have only considered the
electrostatic potential of the surface dipole layer. Besides this there is a second contribution, the image
potential which is of larger range. Outside a metal surface (which is the most obvious example) an
electron repels electrons at the metal surface thus modifying its charge density. Between the positive
charge density at the surface and the electron there is an attraction which is described by the well known
image potential, e2/4z, where e denotes the electron charge and z the distance from the surface. The
positive charge induced at the surface can be considered as the residue of the exchange and correlation
hole the electron created around itself in the bulk.

Ref. p. 4.2-118] 4.2 Electron work function of metals and semiconductors 4.2-3
Therefore, a safe distance from the surface at which all distance-dependent changes of the local potential
have vanished is z0 = 104 ǖ >+@ 7KLV GLVWDQFH LV PDFURVFRSLFDOO\ VWLOO D VKRUW GLVWDQFH ,Q RUGHU WR
avoid any influence of the edge fields the lateral distance to such edges should be larger than z0. This is
easily fulfilled for the case, where single crystalline surfaces of a diameter of several mm are studied.
The above cited method of photoemission from adsorbed rare gases does not fulfill this criterion and has,
therefore, to be used with care. The great advantage on the other hand is the small lateral extension of the
rare gas atom probe which makes it possible to study surfaces of very small patches down to locally
stoichiometric compound surfaces. Actually, the method was invented when it was found that
photoemission from Xe physisorbed at steps gives rise to different binding energies compared to those
from the terrace [79K3].
4.2.1.4 Standardization of work-function change with coverage
In Fig. 1 four different types of work-function changes with coverage are sketched. Types I and II are for
electronegative adsorbates as, e.g., for oxygen or chlorine: the electronegative species attracts some
negative charge which increases the barrier for the outgoing electron. Types III and IV are due to an
inversion of the dipole moments of types I and II. Typical examples for electropositive species are the
alkali metals.
∆Φ1 Type I
0 θ1
∆Φ1 Type II
∆Φ2
Work − function change ∆Φ
0 θ1 θ2
Type III
∆Φ1
θ1 θ2
0
∆Φ2 Type IV
∆Φ1 Fig. 1. Four different types of work-function changes ∆Φ as function

of coverage θ. Characteristic maxima, minima, or saturation values are
Coverage θ marked by (θi, Φi).

For all types in Fig. 1 is common that there is a more or less extended linear change with exposure θ for
θ ĺ 0. This is quite easily understood assuming that each adsorbed species contributes by its own typical
dipole moments p to the overall work-function change ∆Φ which is given by the Helmholtz equation
∆Φ = -4πepNa (6)
where Na is the number of adsorbed atoms per unit area. Eq. (6) describes basically the types I and III.
A linear change of Φ with Na is actually not observed, instead the change of Φ per adsorbed atom
becomes smaller. This is formally explained by depolarisation due to lateral interaction between the
dipoles. This has been modeled by Topping [27T] for mobile adsorption:
∆Φ = -4πeµ0Na(1 + 9αNa3/2)-1 (7)
= 3.77·10-15µθ(1 + 9αθ3/2)-1 (7’)
where µ0 is the initial dipole moment (for Na ĺ 0) and α denotes an effective polarizability. In Eq. (7’) θ
is the surface coverage in atoms cm-2, µ the dipole moment in D, and α the polarizability in cm3. This
Topping formula is often used to extract p0 and α from the measured ∆Φ curves. It should be noted,
however, that the depolarization may be a very involved process and may be differ among different
systems. So, it was shown in calculations for Cs/W(100) that not only Cs 6s and W 5d contribute but also
a significant counter-polarization of the Cs 5p shallow core level was found [83W2].
4.2.1.5 Experimental methods
This short paragraph is not intended to describe the experimental techniques to measure work function
and work-function changes in detail. For this purpose one may look into chapter 2.4 or into older review
articles [69R, 72H2, 79H3]. There are basically three absolute methods: Thermionic emission (Therm),
field electron emission (FEM), and photoelectron emission (PYS, ARUPS). Besides this and even more
important are relative methods which can be divided into three groups: secondary electron edge methods
(SE edge), Kelvin methods (Kelvin) and the reflection of electron beams (diode). We have introduced
here the acronyms used in the tables below. Before we start presenting the data collection we will briefly
comment on the above listed methods:
4.2.1.5.1 Thermionic emission (Therm)
According to the Dushman-Richardson equation, the electron current upon heating a substrate of work
function Φ is given by
I = A(1 – r) T2 exp(-Φ/kT) (8)
where A is a known constant, T the temperature, k the Boltzmann constant and r the reflection coefficient
of the outgoing electron at the surface potential barrier. The experiments to deduce Φ from Eq. (8) are
very difficult; the current depends exponentially on Φ and space charge problems can introduce severe
problems. Also the geometry of the emitting surface and fringe fields have to be controlled. Interestingly,
it could be shown that the maximum of the energy distribution of thermoionic emitted electrons shifts
with Φ [85E]. For many adsorbate-induced work-function changes this method is useless, since the
adsorbate may desorb before the temperature is high enough to produce measurable current densities.
4.2.1.5.2 Field electron emission (FEM)
If an electric field is applied to a metal surface the potential barrier at the surface may become narrower
so that electrons may tunnel through the barrier. The field-emitted electron current I is given by the
Fowler-Nordheim equation [28F]
I = BE2 exp(-βE-1) (9)
where B and β are constants containing Φ, and E is the electric field strength. A so-called Fowler-

Nordheim plot of ln(IE-2) vs. E-1 yields a straight line from which Φ can be derived. Usually, field
emission sets in at fields of the order of 106 Volt cm-1. Such fields can easily be obtained if the metal
surface is formed as a tip. As such a tip is composed of different surfaces with different Φ, measuring the
total current leads to only an average value of Φ, weighted towards the surfaces of low Φ. Much more
sensible results are achieved with the probe hole technique by which the current from different areas of
the tip is analyzed separately. It became possible to follow the arrival of single evaporated atoms in the
current jumps from a W(110) surface [77K].
During the sixties FEM was the best-choice method. Later, some drawbacks were clearly recognized
[71F, 81S]:
(1) The shape of the emitter influences the strength of the electric field. If a planar facet is too large,
the field gets reduced in its center region.
(2) The state of the adsorbate may be influenced by the electric field.
(3) There is a large uncertainty about the actual coverage of an adsorbed metal at an individual facet.
The adsorbate under investigation is usually deposited onto one side of the tip which is kept at low
temperature (room temperature) or below. Later the adsorbate is spread over the whole tip at
elevated temperatures. Assuming that an equilibrium between the different faces is achieved this
way, the coverage at the faces with the higher binding energy may be larger.
(4) There may be also structural changes within the adsorbate layer occurring during the preparation at
higher temperatures.
In spite of these difficulties, reasonable results have been collected using the FEM method [79S2, 81S].
4.2.1.5.3 Photoemission (PYS, ARUPS)
We call this method photoemission yield spectroscopy (PYS) if photons near to threshold are used and all
photoelectrons are collected [77S]. If VUV photons are used and photoelectron spectra are measured, we
call the method ARUPS from angle-resolved UV-light photoelectron spectroscopy. Energy conservation
in photoemission is given by
F
Ekin = hν – E B – Φ , (10)
where the kinetic energy Ekin of the outgoing photoelectron is given by the photonenergy hν, the binding
F
energy of the electron E B (with reference to the Fermi edge) and the work function Φ. Eq. (10) indicates
that there is threshold photonenergy (hν)t so that photoelectrons with Ekin 0 are emitted for hν (hν)t.
For a metal the electronic levels are filled up to EF so that
(hν)t = Φ . (11)
So, the photoemission process establishes the possibility to determine an absolute value of Φ. In practice
there are several ways to make use of Eqs. (10) and (11). The first way was to use UV light with
hν (hν)t § 5 eV. It can be shown [31F] that there is a narrow photon energy range (§ 0.5 eV) above
threshold in which the yield of photoelectrons Y(hν) increases proportional to (hν-Φ)2. If one plots
Y(hν)1/2 as a function of hν (Fowler plot) and extrapolates for hν ĺ 0, one can obtain Φ.
The second way could be realized after development of VUV-light sources and energy analyzers for
the photoelectrons. If one collects all electrons without cutting off some at the low energy end of the
spectrum, one measures the width W of the photoelectron energy distribution curve. For a metal this is
quite easy, since both the secondary electron threshold as well as the Fermi edge exhibit a large enough
intensity. Thus, the work function can be determined from
Φ = hν - W. (12)
By this method absolute work function values can be determined with an accuracy of ±10 meV under the
following conditions:

(1) The measurements have to be performed in an angle-resolved mode of photoelectron spectroscopy

(ARUPS). Angle-integrated modes collect, with increasing kinetic energy, an increasing number
of secondary electrons with kɊ 0. The threshold can therefore have a width of up to 1 eV and is
not a sharp level. Therefore, an extrapolation procedure has to be used which always includes
some degree or arbitrariness.
(2) The spectrometer sample configuration should be of such a geometry that a planar electric field is
built in front of the sample, if one supplies the sample with a bias voltage of, e.g., -2 Volt. This
voltage accelerates all photoelectrons by 2 eV and ensures that the full spectrum, including the
electrons of the true secondary-electron threshold, enters the spectrometer.
Both conditions are fulfilled for the ARUP spectrometer (ADES 400, VG Scientific) which we use in our
laboratory. For a Pt(111) surface and a pass energy of the spectrometer of 5 eV we have measured a linear
increase of intensity from 10...90% within 120 meV at the secondary-electron threshold and a 10...90%
drop of intensity within 140 meV at the Fermi edge. Under these conditions the secondary-electron
threshold is as sharp as the Fermi edge. We have therefore included the energy resolution of our
spectrometer at both edges. Furthermore, one can derive great benefit from the VUV-discharge lamps
(e.g., the He-lamp) whose photon energy is precisely known. The energy of the HeIα line, e.g., is
hν = 21.217 eV [70T]. Alternatively, one can perform two-photon photoelectron emission by using UV
lasers. In this case one overcomes the surface barrier with the help of 2hν and hν is also known with high
precision.
4.2.1.5.4 Secondary electron edge method (SE edge)
If photons or charged particles, like electron or ions, interact with bulk material, inelastic processes occur
and so-called secondary electrons (SE) are created. These electrons are in empty states above EF and
even above the vacuum level. They can leave the bulk if their energy (with wave vector perpendicular to
the surface) is larger than Φ (taking EF as the energy zero). The secondary-electron edge, i.e., the energy
interval in which the current of secondary-electron drops to zero has a width of 0.05 to 1.0 eV depending
on geometry and energy resolution of the electron energy spectrometer. Quite clearly, the SE edge shifts
as Φ is changed. This shift can be used to determine a work-function change ∆Φ. The shift is measured
very often at the half height of the SE edge where the SE current depends linearly from energy in most
cases. In our tables, presented below, we have indicated this experimental method by SE edge (XPS)
including in brackets the process which creates the SE edge, XPS given as an example here. Further
probes to create SEs are electrons (E) or UV photons (UPS).
4.2.1.5.5 Diode method (Diode)
If an electron beam is directed towards a surface, it gets reflected if its potential is equal to - (EP/e + ∆Φ),
the negative value of the primary energy divided by e and corrected for ∆Φ between the surface and the
electron emitter (in the widest sense: cathode, electron gun, etc.). Since the surface serves here as the
anode in a diode configuration, the name diode method has been chosen. This method was introduced
early by P.A. Anderson [35A]. Many details of different experimental set-ups are discussed in [73K2,
79H3]. It was pointed out [85K8] that for carefully chosen conditions and for a patchy surface, i.e., a
surface consisting of a composite of smaller areas of different work function, the diode method measures
the same arithmetical average of Φ as the Kelvin method (see below). How to use a HREEL spectrometer
for the diode method is reported in Ref. [85S3].
4.2.1.5.6 Vibrating capacitor method (Kelvin)
The vibrating capacitor method is based on the work of Lord Kelvin [1898K] and of Zisman [32Z]. A
condensor is formed of the surface to be studied and a reference electrode in front of it which are
connected by a ammeter and a variable voltage source. If the capacitance between the plates (sample and
reference electrode) is changed, e.g., by changing their distance, a current will flow. By compensating the

contact potential difference through the voltage source, the current can be brought to zero. Since Φ of the
surface is part of the contact potential, its changes relative to the reference electrode can be measured. A
more extended description can be found in Ref. [79H3]. A very versatile instrument of this kind was
developed by Besocke [76B].
4.2.1.6 Data collection
Data have been collected for metal as well as semiconductor substrates. In the case of metals only
elemental, single-crystalline samples were considered. There are a few exceptions to this general rule.
Some metallic alloys are listed in case of single-crystalline samples of well defined (stoichiometric)
composition. Some data are also incorporated for evaporated, mostly polycrystalline films of materials for
which no single-crystal data are available. For semiconductor substrates, adsorbate-induced work-
function changes consist of two contributions: band-bending and electron-affinity changes. Systems were
discarded for which the overall change in work function was small (<0.2 eV) or for which the authors did
not report a separation of the two contributions. With respect to the adsorbates, only single-component
adsorption layers were considered, i.e., co-adsorbates were omitted. Furthermore, it should be noted that
completeness – although intended – could not be achieved. It was learned that work-function data are
very often not in the center of a publication. Work-function data even seemed to many authors too
marginal to give explicitly reference to them in the title, abstract or key words. Therefore, also computer
based research could not guarantee completeness.
In the tables the following data are listed:
1. Reference (Ref.),
2. Substrate, polycr. means evaporated film which is very likely polycrystalline.,
3. Sample temperature T [K] during measurements,
4. Method of ∆Φ measurement,
5. The type (Type) of ∆Φ variation with increasing coverage as described in section 4.2.1.5,
6. The work-function change ∆Φ at θ1 (+∆Φ or ∆Φ means increase of Φ, –∆Φ decrease of Φ),
7. Coverage θ1, for which ∆Φ is determined; sometimes θ1 marks a relative coverage for which
extrema of the ∆Φ variation occur; ML stands for monolayer. A coverage notation θindex is defined
as the number ratio of adsorbed index atoms and substrate surface atoms.
8. Comments refer to additional methods applied to characterize the substrate surface and remarkable
results. µ0 is the dipole moment of the adsorbate for coverage extrapolated to zero (in units of
Debye (D)). α is the respective polarizability (in units of cm3).
If the method or substrate temperature are not mentioned in the reference these informations could not be
included in the tables. A missing temperature mostly indicates room temperature measurements (300 K).
If the method was not unambiguously identified it is set into parentheses in the table: (method).
The electron work-function data are presented in tables. Figures are shown only for some remarkable
results. Exception is made for H, CO and Cu for which more figures are shown. These systems may serve
as examples for all the other adsorbates.
4.2.2 Rare gases

In the late forties Mignolet discovered that adsorption of inert gases produces a large decrease in work
function of transition metals [50M]. Although these data [53M] were collected still in the “glass age” of
ultra-high vacuum, they are remarkably correct compared to what we know today. Therefore, we have
added them to the collection. A decrease of Φ by 0.5 to 1 eV was a great surprise at that time since one
did not expect any charge transfer resulting in a dipole formation for physisorbed gases. Only in the
seventies this phenomenon could be explained as a valence charge fluctuation stabilized by the image
force between the metal surface and the center of the rare gas atom.

Table 1. Neon (Ne)
Ref. Ne/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
87J2 Ga Polycr. 10 SE edge -0.15 ML
(UPS)
Table 2. Argon (Ar)
Ref. Ar/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
87J2 Ga 10 SE edge -0.1 ML
(polycr.) (UPS)
82J Ni(110) 20 ARUPS -0.6 multilayer
88J Pb(111) 20 ARUPS -0.13 ML LEED, ARUPS
-0.145 2. layer
70E3 W(100) FEM -0.46... µ0 = 0.31 D at monolayer density
-0.6 of Ar of 7.9·1014 atoms cm-2
70E3 W(110) FEM -0.85... µ0 = 0.29 D at monolayer density
-1.05 of Ar of 7.9·1014 atoms cm-2
70E3 W(111) FEM -0.40 µ0 = 0.16 D at monolayer density
of Ar of 7.9·1014 atoms cm-2
Table 3. Krypton (Kr)
Ref. Kr/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
76R3 Ag(111) 77 Kelvin -0.29 LEED
76R3 Cu(211) 77 Kelvin -0.35 LEED
82J Ni(110) 20 ARUPS -0.6 multilayer
-0.14 2. layer
84M Pd(100) -0.36(5) µ0 = 0.17 (5) D
α = 1.7 cm-24 cm3
70E3 W(100) FEM -0.83 µ0 = 0.38 D at a monolayer atom
density of Kr of 7.2·1014 atoms cm-2

Table 4. Xenon (Xe)
Fig. 2. Xe adsorption on Pd(110)
Ref. Xe/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
73C2 Ag(110) 77 Kelvin -0.45 LEED
73C2 Ag(111) 77 Kelvin -0.44 LEED
76M3 Ag(111) 77 Kelvin -0.45 LEED
76R3
86B5 Ag(111) 20 SE edge III -0.48(1) monolayer TDS, XPS, UPS,LEED
(UPS) -0.6 multilayer UPS angle-integrated
µ0 = 0.2 D
86J3 Ag(111) 58 SE edge -0.48 µ0 = 0.2 D
(UPS)
73C2 Ag(211) 77 Kelvin -0.45 LEED
72K Ag 77 Diode III -0.47
(polycr.)
80C2 Al(111) 40 SE edge -0.29 1 ML
(UPS) -0.33 multilayer
84C Al 15 Kelvin III -0.25 1 ML* *1 ML has been taken as 6·1014
(polycr.) atoms cm-2
74N Au 78 PYS -0.52 ML
(polycr.)
76M2 Au(100) 77 Kelvin -0.45 AES, ELS, LEED
88A Ba 20 ARUPS -0.1 ML
(polycr.) >-0.2 2. layer
53M Ca 77 Kelvin 0.0
(polycr.)
53M Cr 77 Kelvin -0.9
(polycr.)
74K Cs 77 Diode 0.0
(polycr.)
83R2 Cs 10 ARUPS 0.0 ARUPS
(polycr.)
84C Cs 15 Kelvin -0.025 1 ML
(polycr.)
71C4 Cu(100) 77 Kelvin -0.47 45 L LEED
73C2 Cu(100) 77 Kelvin -0.47 LEED
73C2 Cu(110) 77 Kelvin -0.61(2) LEED
82M2 Cu(110) 45 ARUPS III -0.61(2)
73C2 Cu(111) 77 Kelvin -0.48 LEED
86J3 Cu(111) SE edge -0.58 µ0 = 0.24 D
(UPS)
86E3 Cu(111) SE edge -0.58 µ0 = 0.24 D
(UPS)
76R3 Cu(211) 77 Kelvin -0.53 LEED
75P Cu(311) 77 Kelvin III -0.58 LEED, AES


Substrate
75P3 Cu(100) 77 Kelvin III -0.47
Cu(111) -0.48
Cu(110) -0.61
Cu(211) -0.53
Cu(311) -0.55
Cu(755) -0.53
71K Cu 77 Diode -0.57
(polycr.)
74N4 Cu 78 PYS -0.63 ML
(polycr.)
53M Fe 77 Kelvin -0.66
(polycr.)
80P Fe(110) -0.3
74N Fe 78 PYS -0.5 ∆Φ values for surfaces annealed at
(polycr.) higher temperatures do not vary
much
87J2 Ga 10 SE edge -0.25
(polycr.) (UPS)
88P2 Ge(111)- 60 SE edge -0.22(1) ML µ0 = 0.14 D
c(2 × 8) (E)
82L4 Gd(0001) SE edge -0.6
(UPS)
53M Hg 77 Kelvin -0.23
(polycr.)
74N2 Ir(100) 78 FEM -1.6
Ir(110) 78 FEM -0.8
Ir(111) 78 FEM -1.8
Ir(210) 78 FEM -1.3
Ir(321) 78 FEM -1.0
74N Ir 78 FEM -1.05 ∆Φ values for surfaces annealed at
much
53M K (polycr.) 77 0.0
84C K (polycr.) 15 Kelvin -0.05 1 ML* *1 ML has been taken as 6·1014
atoms cm-2
84C Li 15 Kelvin III -0.1 1 ML* *1 ML has been taken as 6·1014
84C Mg 15 Kelvin III -0.3 1 ML* *1 ML has been taken as 6·1014
74M6 Mo -0.70
(polycr.)
71K Na 77 Diode 0.0
(polycr.)
84C Na 15 Kelvin III -0.05 1 ML* *1 ML has been taken as 6·1014
82C Ni(100) 30...100 Kelvin III* -0.38 10 L *very weak Type IV
LEED, TDS, UPS
µ0 = 0.29 D
86M2 Ni(100) 20 SE edge -0.3 ML TDS, AES, influence of K
(UPS)


Substrate
82J Ni(110) ARUPS -0.75
83R2 Ni(110) 20 ARUPS -0.75 ML ARUPS
-0.90 2. layer
53M Ni 77 Kelvin -0.85
(polycr.)
74N Ni 78 PYS -1.01 *film annealed at 590 K
(polycr.) 590* -0.6
74N4 Ni 78 PYS -0.82 ML
(polycr.)
88J Ni(111)- 20 ARUPS 0.0 Xe 5p and 4d levels
(7 × 7)Pb
85D2 NiO SE edge -0.4(2)
(UPS)
-0.135 2. layer
71P Pd(100) 77 Kelvin -0.94 at 6 L LEED, AES, Fig. 2
µ0 = 0.95 D
α = 8.2·10-24 cm3
80K Pd(100) 40 SE edge -0.65 1 ML
(UPS)
84M Pd(100) SE edge III -0.70(2) LEED: no 2D island at 10 K
(E) µ0 = 0.45(3) D
α = 3.6(8)·10-24 cm3
84W Pd(100) 95 SE edge III -0.86(2) LEED, AES, UPS; hcp Xe layer
(UPS) µ0 = 0.61 D
α = 8.4·10-24 cm3
79K2 Pd(110) 100 SE edge III -0.92(1) LEED, TDS, UPS
(UPS) µ0 = 0.42 D
84W Pd(110) 95 SE edge III -0.96(2) LEED, TDS, UPS; hcp Xe layer
(UPS) µ0 = 0.44 D
84W Pd(111) 95 SE edge III -0.85(2) LEED, TDS, UPS;
(UPS) (¥î¥5ÛVWUXFWXUH
µ0 = 0.70 D
83M2 Pd(810) 40 SE edge -0.27(2) step edges µ0 = 1.12 D
[8(100)î (UPS) -1.03(2) full layer µ0 = 0.49 D
(110)] -1.26 2. layer µ0 = 0.11 D
74N Pd 78 PYS -1.12 ∆Φ values for surfaces annealed at
much
74N3 Pt(100) FEM -1.0 *values taken from Fig. 3 of
Pt(111) FEM -0.85* [74N3]
Pt(110) FEM -0.95*
Pt(210) FEM -1.1
Pt(311) FEM -0.9
Pt(321) FEM -0.9
86S2 Pt(111) 40 SE edge -0.6 AES, UPS
(UPS)
89A Pt(111) 95 SE edge III -0.55 θXe = 1 UPS
(UPS)


Substrate
96O3 Pt(111) < 50 Diode IV -0.58 at 2θ1 ARUPS
-0.53 at 3θ1 dips in ∆Φ var
3 different ordered structures
µ0 = 0.3(1) D
74N Pt 78 PYS -0.90 *film annealed at 573 K
(polycr.) 573* -0.65
74N4 Pt 78 PYS -0.95 ML
(polycr.)
74N Rh 78 PYS -1.09 ∆Φ values for surfaces annealed at
much
74N4 Rh 78 PYS -1.08
(polycr.)
81W Ru(0001) SE edge III -0.50 µ0 = 0.25 D
stepped (UPS) µ0 = 1.0 D at step edges
µ0 = 0.34 D at step edges
86J3 Ru(0001) SE edge -0.72 µ0 = 0.3 D
86E3 (UPS)
87S5 Ru(0001) -0.65
74N Ru 78 PYS -0.95 ∆Φ values for surfaces annealed at
much
53M Se 77 Kelvin -0.1
(polycr.)
74K Sn 77 Diode 0.0
(polycr.)
53M Ti 77 Kelvin -0.84
(polycr.)
70E3 W(100) FEM -1.35 µ0 = 0.97 at a Xe atom monolayer
density of 6·1014 atoms cm-2
75W W(100) 80 SE edge -0.99(5)
(UPS)
80W W(100) Kelvin -1.05(2) at 4·1014 also co-adsorption of oxygen
atoms cm-2 µ0 = 0.98 D
α = 6·10-24 cm3
70E3 W(110) FEM -2.4 µ0 = 1.67 D at a Xe atom density of
6·1014 Xe atoms cm-2
later it was noted that Fowler
Nordheim equation breaks down
for Xe/W(110) [80W]
80C W(110) FEM -2.0 ML
80L W(110) FEM -2.0 1 ML
80W W(110) Kelvin -0.45(2) also co-adsorption of oxygen
µ0 = 0.35 D
α = 6.6·10-24 cm3
83O W(110) 30 FEM -2.1
of 6·1014 Xe atoms cm-2


Substrate
74D W(111) 104 Diode III* -1.1 (1) at 1·1015 ∗shows a weak Type IV behavior,
atoms cm-2 TDS
µ0 = 0.66...0.75 D
α = 3.5...4.9·10-24 cm3
70E3 W(120) FEM -1.4 µ0 = 0.6 D at monolayer density of
6·1014 Xe atoms cm-2
of 6·1014 Xe atoms cm-2
53M W 77 -1.14
(polycr.)
53M Zn 77 Kelvin -0.21
(polycr.)
4.2.3 Atomically chemisorbed adsorbates

4.2.3.1 Atomic Hydrogen (H), Atomic Deuterium (D)
Fig. 3...10
Table 5. Atomic Hydrogen (H), Atomic Deuterium (D)
Ref. H, D/ T [K] Method Typ ∆Φ [eV] at θ1 Comments, interpretation

Substrate
89Z3 Ag(111) 100 SE edge -0.17 at saturation TDS, UPS
(UPS)
93S3 Ag(110) 100 Diode I 0.22 1L LEED, TDS, HREELS
95G Ag(111) 100 Diode I 0.32 0.55 LEED, TDS, HREELS
TDS: β2 (180 K), β1 (160 K)
(shoulder)
LEED: (2 × 2); 0.25 < θH < 0.5
(2 × 2) + (3 × 3); θH > 0.5
HREELS: threefold-hollow site;
µ0 = 0.18 D
80K3 Al(100) 300 Kelvin I +0.24 2L
+0.25 200 L
90R Be(0001) 100 -0.55 θ = 0.04 HREELS
-0.45 θ = 1.0
94E Co(10 1 0) 85 Kelvin II 0.20 θH = 1 LEED, TDS, HREELS
0.10 θH = 1.5 α and β states in TDS
LEED: c(2 × 4), p2mg(2 × 1);
p2mg(2 × 1) at θH = 1.5 used for
calibration.
(1 × 2) at θH = 1.5 assigned to a
paired row structure.
94R Cu(110) 90.... Kelvin IV 0.11 20 L LEED, TDS
400 -0.5 500 L The main effects in ∆Φ are due to
changes in reconstruc-tion from
(1 × 1) into (1 × 2).


Substrate
77B2 Fe(110) 140 Kelvin III -0.08 500 L LEED, TDS, UPS
Fe(100) 140 Kelvin I +0.07 500 L
Fe(111) 140 Kelvin I +0.23 500 L
81E Fe(111) 140 I +0.22 20 L TDS
84S Ge(100) 300 Kelvin II +0.18 0.05 ML ELS
+0.05 0.5 ML surface conductivity
+0.05 1.0 ML
Ge(111) 300 Kelvin IV -0.05 0.05 ML
+0.12 0.6 ML
82D Ir(100) 77 FEM IV -0.22 1L
-0.14 100 L
80I Ir(110) 140 Diode +0.3 0.25 L TDS
-(1 × 2) -0.05 25 L β2 sites
β1 sites
77D Ir(111) FEM -0.8
Ir(100) -0.8
73C Mo(110) FEM II 0.48 5L
0.3 7L
0.45 16 L
Mo(100) I 0.68 40 L
Mo(111) I 0.42 50 L
89E Mo(110) 350 Diode IV -0.015 0.2 L TDS, ESD
+0.12 3L
74H2 Nb(100) 90 Kelvin +0.52 at 10 L
74D3 Ni(001) 300 Kelvin +0.08 LEED
Ni(110) 300 Kelvin +0.40 max LEED (1 × 2)
83K Ni(100) 100 SE edge II +0.17 0.5 L UPS, TDS
(UPS) +0.11 17 L (sat.)
84P5 Ni(100) 95 SE edge +0.1 θD = 0.5 TDS, XPS
(UPS, E) +0.05 θD = 1.0 co-adsorption with D
74T Ni(110) 170 Diode? I 0.58 2L LEED, AES
300 0.50 9L
85G Ni(110) 175 ? +0.23 (2 × 1) phase in LEED
+0.50 (1 × 2) phase in LEED
87J Ni(110) 175 Kelvin 0.25 θH = 1 (2 × 1) θH = 1.0 (β2 state)
88H µ0 = 0.054 D
86N3
0.5 θH = 15 (1 × 2) θH = 1.5 (α state)
µ0 = 0.1 D
LEED, TDS, RBS, NRA
See Figs. 3, 4.
98V Ni(110) (300) Diode I 0.35 4L LEED, AES, TDS


Substrate
74C3 Ni(111) 300 Kelvin, I 0.20 sat. (1 × 1)
Ni(100) 300 Diode I 0.16 sat. (1 × 1)
Ni(110) 120 I 0.53 sat. streaks, than 1 × 2
LEED, AES, TDS
77D4 Ni(111) 80 SE edge 0.16 14 L
(E)
300 0.12 6L
86I Ni(111) SE edge II 0.45 6L LEED, AES, TDS, ESD
(E) 0.10 20 L
79C2 Ni(111) 150 Kelvin II 0.18 0.5 θmax LEED, TDS; see Fig. 5
0.09 0.9 θmax Delocalisation of H discussed
94W2 Pd(100) Theory 0.18 θH = 1.0 4-fold hollow site for θH = 1.0 in
0.21 θH = 1.25 addition subsurface sites up to θH
0.15 θH = 2.0 = 2. See Fig. 6.
Rh(100) Theory
80B4 Pd(100) 170 Kelvin I +0.2 θ = 1.35 LEED, TDS. See Fig. 7.
83C Pd(110) 120 Kelvin I 0.33 1L (2 × 1) at 0.3 L
(1 × 2) > 0.5 L not observed as
discontinuities in ∆Φ.
LEED, TDS
88H4 Pd(110) 140 Kelvin I 0.30 4 L; θ = 1.5 LEED, TDS
(2 × 1): θ = 1
(1 × 2): θ = 1.5
Authors discuss 2 surface phases
and a subsurface hydrogen phase.
89M Pd(110) 130 Kelvin I 0.30 LEED, TDS, NRA, RBS
Authors discuss subsurface D!
90H2 Pd(110) 100 Kelvin I 0.30 1.5 ML TDS
98M Pd(210) 120 Kelvin I 0.17 5L LEED, TDS, HREELS
77D4 Pd(111) 80 SE edge 0.14 1L
(UPS) 0.18 2L
98D Pd(111) Theory 0.18 [74C] good agreement with the given
Pd(110) Theory 0.32 [74C] references
Pd(100) Theory 0.20 [80B]
99F Pd(311) 120 Kelvin I +0.25 θH = 1 LEED, TDS, HREELS
91P3 Pt(100) 100 Kelvin IV +0.07* b state LEED, TDS
-0.18* a1, a2, b three (a1, a2, b) states; state b
states transfers the Pt(100) hex into the
Pt(100) (1 × 1) surface at 330 K.
*with respect to Pt(100) hex
phase; see Fig. 8.
91P2 Pt(100) 35 Kelvin -0.37 at 100 L LEED, TDS
4 H-states: a1, a2, a3, b
At 35 K (100)hex structure not
lifted by H adsorption.


Substrate
76N Pt(111) 78 FEM -0.56 p H 2 = 2·10-9 Torr
Pt(100) probe-hole -0.37
~Pt(110) +0.10 p H 2 = 2·10-9 Torr
Pt(210) +0.14
p H 2 = 2·10-9 Torr
p H 2 = 2·10-9 Torr
76C Pt(111) 130 Kelvin, III -0.35 sat.
76C2 Pt(997) Diode II +0.02 0.25θsat
-0.35 θsat
76C2 Pt(111) 300 Kelvin, III -0.23 ∆φ = -0.23 × θ1.33 eV
Diode LEED, TDS, ELS
77D4 Pt(111) 80 SE edge -0.2
(E)
79N2 Pt(111) 95 Kelvin III -0.45
87E Pt(110) 120 Diode II 0.17 θH = 0.3 β2 state
-(1 × 2) -0,5 θH = 1.0 β1 state; saturation
LEED, TDS
92S Pt(110) 170 Diode IV 0.15 θrel = 0.05 LEED, TDS
-(1×2) (LEEM) -0.7 θrel = 1 two H states in TDS: β1, β2
92S6 Pt(110) Diode +0.14 0.1 L
0.0 0.2 L
-0.4 0.6 L
-0.65 20 L
94F2 Pt0.5Ni0.5 120 Diode I +0.60 θH = 0.9 LEED, TDS, NRA
(110)
76E2 Re film 300 Diode I 0.2 1.5·1014 molecules cm-2 (sat.)
Also results for O, CO, C2H4
82D2 Re* 300 FEM II 0.52 50 L * The central plane of the tip is
0.35 1000 L (10 1 0).
95M2 Re(10 1 0) 120 Kelvin II 0.37 2L LEED, TDS
0.15 40...2000 L TDS: α, β1, β2 states
LEED: c(2 × 2)-2H, (1 × 1)-2H
84P Rh(100) 100? SE edge I 0.2 sat. UPS, XPS, ELS
(UPS) A weak max. in ∆Φ is observed
with coverage.
84H2 Rh(100) 100 Diode I 0.2 sat. LEED, TDS
84P6 Rh(100) 100 SE edge +0.20 θD = 0.9 UPS, TDS
(UPS, E)
87K Rh(100) 300 PYS I 0.27 7·104 L AES
Rh(111) 300 PYS II 0.23 (sat).
0.18 6·103 L
7·104 L
(sat.)
87C2 Rh(110) 100 Kelvin I 0.9 sat. LEED, TDS
88E There are several changes in slope
in ∆Φ (exposure) and several
LEED structures.


Substrate
87K Rh(111) 300 PYS IV -0.23 min
-0.20 saturation
Rh(100) 300 PYS III -0.28 saturation
91N Rh(113) 90 0.97 θH = 1 LEED, TDS
Low-coverage structures
(1×3)−Η, (1×2)−Η, (1×3)−2Η
have no influence on Rh surface
structure.
High-coverage structure
(1×2) opens diffusion channels to
subsurface sites.
85F Ru(0001) 95 Kelvin II 0.025 70 Ex There are two states.
-0.01
0.03 depending on temperature
LEED, TDS
86H3 Ru(0001) 80 Kelvin II some small changes of Φ as
observed in [85F]
91S2 Ru(0001) 45 Kelvin +0.030 0.5 L LEED
+0.048 0.8 L 3 phases in LEED
+0.030 1.1 L
+0.005 2.5 L
89L2 Ru(10 1 0) 100 Kelvin II 0.42 θ =1 LEED, TDS, HREELS
96C 0.30 θ =2 three structures in LEED
96B Si(100) 300 Diode -0.25 TDS
-(2 × 1) atomic H used
66E W(100) 300 Diode I 0.9 1×1015 mole LEED
(ribbon) -cules cm-2
69A W(100) 300 Thermo- 0.2 sat.
emission
72P W(100) 300 FEM I 0.9
W(110) 300 FEM II -0.5
73C W(110) FEM II 0.83 0.1 L
0.0 10 L
W(100) I 0.73 6L
W(112) I 0.65 1.2 L
74F2 W(100) 300 SE edge +0.9 UPS
(UPS)
84H5 W(100) 300 Diode I +0.55 θH = 0.45
450 Diode I +0.27 θH = 0.45
86H2 W(100) 300 Diode I 0.97 3L step at 0.2 L;
W(110) 300 III -0.46 35 L ∆Φ = 0.25 eV
73R W(112) Kelvin II 0.61 1/2θsat linear increase
β2 state (TD = 675 K) filled
0.27 θsat linear decrease
β1 state (TD = 330 K) filled


Substrate
74B W(110) * Kelvin III -0.5
W(111) I +0.26
W(112) II 0.6 0.5θsat linear increase
+0.32 θsat linear decrease
W(100) I 0.9 linear increase
See Fig. 9.
TDS
*dosed at 135 K
97N W(110) 90 Kelvin III -0.3 8L LEED
-0.5 240 L See Fig. 10.
72M3 W(111) 300 Diode I +0.07(2) TDS
125 +0.21(2)
70A W(112) (300) Kelvin I 0.7 LEED, TDS
97C W(310) 77 FEM II 0.56 0.5 L
probe hole 0.43 4L
0.43 20 L
77M ZnO
(0001)Zn FEM -0.2
(000 1 )O FEM -0.7
96Z Zr(10 1 0) 100 Kelvin IV -0.01 0.25 L AES, NRA, SIMS

96C +0.075 3.0 L
370 III -0.06 >0.7 L Results are discussed in terms of
two H sites: one site above the
surface (∆Φ > 0) and one
subsurface site (∆Φ < 0).
4.2.3.2 Atomic Carbon (C, C60)
Table 6. Atomic Carbon (C)
Ref. C/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
74D3 Ni(001) 300 Kelvin ~+0.5 LEED p(2 × 2)
74G Pt(111) 1170 -1.1 LEED:
-(1 × 1) ringlike diffraction features
Pt(100) 1170 -1.1 LEED:
-(5 × 1) ringlike diffraction features
86A3 Pt(111) * Kelvin -0.5 θC = 0.75 *hydrocarbons at a hot (500 K)
Pt(111) surface
AES gives coverage

Table 7. C60
Ref. C60/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
96M3 Al(111) SE edge +0.95 1 ML XPS
(UPS)
Al(110) +0.95 1 ML
97K3 Cu(111) SE edge -0.08 1 ML LEED, UPS, XAS
(UPS) See also Table 8.
94G2 GeS(001) SE edge 0.1 1 ML LEED, X-Diffraction, SEM, XPS,
(UPS) UPS
C60(111)-lage
94J Rh(111) SE edge III -0.5 1 ML UPS, EELS
(UPS)
93R3 Ta(110) SE edge +0.6 1 ML ARUPS
(UPS) first C60 molecules are decomposed
Table 8. Work functions of clean metal surfaces and after adsorption of a monolayer C60. From [97K3].
Conclusion: All C60 monolayers are metallic showing a work function of about 5 eV. The dipole layer at
the substrate-C60 interface is screened out by the C60 film.
Ref. Surface Clean surface Φ [eV] of 1 ML ∆Φ [eV]

Φ [eV] C60 on surface
[97K3] Cu(111) 4.94 4.86 -0.08
[97K3] Ni(111) 5.36 4.93 -0.43
[96M3] Al(110) 4.35 5.25 +0.95
[96M3] Al(111) 4.25 5.15 +0.95
Au(119)a 5.37 4.82 -0.45
[94J] Rh(111) 5.4 4.9 -0.5
[93R3] Ta(110) 4.8 5.4f +0.6b
a
) P. Rudolf et al, unpublished, quoted in [96M3]
b
) for reference only, since C60 decomposes on this surface at RT
4.2.3.3 Atomic Nitrogen (N)
Table 9. Atomic Nitrogen (N)
Ref. N/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
90S Cr(110) 300 SE edge -0.55 UPS
(UPS) adsorbed at 90 K and annealed
stepwise to 300 K;
transformation N2 ĺ1IROORZHG
by UPS
98G Cu(100)/ 75 Kelvin I 0.8 ± 0.1 for epitaxial fcc-Fe films of
Fe(100) thickness 1.2...8 ML
fcc Exposure 3000 L
79G Ni(110) 590 Kelvin III -0.5 4·105 L LEED, TDS
p(2 × 3), authors discuss formation
of surface nitride

Ref. N/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
91B4 Rh(111) SE edge I +0.45 θN = 0.4 microwave discharge to produce
(UPS) atomic N
69A W(100) 300 Therm -0.7 saturation
71A W(100) 300 Kelvin IV -0.55 2L
-0.50 4L
W(210) 300 Kelvin I 0.25 4L
W(310) 300 Kelvin I 0.18 4L
74F2 W(100) 300 Kelvin -0.3 UPS
93O W(100) 400 Kelvin IV -0.4 5L ELS
-0.35 300 L
89S2 W(110) 200 Kelvin? 0.2 Chemisorbed N2 at 90 K irra-diated
with electrons and heated to 200 K
4.2.3.4 Atomic Oxygen (O)
Fig. 11 and 12
Table 10. Atomic Oxygen (O)
Ref. O/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
76E Ag(110) 300 Kelvin I 0.85 sat. (n × 1) LEED structures
Ag(100) 300 III -0.15 1000 L
400 I +0.3 1000 L
Ag(111) 300 0.04 p=10-5 Torr no Auger signal!
O2 i.e. sticking coefficient very small
85S3 Ag(110) 300? Kelvin I 0.625 sat. 5000 L LEED, AES
Diode 0.32 θ = 0.25 LEED: (4 × 1)
0.5 θ = 0.3 LEED: (3 × 1)
0.72 θ = 0.50 LEED: (2 × 1)
73D Ag(111) 300? photo- I 0.4 1400 L
electric
78M2 Ag(331) 300 Diode +0.7(1) LEED, AES
facetted (2 × 1)
77B5 Al(111) 300 Kelvin -0.17 50 L chemisorbed layer
-0.21 300 L oxidation
79H4 Al(111) 300 Kelvin III -0.2 500 L
Al(110) 300 Kelvin III -0.48 500 L
Al(100) 300 Kelvin III -1.08 500 L
77G4 Al(111) 300 PYS I +0.12 100 L AES
Al(110) III -0.05 200 L
Al(100) III -0.48 300 L
80M Al(111) Kelvin III -0.2 350 L LEED, AES
Al(110) -0.8 350 L
-1.25 350 L
88M Al(100) 300 Kelvin III -0.7 3·103 L
-0.8 8·103 L depending on pressure
116 II +0.25 400 L At low temperatures oxygen stays
+0.05 1600 L first on top.


Substrate
98S3 Au(111) 300 I 0.85 1.3 ML LEED, AES, TDS, HREELS, XPS
oxidation through O3;
see Fig. 11
78G5 Be(0001) PYS III -1.8 3000 L LEED, AES
83T Bi(0001) 300 SE edge III -1.1 sat. LEED, AES, ELS
(E) presumably oxide formation
82C3 Co(0001) 300 Kelvin? I 0.55 5L LEED, AES, UPS
93K3 Co(11 2 0) 100 SE edge 1.1 LEED, UPS, XPS

(UPS)
300 -1.0 oxide formation
95G2 Co(11 2 0) 100 SE edge I 1.0 3L AES, UPS, XPS
(UPS)
320 IV 0.8 1L island growth of oxide
0 5L
-0.1 12 L
97K2 Co(11 2 0) SE edge -0.4 at 1.5 L LEED
(UPS) CoO(100) formation
79P Cr(100) 300 SE edge IV -0.2 2L LEED, AES
(UPS) +1.7 20 L at ∆Φ = 0.4 (5 L) oxidation starts
78G Cr(111) 300 SE edge 0 <1 L XPS, UPS
300 (UPS) II 0.9 10 L C2O3 formation
0.4 1000 L C2O3 formation
300* III -1.2 * plus annealing at 770 K
82S7 Cr(110) 300 Diode II +0.2 2L LEED, AES, ELS
0.0 3L
-0.25 6L
0.0 10 L
+0.3 15 L
+0.15 40 L
85F2 Cr(100) 300 Diode I +2.4 300 L
Cr(110) 300 Diode I +1.2 300 L
86F4 Cr2O3 I +2.0 1.5 L
(0001)
71D Cu(111) 300 Kelvin I 0.13 sat.
Cu(100) 300 Kelvin 0.40 sat.
Cu(110) 300 Kelvin 0.68 sat.
72E Cu(110) Kelvin 0.25 LEED: O(2 × 1) structure; AES
78H Cu(100) 350 Kelvin 0.33 100 L LEED; at higher T decrease of Φ
at higher exposures
79H Cu(110) 475 Kelvin I 0.38 12 L LEED
80H Cu(100) 600 Kelvin II 0.3 80 L LEED, AES, Ellipsometry
0.0 500 L
83N2 Cu(110) 300 Kelvin 0.25 LEED, AES, ISS
Cu(111) 300 Kelvin <0.02 oxygen on top, disordered layer
84B Cu(110) 300 Kelvin I 0.36 10 L LEED, UPS, TDS
110 II 0.43 0.8 L
0.37 10 L


Substrate
82S3 LEED, AES, UPS, ELS
Cu(111) 300 SE edge 0.0 1000 L AES indicates θ0 = 0.32 ML;
(UPS) therefore the authors conclude
surface penetration of O atoms.
100 -0.4 1000 L
82S4 Cu(111) 300 SE edge I 0.0 up to LEED, AES, UPS, ELS
(UPS) 1000 L At 100 K: 2-peak spectrum in
100 III -0.4 1000 L (UPS); chemisorbed O2.
At 300 K: incorporation of atomic
O into the Cu surface discussed.
95S7 Cu17Al83 +0.43 at 6 L O2 UPS
(100)
84S10 Fe(100) 300 Diode II 0.25 3L LEED, AES, ELS
0.02 20 L
0.20 45 L
86M3 Fe(110) 300 Diode II 0.58 6L AES, LEED, ELS
0.0 60 L
-0.1 100 L
81S2 Ga polycr. 300 SE edge IV +0.4 10 L O2 condensed at 20 K and
(UPS) annealed to 300 K
76D GaAs(110) 300 Diode I 1.2 6·105 L
85I GaAs(110) Kelvin
cleaved
p-type -0.7 30 L O2
n-type 0.0 100 L O2
86I2 GaAs(110) Kelvin
cleaved
p-type -0.52 2·104 L O2
n-type +0.42 2·104 L O2
93N GaAs(110) 60...300 Kelvin oxygen induced surface acceptors
cleaved
p-type 0.0 < 103 L O2
-0.3 5·104 L O2
n-type +0.4 5·104 L O2
87B3 GaSb(110) 300 Kelvin
cleaved
p-type -0.05 4·102 L O2
-0.15 4·103 L O2
n-type +0.5 4·102 L O2
+0.35 4·103 L O2
72M Ge FEM 0.8
85I InAs(110) Kelvin
cleaved
p-type -0.7 30 L O2
n-type 0.0 100 L O2
86B2 InAs(110) 300 Kelvin
p-type -0.4 104 L O2
n-type -0.15 104 L O2
76I Ir(111) 300 Diode +0.56(4) saturation


Substrate
79T Ir(110) 90 Diode I +0.65 10 L LEED, AES, TDS
300 +0.45 10 L
725 +0.1 10 L
82D3 Ir(100) 77 FEM 0.6 1L
Ir(111) 77 FEM 0.95 <0.1 L
97L3 Ir(110) 300 Kelvin I +0.7 1L XPS
+1.1 15 L
78G4 LaB6(100) 100 Diode I +1.3 20 L LEED, AES, TDS
80N LaB6(100) SE edge I +1.6 LEED, UPS
(UPS) µ0 = 0.54 D
82N LaB6(110) 300 SE edge I 1.3 1.5 L LEED, UPS, XPS
LaB6(100) 300 (UPS) I 1.7 3L
LaB6(111) 300 I 1.1 1.5 L
81N2 Mg(0001) 300 Kelvin IV -0.8 8L LEED, ELS
-0.1 100 L
0 150 L
81H Mg(0001) Kelvin IV -1.3 12 L LEED, ELS, Ellipsometry
-0.9 50 L
Mg(10 1 0) Kelvin IV -1.4 14 L
-1.2 50 L
82L5 Mg(0001) 300 Kelvin IV -1.2 min at 12 L
-1.0 20 L
Mg(10 1 0) 300 Kelvin IV -1.4 min 15 L
-1.25 22 L
74M3 Mo(100) FEM I +0.9 1016 atoms cm-2
+1.4 1018 atoms cm-2
Mo(110) I +0.8 2·1015 atoms cm-2
Mo(111) II +0.5 intermediate max. at 7·1014 atoms cm-2
Mo(112) II +0.55 2·1015 atoms cm-2
+0.1 1018 atoms cm-2
75Z Mo(110) 300 Diode I 1.35 LEED also at 900, 1100, 1300 K
75R Mo(100) 370... Diode IV -0.4 1L LEED, AES
500 1.3 12 L
79B3 Mo(100) 300* Diode IV -0.35 1L LEED, AES, TDS
+1.4 12 L *also at 1100 K similar behavior
75Z2 Nb(110) 300 Kelvin IV -0.6 θ1 LEED
+1.0 4 θ1
77P Nb(100) 300 Diode IV -0.4 0.5 L LEED
1.5 5L
Nb(110) 300 Diode IV -0.45 1L for Nb(110) see also [79J]
+0.7 25 L
Nb(111) 300 Diode -0.16 0.5 L
+1.1 6L
85K3 NbC(100) 300 I 1.2 8L LEED, AES, UPS
NbC(111) 300 -0.2 10 L
71S Ni(100) 300 INS* +0.30(5) LEED p(2 × 2)
+0.37(5) LEED c(2 × 2)
*ion neutralization spectroscopy;
assuming ΦNi(100) = 4.75 eV
72E Ni(110) Kelvin 0.60 LEED, AES


Substrate
73B2 Ni(111) Diode* +0.70 LEED (2 × 2), *using ions
Ni(110) Diode* +0.33 LEED (2 × 1), *using ions
+0.44 LEED (3× 1)
74D3 Ni(100) 300 Kelvin +0.22 LEED p(2 × 2)
+0.36 LEED c(2 × 2)
Ni(110) 300 Kelvin +0.26 LEED (3 × 1), θΟ = 0.33
+0.46 LEED (2 × 1), θΟ = 0.50
+0.42 LEED (3 × 1), θΟ = 0.60
NI(111) 300 Kelvin ~+0.7 LEED p(2 × 2)
74H Ni(100) LEED, AES
300 Diode II 0.3 θ = 0.25 p(2 × 2)
~0 θ ~ 0.5 c(2 × 2) at max. intensity
-0.65 NiO formation
76E3 Ni(111)* SE edge II +0.5 4L UPS
Ni(110)* (UPS) 0.0 20 L * ∆Φ curve is independent of
Ni(100)* -0.5 100 L surface orientation
Ni,
polycr.*
76K Ni(100) SE edge I 0.6 at p(2 × 2) LEED, UPS, XPS
(UPS) µ0 = 0.37 D
79A Ni(100) 300 SE edge II +0.17 5L p(2 × 2) in LEED
(E) 0.0 20 L c(2 × 2)
-0.15 120 L NiO
91P7 Ni(100) 325 Kelvin II +0.35 at 1 L p(2 × 2), c(2 × 2) O phases
+0.35 at 30 L then nucleation of NiO
0.0 at 50 L
-0.50 at 90 L
80B5 Ni(110) 300 Kelvin II +0.5 10 L AES, TDS, ELS
0.0 25 L
-0.4 50 L
81C Ni(111) 610 Kelvin I 0.6 ± 0.1 LEED, TDS
370 Kelvin I 1.05
82H Ni(110) 20 SE edge I 0.95 2L chemisorbed atomic oxygen
(UPS) >2 L physisorbed O2 on top
no additional change in Φ
84B3 Ni(111) 300 SE edge I 1.0 3L TDS, MDS
(E)
84S5 Ni(111) 77 Diode I 0.31 θ = 0.5 ∆Φ = 0.31 eV = constant
for 0.5 < θ < 1
86N2 Ni(110) 420 Kelvin I 0.3 1.5 L LEED, XPS, TDS, NRA
300 Kelvin II 0.55 1.5 L At 420 K three ordered phases are
0.0 30 L found.
(3 × 1): θ = 0.33
(2 × 1): θ = 0.5
(3 × 1): θ = 0.66
87J Ni(111) 300? SE edge II 0.85 4L LEED, AES
(E) -0.7 15 L
88B Ni(111) 8 Diode I 1.2 3.5 L
77 I 1.3 1.5 L


Substrate
89P Ni(111) 100? SE edge 0.6 θ = 0.25 p(2 × 2)
(E) LEED, ARUPS, XPS, TDS
95K2 Ni(775) 300 Kelvin I 0.75 2L LEED, UPS, TDS
96S3 Ni(311) 300 Kelvin I 0.5 0.3 L HREELS
At 0.3 L O2 ∆Φ for the fully oxided
surface (40 L) is already reached.
84S3 Pd(111) 300 Diode I 0.8 2L AES, ELS, TDS
89H Pd(110) 100... Kelvin
900
475 I 0.7 c(2 × 4) + (2 × 3) – 1D
300 I 0.45 c(2 × 4)
200 I 0.4 pseudo (2 × 1)
90H2 Pd(110) 100 Kelvin I 0.7 θ = 0.9* * from NRA
88H5 Pd(110) 100 Kelvin I 0.7 1.2...1.5 L LEED, TDS, NRA
θ0 = c(4 × 2) in LEED
0.50±0.05
96B2 Pd(110) 300 SE edge +0.55 at 1 L
(UPS) +0.42 at 2.5 L
+0.42 at 10 L
78N Pt(111) 300 SE edge I 0.35 1L LEED, AES, TDS
stepped* (E) 0.55 500 L * 9(111) + 1(111)
84G2 Pt(100) 400... Kelvin LEED, RBS, NMA
84N 700 reversible structure and oxygen
coverage changes with T at
p = 5.3·10-3 Pa = const.
0 θ= 0 structure: hex; T = 770 K
0.48 θ = 0.63 structure: (3 × 1); T = 670 K
0.37 θ = 0.44 structure: complex; T < 650 K
93R2 Pt(100) 650 PYS -1.2 sat. due to subsurface oxygen
PEEM
85D Pt(111) 370 Kelvin I 0.30 7·1014 UPS, XPS
570 atoms cm-2 570 K for coverages > 4·1014 atoms
cm-2
Pt(100) 370 Kelvin I 0.75 1.4·1015 570 K for coverages > 2.7·1014
570 atoms cm-2 atoms cm-2
86F2 Pt(110) 300 Diode I 0.3 θ = 0.4
-(1 × 2) 120 Diode I 0.75 θ = 1.3
92S6 Pt(110) 560 Diode +1.15 θO = 0.33
1100 Diode +1.65 θO = 0.07
+2.5 θO = 0.5
89R Pt(111) 90...300 SE edge I 0.2 UPS
(E)
89F Pt(112) 100 Kelvin I 0.75 3.5 L UPS
(1 × 2) and SE good agreement between the two
edge methods and with Ref. [86F2]
(UPS)
89P2 Pt(111) 400 SE edge I 0.55 0.8 ML LEED, AES, TDS, UPS, HREELS
(UPS) (2 × 2)-O at θ0 = 0.25
Exposure to NO2; see Fig. 12


Substrate
92S2 Pt(210) 330 Kelvin 0.65 500 L LEED, STM, TDS
430 0.75 500 L For T .D(5 × 2)-rect
>480 0.77 500 L structure is observed which is
found by STM as due to (110) and
(310) microfacets
72Z Re(0001) 300 Diode 0.5 LEED: (2 × 2) or (2 × 1)
Re(10 1 0) 300 Diode 1.2 LEED: (1 × 3)
74F Re(0001) 300... Diode I 0.9
(ribbon) 850 I 1.2
82D2 Re* 300? FEM I 0.94 0.5 L * The central plane of the tip is
1.15 1L Re(10 1 0).
1.33 1L
82L3 Re(10 1 0) 300? FEM? I 1.3 p = 10-5 Pa
88R Re(0001) 80 Diode I 0.45 2L SHG
97B2 Rh(111) 40 SE edge I 0.75 2.3 L for exposures larger 2.3 L physi-
(UPS) sorbed O2 appears in UPS.
87K Rh(100) 300 PYS I 0.38 2·104 L AES
(sat).
Rh(111) 300 PYS I 0.28 3·104 L
(sat).
99S3 Rh(111) 450 Kelvin I +0.75 θO = 0.2 LEED, TDS, PEEM
Rh(533) 340 +0.95 θO = 0.25
75M Ru(0001) 300 Kelvin I 0.2 1.6 L p(2 × 2)
0.8 2.5 L two states
100 Kelvin 1.0 2.5 L LEED, AES
77K5 Ru(10 1 0) 300 Diode I +1.0 3L FEM pictures
85S7 Ru(0001) 300 Diode I +0.2 θO = 0.25 AES, TDS
+0.85 θO = 0.50
+1.15 θO = 0.70
86H3 Ru(0001) 80 Kelvin I 1.1 2.5 L TDS
300 Kelvin I 0.7 6L
87S Ru(0001) 300 Diode I 0.5 4L AES, TDS, ELS
93S2 Ru(0001) 400 Kelvin 0.3 1L p(2 × 2) ĺSî
0.92 10 L
640 0.3 1L
1.12 10 L
99B Ru(0001) 300 II +1.2 1 ML TDS, UPS
+0.4 6 ML
93S Si(100) 300 Diode +0.35 30 L
-(2 × 1) 500 +0.35 50 L
+ Ge
88S Si(111) 20 Diode I +1.6 1L
99P Si(111) 300 Kelvin II +0.95 2.5 L
-(7 × 7) +0.2 70 L
89B2 SiC(001) SE edge III -0.25
(E)
92S3 SnO2(110) 150 SE edge 0.25
(UPS)


Substrate
67F Ta(110) 300 Diode IV -0.45 at θ1
0 at 2θ1
+0.2 at 3θ1
76T Th(100) 300 Diode IV -0.60min 8L LEED, AES
-0.46 36 L
69A W(100) Therm 0.94 sat.
72B W(100) 300? Kelvin 1.45 µ0 = 2.2 D
72M2 W(100) 300 Diode I 1.6 50 L (sat.) ESD
73P3 W(100) 300 Diode 1.4 6L LEED
73B2 W(100) 350 Diode 1.75
73D2 W(100) 300 Kelvin I +1.5 saturation
74F2 W(100) 300 SE edge +1.5 UPS
(UPS)
76B2 W(100) 300 Diode I 1.4 LEED, AES
1050 Diode IV -0.2 1L
+0.8 3L
84S7 W(100) 300 SE edge 1.2
(E)
69T2 W(110) 300 Kelvin +0.70 6L p(2 × 2), AES, LEED
+0.75 8L
W(112) +0.75 1.2 L p(2 × 1)
+0.92 2L
+0.91 3L p(1 × 1)
+1.05 8L
69W W(110) 90 FEM I 1.3
W(111) 90 FEM I 1.4
W(211) 90 FEM I 1.6
W(100) 90 FEM I 1.7
70E W(100) 20 FEM 1.2
100 1.4
W(211) 20 FEM 1.4
100
20
W(110) 20, 100 0.6
W(111) 20 1.4
W(120) 20 1.3
74M3 W(100) FEM I +1.9 1018 atoms cm-2
W(110) FEM II +0.9 2·1015 atoms cm-2
+0.7 1016 atoms cm-2
+1.3 1018 atoms cm-2
W(111) FEM II +0.85 7·1014 atoms cm-2
+0.4 8·1015 atoms cm-2
+0.7 2·1017 atoms cm-2
W(112) FEM II +2.1 2·1015 atoms cm-2
+1.5 1018 atoms cm-2
75E2 W(110) 300 Kelvin IV -0.05 0.1 ML LEED
+0.2 0.5 ML
77B3 W(110) 700 Kelvin I +0.1 θO = 0.5
+1.3 θO = 1.0


Substrate
72M3 W(111) 300 Diode I +1.2 TDS
125 Diode I +1.7
72W W(110) 90 FEM I 1.2
W(112) 90 FEM I 1.7
W(111) 90 FEM I 1.45
W(013) 90 FEM I 1.65
77E3 W(110) 300 Kelvin I LEED, TDS
stepped
24(110)× 0.0 θO = 0.1
(011) +0.25 θO = 0.4
10(110)× 300 Kelvin I +0.1 θO = 0.01 LEED, TDS
(011) +0.12 θO = 0.15
+0.48 θO = 0.45
78B4 W(110) 300 Kelvin IV -0.15 θO = 0.25 LEED, TDS, AES
0.0 θO = 0.5 oxygen dosing by adsorption of
+0.8 θO > 1 ML WO2
300* Kelvin I +1.1 θO > 1 ML *plus annealing to 1300 K for 30 s
78W W(110) 50 FEM I +0.9
100
80R W(110) 300 Diode IV -0.07 θ1 LEED, AES
+0.3 3 θ1
81M2 W(110) 300 Diode I 0.0 up to 0.8 L
0.4 10 L
83A3 W(110) 300 SE edge 1.0 11 L
(E)
88L W(110) 90 Kelvin I 1.0 LEED, AES, TDS, XPS
800 I 1.5
89S3 W(110) 90 Kelvin I 0.95 LEED, AES, TDS
92Y W(100) 300 FEM 1.6 sat.
W(111) 300 FEM 1.1 sat.
98W W(110) 90 Kelvin I 1.0 θ = 0.65 XPS, TDS
80F Zr polycr. 300 Diode IV -0.2 0.5 L
+0.55 30 L
88G Zr(0001) 80 Kelvin IV -0.2 0.8 L LEED, AES
+0.9 12 L initial decrease of Φ is believed to
be due to incorporation of oxygen
into the bulk
91Z4 Zr(0001) 475 Kelvin -0.32 θO = 0.5
94Z Zr(10 1 0) 90 Kelvin IV -0.14 0.8 L LEED, AES, NRA
+0.55 5L Although ordered surfaces are
300 Kelvin IV -0.20 1L observed, the sticking coefficient
+0.25 5L of O2 is high. Only after a film
470 Kelvin IV -0.24 1.5 L thickness of 12.4 ǖSDVVLYDWLRQLV
+0.06 5L observed. It is concluded that
atomic oxygen penetrates the bulk
even at low temperatures.


Substrate
98N ZrC(111) 300 SE edge I 1.0 1.5 L UPS
1050 (E) IV -0.2 0.2 L
1170 +0.6 4L
1270 <0 0...10 L
4.2.3.5 Sulfur (S)

A summary of the results for S adsorbed on Ni and Cu surface has been given by Oudar [80O, 80O2].
Table 11. Atomic Sulfur (S)
Ref. S/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
79S3 Ag(111) 300 Diode +0.60 saturation AES, LEED, TDS
78P Cu(111) 300 Kelvin 0.43 Single-crystalline Cu cylinders
Cu(110) 0.66 with [100] and [110] axes exposed
Cu(100) 0.70 a variety of different Cu faces.
Cu(311) 0.63
93L Cu(001) UPS I 1.0 sat. at prep. H2S
p(2 × 2) LEED, AES
78P Cu Kelvin
88N Fe(001) 80-670 Kelvin I 0.7 sat. LEED, AES
prep: S-beam
84M2 Mo(100) 300 Kelvin I +0.55 1.1 ML LEED, AES
For interpretation a variety of
structures with bonding sites other
than hollow sites have to be
included.
85B4 Mo(110) ~500 FEM I 1.1 sat. Preparation by S-beam
Mo(100) I 0.8 sat.
Mo(211) I 1.0 sat.
Mo(111) I 1.2 sat.
71S Ni(100) 300 INS* +0.63(5) LEED c(2 × 2)
73B2 Ni(111) Diode* +0.35 LEED (2 × 2), *using ions
Ni(110) Diode* +0.59 LEED (2 × 2), *using ions
74D3 Ni(100) 300 Kelvin +0.24 LEED p(2 × 2)
+0.38 LEED c(2 × 2)
Ni(111) 300 Kelvin ~+1.0 LEED p(2 × 2)
83B3 Ni(110) 530 FEM I +0.4
(tip)
84G Ni(100) 300 Diode I +0.3 prep. S2-beam
970 similar LEED, AES
86H6 Ni(100) 300* SE edge +0.36 θS = 0.4 AES, TDS
(UPS) + H2S-adsorption
Diode θS = 0.4
*plus heating to 600 K
88B2 Ni(111) 570 PYS I 0.5 θ = 0.8 LEED, AES

Ref. S/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
95P Ni(100) Kelvin I 0.18 p(2 × 2) LEED, AES, TDS
prep. H2S
0.25 c(2 × 2)
87P3 Pd(111) 100 Diode III -0.23 LEED, TDS
complicated dependencies of ∆Φ
from S2 doses at higher tempe-
ratures; at 550 K sulfide forma-tion
77F Pt(100) 300 UPS III -0.25 θS = 0.25 H2S Langmuir kinetics
p(2 × 2) LEED, UPS
-0.7 θS = 0.48
c(2 × 2)
83P Pt(111) 300 Kelvin I 0.4 θ = 0.1 LEED, µ0 = 0.8 D
0.4 θ = 0.27 p(2 × 2)
0.55 θ = 0.33 (¥î¥5Û
Pt(110) 350 Kelvin I 0.55 θ = 0.8
84B4 Pt(111) 900 Diode + IV -0.38 0.25 ML p(2 × 2)
Kelvin -0.05 0.33 ML ¥
LEED, AES, TDS
prep. H2 + H2S
flash to 900 K
96P Si(100) 300 Kelvin II 0.25 0.5 ML (2 × 1)
-(2×1) 0.3 1 ML (1 × 1)
97P 0.15 2 ML subsurface
LEED, AES, TDS
97P2 Si(100) Kelvin +0.33 1 ML LEED, AES, TDS
-(2 × 1) +0.42 2 ML
99L3 Si(100) PYS I +0.4 LEED, AES,
-(2 × 1) dosing of S2
82P3 W(100) 300 Diode IV -0.12 θ = 0.3 LEED, AES, TDS
+0.48 θ=1
900 about
the same
82P3 W(110) 300 Diode IV -0.15 θ1 LEED, AES, TDS
0 2θ1 S- sublimation for preparation.
0.25 4θ1 Similar results for T = 1000 K.
92M4 W(100) * SE edge IV -0.4 θS = 0.4 *annealed at 900 K
(UPS) 0.0 θS = 0.5
+0.4 θS = 0.8

4.2.3.6 Atomic Selenium (Se)
Table 12. Atomic Selenium (Se)
Ref. Se/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
83N3 Fe(100) SE edge I 0.7 0.5 ML LEED c(2 × 2), AES
(E)
71S Ni(100) 300 INS* +0.25(5) LEED c(2 × 2)
73B2 Ni(111) Diode* +0.13 LEED (2 × 2)
*using ions
Ni(110) +0.40
74D3 Ni(001) 300 Kelvin +0.08 LEED p(2 × 2)
-0.07 LEED c(2 × 2)
76C3 W(100) FEM IV -0.3 θ = 0.2
probe hole +1.1 θ = 1.0
Mo(100) IV -0.5 θ = 0.5

+0.85 θ=2
Mo(112) IV -0.2 θ = 0.5
+1.1 θ=2
Mo(111) I +0.5
θ=2
Mo(110) II +1.2
θ = 1.5
+1.0
θ=2
82P W(100) 300 Diode I 0.45 sat. LEED, AES, TDS
several structures during warming
to 1800 K
82P5 W(110) 300 Diode LEED, AES
two phases 0.2 θSe 0.4
4.2.3.7 Tellurium (Te)
Table 13. Atomic Tellurium (Te)
Ref. Te/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
83N Fe(100) 300 I 0.45 sat. LEED, AES
600
77C2 Mo(110) FEEM IV -0.11 θTe = 0.1
0.0 θTe = 0.3
+0.4 θTe = 1.0
78C Mo(110) FEM IV -0.1 0.1 ML
0.7 1.2 ML
Mo(111) IV -0.3 0.3 ML
0.4 1.0 ML
Mo(100) IV -0.2 0.5 ML
0.1 1.2 ML
Mo(211) IV -0.4 0.5 ML
0.3 1.2 ML

Ref. Te/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
74D3 Ni(001) 300 Kelvin -0.29 LEED p(2 × 2)
-0.43 LEED c(2 × 2)
77C2 W(110) FEEM IV -0.13 θTe = 0.2
0.0 θTe = 0.4
+0.12 θTe = 1
78C W(110) FEM IV -0.25 0.5
-0.1 1.0
W(111) IV -0.4 0.5
-0.2 1.0
W(100) IV -0.15 1.0
-0.1 1.5
W(112) IV ∆Φ > <2
- 0.1
82P2 W(100) 300 Diode II 0.25 2θ1 LEED, AES, TDS
500 0.15 3θ1
4.2.3.8 Chlorine (Cl)
Fig. 13 and 14
Table 14. Atomic Chlorine (Cl)
Ref. Cl/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
75R2 Ag(100) 300 Diode +1.0 LEED
80K2 Ag(100) 300 Diode? I 1.4 sat. LEED
77G Ag(111) Diode I +1.8 sat. LEED, AES
different ordered phases
92W Ag(111) SE edge I +1.5 AES, UPS, HREELS
(UPS)
78M2 Ag(331) 300 Diode +1.6 LEED: (6 × 1)
89B Al(111) 300 Diode I 1.08 sat. µ0 = 0.4 D at θ = 0.6
93K Au(111) 120 SE edge I 1.2 sat.
500 (UPS) 0.9 sat.
82C2 Bi(0001) 300 ? I 1.6 sat. LEED, AES, TDS
cleaved
82F Cr(100) 300 Diode I -1.1 1.2·1015 LEED, AES, TDS, UPS
atoms cm-2 several LEED structures, solid-
state source for Cl
87F Cr(110) 300 ? IV -0.25 θ1 LEED, AES, TDS
0 > 2θ1 solid-state source for Cl
77G Cu(111) Diode I +1.2 sat. LEED, AES
different ordered phases
96W2 Co50Ni50 300 SE edge I +1.3 AES
(111) (UPS) also studied at higher temperatures
79D Fe(100) Diode I 1.43 sat. c(2 × 4), LEED
CMA
88J3 n-MoSe2 300 SE edge 1.8 sat.
(0001) (UPS)


Substrate
77E Ni(111) Diode I +0.47 0.5 LEED, AES
¥DQGDPRUHFRPSOH[VWUXFWXUH
82E2 Ni(110) 300 Diode II 1.1 1.3 L c(2 × 2), LEED, AES, TDS
0.9 1.7 L diffuse p(10 × 1)
1.1 3.5 L for exposures > 1.5 L
µ0 = 0.51 D
A dip in ∆Φ occurs at θCl = 0.5.
91Z2 Ni(110) 300 SE edge I 1.1 sat. AES, UPS
(UPS)
82E2 Pd(110) 300 Diode I 1.22 1.7 L diffuse c(16 × 2), µ0 = 0.63 D
80E Pd(111) 300 Diode I 0.57 1.8 L (¥î¥5Û/(('VWUXFWXUH
at 1.2...1.6 L Cl2;
see Fig. 13.
88T2 Pd(111) 300 I 0.7 sat. 4·1014 molecules cm-2
(¥î¥5ÛDW
2.5...3.0·1014 molecules cm-2
LEED, AES, TDS
solid-state source for Cl2
82E2 Pt(110) 300 Diode I 0.55 1.0 L diffuse p(2 × 1) for exposures > 0.8
L, for 0.3 L Pt(110)- (21× 2)
reconstruction spots appear
80E Pt(111) 300 Diode IV -0.08 1L LEED, AES, TDS
+0.34 2.3 L (3 × 3) LEED structure at
1.6...1.9 L Cl2;
see Fig. 14.
98H2 Pt(111) Kelvin IV -0.04 1.2·1014 atoms cm-2
+0.38 7·1014 atoms cm-2
83G Ru(10 1 0) 300 ? I 0.55 sat. LEED, AES, TDS, UPS
4 ordered surface structures
83S Ta(100) ? I 1.0 sat. For (110): high electronegativity,
Ta(110) II -1.0 sat. so that differences to Cl smaller so
that Smoluchowski smoothing and
polarization effects take over.
97W Ta(110) Theory +0.6 top site explains decrease of Φ
-0.4 bridge site
-1.0 hollow site
-1.2 threefold
site
71A2 Ti, 300 FEM I 0.8 ML average ∆Φ
1.4 2ML
69F2 W(100) 300 Diode I +0.64(2)
81K W(100) 300 Diode I 0.75 sat. AES, LEED, TDS
70J W(110) 300 K III -0.26 sat.
W(100) I +0.58 sat.
W(111) I +1.03 sat.
72H W(211) 300 FEM ±∆Φ depending on pressure
W(110)
79B4 W(100) 370 SE edge I 0.65 1.5 L UPS
(UPS)


Substrate
80B W(110) Diode III -0.5 sat. LEED, TDS
W(111) I +0.7 sat. Prep.: surface ionization of KCl.
W(111) facettes at higher cover-
ages.
79C ZnO 900* Diode I 0.64 * temperature before dosing Cl
(000 1 )O 1000* 0.73
1100* 0.81
ZnO(0001) 300 Diode I 1.0
ZnO 300 Diode I 0.85
(10 1 0)
4.2.3.9 Bromine (Br)
Table 15. Atomic Bromine (Br)
Ref. Br/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
78G2 Ag(111) 300 Diode? I 1.4 3.5·1014 LEED, AES,TDS
molecules
cm-2
85B Ag(110) 120 Kelvin I 1.4 sat. LEED, AES, TDS
p(2 × 1) at θBr = 0.5, fourfold-
hollow site
320 Kelvin c(4 × 2) at θBr = 0.75, AgBr bilayer
80B3 Au(100) 300 Kelvin I 0.78 16·1014 LEED, TDS
molecules
cm-2
83R Cr(100) 300 (Diode) I 1.1 0.4·1015 LEED, AES, TDS
atoms cm-2 solid-state source for Br
1.6 3.3·1015
atoms cm-2
84F Cr(110) 300 (Diode) IV -0.45 8·1014 LEED, AES, TDS
atoms cm-2 solid-state source for Br; authors
-0.2 40·1014 assume Br to metal charge transfer.
atoms cm-2
79D2 Fe(100) 300 SE edge I 1.10 sat. LEED, AES
(E)?
(0001) (UPS)
82T2 Pd(111) 300 Diode I +0.45 sat. TDS
79B Pt(111) 300 Kelvin IV -0.28 0.7·1014 LEED, AES, TDS
molecules little charge transfer
cm-2 (3 × 3) ordered overlayer at 300 K
6·1014 order-disorder transition at 520 K
520 +0.25 molecules
cm-2
70J W(110) 300 Kelvin III -0.32 sat.

W(100) I +0.80 sat.
W(111) I +0.88 sat.

Ref. Br/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
69F2 W(100) 300 Diode I +0.41(2)
79B4 W(100) 370 SE edge I 0.4 3L UPS
(UPS)
96M2 WSe2(0001) Kelvin I +1.1 UPS
n-type
4.2.3.10 Iodine (I)
Table 16. Atomic Iodine (I)
Ref. I/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
93N2 Au(100) 300 Kelvin IV -0.1 0.5 ML LEED, TDS
+0.08 1 ML Correlated with LEED structures
130 +0.6 I2 on top of chemisorbed layer
79J2 Fe(100) 300 Diode III -0.55 LEED, AES, TDS
93T GaAs(110) 300 Kelvin I +0.6 sat. Surface states of acceptor charac-
ter within the bulk band gap, Fig.3
(0001) (UPS)
92J Pt(111) 300 SE edge IV -0.7 0.33 ML threefold-hollow site: ∆Φ < 0
(UPS) on-top site: ∆Φ > 0
1000 -0.55 sat.
93C Si(111) 300 SE edge I 0.35 sat.
-(7 × 7) (UPS)
83S Ta(100) ? I +0.8 sat.
Ta(110) ? III -0.9 sat.
70J W(110) 300 Kelvin III -0.78
W(100) III -0.18
W(111) III -0.13
74A W(110) 300 Diode III -0.4 0.5 ML LEED, AES
some different LEED patterns
69F2 W(100) 300 Diode IV -0.4 min
+0.08 saturation
79B4 W(100) 370 SE edge IV -0.37 1L UPS
(UPS) -0.1 /
4.2.4 Small molecules

4.2.4.1 Molecular Hydrogen (H2)
Table 17. Molecular Hydrogen (H2)
Ref. H2 / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
83A Cu(100) 10 III -0.18 normal H2 HREELS
10 -0.19 para- H2
15 -0.23 D2
87J2 Ga 10 SE edge -0.1 UPS
(polycr.) (UPS)

4.2.4.2 Molecular Nitrogen (N2)
Table 18. Molecular Nitrogen (N2)
Ref. N2 / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
91H Ag(111) 20 SE edge III -0.45 1 ML LEED, UPS, HREELS
(UPS)
89J2 Al(111) 20 SE edge III -0.15 1 ML LEED, UPS, HREELS
(UPS) physisorbed N2
82E Fe(111) 125 I 0.10* 180 L TDS

desorption temperature 155 K
* at 2·10-6 Torr
max. coverage 1·1014 molecules cm-2
85S2 Fe(111) 65 (Kelvin) IV -0.27 θ1 TDS, this is the γ-N2
-0.23 3 θ1
87J2 Ga 10 SE edge 0.0 UPS
(polycr.) (UPS)
73N Ir(111) 80 FEM -0.2
Ir(100) 80 probe -0.7
~Ir(110) 80 hole +0.1
Ir(210) -0.3
Ir(731) -0.1
79G Ni(110) 90 Kelvin I 0.1 LEED, TDS
82H Ni(110) 20 SE edge 0.0 LEED, ARUPS
(UPS) chemisorbed + physisorbed N2
86B4 Ni(111) Kelvin -0.56 chemi- XPS, UPS, TDS
sorbed chemisorption saturates for
-0.08 physi- coverages smaller than 1 ML
sorbed leading to coadsorption of a
physisorbed species
92B3 Pd(111) 20 SE edge III -0.7 1 ML* * from UPS
(UPS) chemisorbed + physisorbed N2
60 -0.6 only chemisorbed N2
73N2 Pt(111) 80 FEM -0.34
Pt(100) -0.31
Pt(331) -0.76
Pt(320) -0.77
81N3 Rh(111) -0.15
Rh(100) -0.5
Rh(110) +0.2
Rh(210) +0.3
77K5 Ru(10 1 0) 120 Diode III -0.04 0.8 L
87D Ru(0001) 85 Kelvin III -0.54 LEED, AES, TDS
86D
92S7 Ru(0001) 40 SE edge III -0.67 1 ML ARUPS, HREELS
(UPS) ML from UPS
76Y W(110) 120 -0.19
80F Zr 300 Diode III -0.15 100 L Authors conclude on dissociative
(polycr.) adsorption. No proof that N2 sticks!

4.2.4.3 Molecular Oxygen (O2)
Table 19. Molecurlar Oxygen (O2)
Ref. O2 / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
79H2 Al(111) 20 SE edge +0.85 5 L O2 condensed O2 on Al(111)
(UPS) ΦAl(111) = 4.25 eV
82S4 Cu(111) 100 SE edge III -0.4 1000 L LEED, AES, UPS, ELS
(UPS) chemisorbed O2
2-peak spectrum in UPS
81S2 Ga polycr. 20 SE edge +0.2 condensed O2 layer (10 L)
(UPS) ΦGa = 4.0 eV
+0.5 physisorbed O2 monolayer
+1.4 after warming to 70 K unidenti-
fied O2 intermediate
-
(presumably O )
2
84S5 Ni(111) 5.5 Diode I 0.07 6 L O2 ∆Φ = 0.07 eV = const.
for exposures up to 12 L
89R Pt(111) 20 SE edge I -0.45 UPS, XPS
(UPS)
4.2.4.4 Carbonmonoxide (CO)
Fig. 15...21
Table 20. Carbonmonoxide (CO)
Ref. CO/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
76M3 Ag(111) 77 Kelvin -0.2 LEED
82K Al(100) 300 Kelvin 0.0 <100 L LEED, AES, ELS
no interaction for doses <100 L
0.5 105 L dissociation
83K2 Al(111) 300 Kelvin 0.0 <100L no interaction for exposures
< 100 L
I 1.35 105 L dissociation for exposures >103 L
76M2 Au(100) 77 Kelvin -0.85 AES, ELS
78P4 Co(10 1 2) +1.0 1L
83P Co(0001) 100 Kelvin I +1.35 2.5 L LEED, AES, UPS
300 I +0.85
98L Co(0001) 180 SE edge I +0.3 θCO = 0.3 LEED, AES, TDS, LEIS, XPS
(XPS) +1.2 θCO = 0.65
82K2 Cr(110) 300 Diode I +0.1 1L
71C4 Cu(100) 77 Kelvin IV -0.22 1.5 L
-0.09 4L
75P3 Cu(100) 77 Kelvin IV -0.24
-0.12
Cu(111) 77 Kelvin IV -0.45
-0.09


Substrate
Cu(110) 77 Kelvin IV -0.31
-0.18
Cu(211) 77 Kelvin IV -0.33
-0.15
Cu(311) 77 Kelvin IV -0.32
-0.19
Cu(755) 77 Kelvin IV -0.42
-0.18
77K3 Cu(111) 120 Diode I 1.0 LEED: two structures
AES, TDS
79H5 Cu(111) 82 Kelvin IV -0.47 1L IRAS
-0.05 2.5 L
82L Cu(111) 300 (Diode) -0.5 1L UPS
86K Cu(111) 100 Kelvin IV -0.4 2L LEED, UPS, TDS
-0.28 4L
75P Cu(311) 77 Kelvin IV -0.32 0.6 L
-0.22 1.5 L
94B2 Cu(332) 180 Kelvin III -0.27 1L LEED, TDS
107 IV -0.4 1.5 L
-0.33 3L
96S4 Cu(111) 90 Kelvin -0.35 0.9 L HREELS, TDS
96S5 -0.08 4L
98B Cu(332) 95 Kelvin IV -0.36 1.7 L LEED, AES., TDS, UPS
-0.17 3L
84S2 Fe(111) 220 Kelvin I 1.6 5L LEED, HREELS, TDS
88U Fe(110) 300 Diode I 0.43 7L LEED, TDS
91B2 Fe(111) 80 Kelvin I 1.0 1L UPS
78T2 Ir(110) ? 0.23 sat.
78T2 Ir(110) 90 Diode I 0.29 3L LEED, AES, TDS
300 Diode I 0.21 3L
97L3 Ir(110) 300 Kelvin I +0.7 1L XPS
+1.1 15 L
73L Mo(100) 300 Diode IV -0.10 θCO = 0.3 1L
0.0 1.2 L
+0.07 θCO = 0.5
+0.50 5 L saturation
78F Mo(100) 300 IV -0.2 0.6 L AES, TDS
0.0 0.8 L
+0.4 1.5 L
205 I +1.1 at 4 L
73T Ni(110) 300 Diode I 1.3 θ = 0.66 LEED, AES, TDS
170 I 1.6 θ = 1.0
74C4 Ni(111) 300 Kelvin I 1.3 LEED, AES, TDS
74D3 Ni(001) 300 Kelvin +1.1 LEED c(2 × 2)
Ni(110) 300 Kelvin +0.95 1.8 L LEED
Ni(111) 300 Kelvin ~+0.7 ~2 L LEED
79A2 Ni(100) 300 SE edge I +1.0 3L AES, ELS
(E)
81C Ni(111) 300 Kelvin I 1.1 0.5 L LEED, µ0 = 0.28 D


Substrate
81N Ni(110) 300 SE edge I 1.1 1L LEED, AES
(E) θ high ĺîVWUXFWXUH
82H Ni(110) 20 SE edge I 1.55 ARUPS
(UPS) see Fig. 15.
82M Ni(100) 300 FEM I 0.85 sat.
Ni(510) 300 FEM I 1.1 sat.
Ni(310) 300 FEM I 1.25 sat.
Ni(110) 300 FEM I 1.35 sat.
83K Ni(100) 100 SE edge I 1.1 1L
(UPS)
85B3 Ni(110) 130 Kelvin I 1.5 4L LEED, TDS
c(8 × 2) at θ = 0.62
c(4 × 2) at θ = 0.75
(2 × 1)p2mg at θ = 1.0
see Fig. 16.
85D2 Ni(111) SE edge +0.7(2)
(UPS)
85S Ni(111) 5.5 Diode I 0.16 8L CO precursor + finite amount of
chemisorbed CO
80 Diode I 0.9 6L chemisorbed CO
88B Ni(111) 8 Diode I 1.3 3L molecular beam, HREELS, no
evidence for physisorbed CO at
8 K contradicts [85S].
88S2 Ni(111) 90... SE edge I 1.4 θ = 0.5 IRAS
300 (XPS) µ0 = 0.65 D for bridge CO
µ0 = 0.17 D for on-top CO
temperature-dependent site swit-
ching from bridge to on top with
increasing temperature; see
Fig. 17.
95S2 Ni(110) 300 SE edge I 1.1 sat. AES, UPS
(UPS)
95K2 Ni(775) 300 Kelvin I 0.5 1L (775) = 6(111) + 1(11 1 )
145 I 1.1 2L = 5(111) + 2(110)
LEED, UPS
70E2 Pd(111) 300 Diode + I 0.99 sat. LEED, TDS
Kelvin 3 L CO At = 3.3 (¥î¥5ÛVWUXFWXUH
θCO = 0.5 in LEED.
74C5 Pd(111) 300 Kelvin I 0.98 θmax = 0.5 LEED,TDS at µ = 0.33D
Pd(100) 300 Kelvin I >0.75 ~0.7 max. coverage: 0.29 D
Pd(110) 300 Kelvin I 1.26 1.0 0.35 D
Pd(311) 300 Kelvin I 1.27
Pd(201) 300 Kelvin I 1.06 1.5 0.33 D
79B4 Pd(100) 0.94
80B2 Pd(100) 300 Kelvin I 0.9 sat. LEED, UPS, TDS
88H5 Pd(110) 100 Kelvin I 1.06 θ* = LEED: (4 × 2), *from NRA
100 I 1.09 0.73(5) LEED: (2 × 1), *from NRA
100 I 0.980 θ* = LEED: c(2 × 2), **from [89H]
1.00(5)
θ** = 0.55


Substrate
89O Pd(111) 300 Kelvin I 0.68 Cu = 0 Å
Pd(111)/ 0.1 Cu = 1 Å
Cu 0.04 Cu = 2 Å
0.00 Cu = 6 Å
77E2 Pt(111) 323 Kelvin IV -0.17 θ = 0.33 LEED, TDS
0.0 θ = 0.5 Assume two different adsorption
sites.
79N Pt(111) 95 Kelvin IV -0.25 θ = 0.33 XPS, UPS, TDS
0.05 θ = 0.4
300 Kelvin -0.15 θ = 0.33
0.05 θ = 0.4
81N3 Pt(111) 77 FEM 0.0 sat.
Pt(100) +0.1 sat.
Pt(210) +0.4 sat.
82P4 Pt(111) 300 Kelvin IV -0.24 1.5·1014 LEED, AES, HAS
molecules
cm-2 at
θCO = 0.1
-0.1 4·1014
molecules
cm-2
83B Pt(100)- 310 Kelvin I 0.18 θ = 0.5 LEED, ELS, TDS
(1 × 1) 0.4 θ = 0.75 (1 × 1) prepared following [78B3]
θ = 0.5 was calibrated from the
maximum of the LEED c(2 × 2)
intensity.
83J Pt(100) 300 SE edge I 0.3 θ = 0.68 LEED; RBS, NRA
(UPS) hex to (1 × 1) starts at θ = 0.08
(1 × 1) to hex starts at θ = 0.25
86E Pt(110) 460... Kelvin LEED, oscillations in ∆Φ,
620 see Fig. 18.
86F Pt(110)- 140 SE edge IV -0.17 θ = 0.5 LEED, XPS
-(1 × 2) (UPS) -0.04 θ=1
-(1 × 1) 140 SE edge -0.23 θ = 0.5
(UPS) IV -0.19 θ = 0.9
-(1 × 2) 300 SE edge IV -0.11 θ = 0.5
(UPS) +0.05 θ=1
88K2 Pt(111) 90 SE edge IV -0.14 1.5 L LEED, TDS, ESDIAD
(E) -0.05 6L Also co-adsorption of S.
90L Pt, Rh 300 FEM see FEM
high index Fig. 19 Figs. 19 and 20
90E Pt(120) 300 Kelvin I 0.12 3L LEED, AES, TDS
93A Pt50Ni50 300 Diode I +0.60 TDS
(110) 120 +0.90
Pt50Ni50 300 III -0.10
(111) 120 -0.23
94A Pt80Fe20 120 Diode IV -0.3 min, 0.8 L LEED, TDS, HREELS
(111) 0.0 2L
+0.12 7L


Substrate
76E2 Re film 300 I 0.47 2·1014 β state
molecules
cm-2
0.72 6·1014 β + α state
molecules
cm-2
72Z Re(0001) 300 Diode 0.35 LEED: (2 × 2) or (2 × 1)
Re(10 1 0) 300 Diode 0.32 (1 × 1)
85T Re(0001) 100 Kelvin II 0.50 3L XPS, TDS
0.45 20 L
300 I 0.50 20 L
90R2 Re(0001) 80 Kelvin I 0.3 θ = 0.5 θsat. SHG, TDS
0.45 sat.
77M4 Rh(110) 300 (Kelvin) I 0.97 5L LEED, AES, TDS
84P Rh(100) (100) SE edge I 0.6 θ = 0.3; 1 UPS, XPS, ELS, TDS
(UPS) 1.3 L
θ = 0.6; 15
L
84P6 Rh(100) 100 SE edge I +1.3 θCO = 0.6 TDS, UPS
(UPS, E)
88M2 Rh(111) 170 Diode I +0.3 θCO = 0.33 ¥VWUXFWXUH
+0.5 θCO = 0.55
+1.1 θCO = 0.75 (2 × 2) saturation
89K Rh(111) 90
SE edge I 0.5 1L UPS, XPS, TDS
(UPS)
83P2 Ru(0001) 200 Kelvin I 0.76 θ = 0.66 Fig. 21
88H2 Ru(0001) 85 SE edge I 0.6 10 L MDS, IRAS, TDS
(MDS)
Ru(0001) 85 SE edge -0.8 10 L 1 ML Cu on Ru(0001)
+1 ML Cu (MDS)
Ru(0001) 85 SE edge -0.9 10 L 2.4 ML Cu on Ru(0001)
+2.4 ML Cu (MDS)
88K Ru(10 1 0) 300 Diode I 1.1 θ = 0.7 LEED, AES, ELS
89L Ru(10 1 0) 120... Kelvin I 1.15 θ = 1.2 LEED, HREELS, TDS
650
76T Th(100) 300 Diode IV -0.40 3L LEED, AES
-0.28 15 L
67A W(100) 300 (Diode) I +0.43 10·1014 LEED
atoms cm-2
-0.16 θCO = 0.5 if irreversibly transferred into the
β state by heating to 1000 K
79W2 W(100) 87 Kelvin I 0.55 7·1014 LEED, TDS
molecules
cm-2
300 I 0.36 6·1014
molecules
cm-2
400 I 0.36 5.5·1014
molecules
cm-2


Substrate
69E W(110) 100 FEM I 1.2 sat.
W(111) 1.0 sat.
W(120) 0.85 sat.
W(100) 0.65 sat.
72A W(210) 300 Kelvin I 0.7 sat.
74F2 W(100) 300 SE edge +0.4 UPS
(UPS)
77L W(110) 20 FEM I 0.6 sat.
78W W(110) 100 FEM I +0.8 10·1014 “virgin CO”
molecules
cm-2
87C W(110) 95 Kelvin I 0.34 3L Cu layers on W(110)
+ 1 ML Cu
W(110) 25 Kelvin IV -0.1 0.2 L
+4 ML Cu +0.18 3L
91H3 W(110) SE edge +0.08 θCO = 0.33 TDS, HREELS
(UPS) +0.85 θCO = 0.70 µ0 = 0.015 D
µ0 = 0.12 D
80F Zr polycr. 300 (Diode) IV -0.12 1L dissociative adsorption; atoms
0.2 10 L penetrate the bulk
4.2.4.5 NO, N2O
Table 21. NO
Ref. NO/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
84S6 Cu(110) 90 SE edge II 0.25 0.5 L first dissociative adsorption
(UPS) 0.08 1L For θO = 0.25 ML N2O stays un-
dissociatively adsorbed.
81I Ir(110) 100 (Diode) IV -0.08 θ = 0.5 LEED, AES, TDS, UPS, XPS
-0.04 θ=1
300 IV -0.11 θ = 0.75
-0.10 θ=1
80S Ni(100) 300 SE edge LEED, AES, TDS
(E) I 0.75 0.8 L dissociative adsorption
III -0.25 0.8...2.0 L NO coadsorbed
84B3 Ni(111) 90 SE edge I MDS/TDS
(UPS) 0.9 3.2 L at least partial dissociation;
If NO is adsorbed to a O
precovered surface, Φ falls 0.2 eV
below the value for the clean
Ni(111) surface.
84P5 Ni(100) 95 SE edge +0.77 0.42 ML TDS, XPS
(UPS, E) +0.75 0.55 ML co-adsorption with D
90B Pd(111) 100 SE edge LEED, ARUPS, HREELS
(UPS) γ state bridge sites
§ β state bridge sites
α state bridge and on-top sites
20 thick layer containing (NO)2

Ref. NO/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
84K5 Pt(111) 120 SE edge II +0.14 θNO = 0.17 XPS, UPS
(UPS) -0.16 θNO = 0.52 µ0 = 0.42 D
86F Pt(110) 140 SE edge III -0.40 θNO = LEED, XPS
-(1 × 2) (E) 0.8 ML
Pt(110) 140 III -0.34 θNO =
-(1 × 2) 0.5 ML
Pt(110) 300 III -0.46 θNO =
-(1 × 2) 0.6 ML
88I Pt(110) 315 Kelvin -0.045 1L LEED, TDS
0.0 3.5 L pCO = 5·10-8 Torr
+0.040 6L
89R Pt(111) 20 SE I -0.85 UPS, XPS
edge
(UPS)
77B6 Pt(100) 500 SE edge +0.4 LEED, UPS, XPS
(UPS) NO dissociates.
85T3 Re(0001) 120 SE edge +0.8 1.5 L UPS, XPS
(UPS) +0.3 >3L
85H2 Rh(100) 300 SE I 0.4 2L
edge
(UPS)
86H Rh 77 FEM I At 77 K molecularly adsorbed on all surfaces.
several At 300 K 30% at rough surfaces dissociate.
faces ∆Φ: 0.9 eV = (100) < (111) < (511) < (410) < (331),
(533) < (321) < (110) < (650) < (531), (210) = 1.4 eV
84H Rh(100) 100 SE edge I 0.9 0.4...0.65 LEED, AES, TDS
(E) ML
84H2 Rh(100) 100 SE edge I 0.9 0.5 ML LEED, TDS
(E)
77K5 Ru(10 1 0) 295 Diode I +0.4 6L
80F2 Ru(0001) 86 Kelvin I 0.9 10 Ex LEED, TDS, XPS
1 Ex = 1018 cm-2
At higher T different curves with
some dips occur. Authors discuss
the results in terms of two different
NO species.
80F Zr 300 (Diode) I 0.9 30 L dissociative adsorption
(polycr.) Small (-0.15 eV) dip at the
beginning due to subsurface
species.
Table 22. N2O
Ref. N2O/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
84S6 Cu(110) 90 SE edge II 0.25 0.5 L first dissociative adsorption
(UPS) 0.08 1L For θO = 0.25 ML N2O stays un-
dissociatively adsorbed.

4.2.4.6 NH3, PH3, PF3, P(CH3)3, AsH3
Fig. 22
Table 23. NH3
Ref. NH3 / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
78G3 Fe(111) 135 Kelvin III -2.0 sat. LEED, AES, TDS, UPS
Fe(100) 135 Kelvin III -2.0 sat.
79W Fe(110) 120 (Kelvin) III -2.3 15 L LEED, AES, UPS, TDS
µ0 = 2.2 D
80P Ir(111) 190 SE edge III -2.5 sat. ARUPS
(UPS)
77A Mo(110) 200 FEM -2.25 For all faces:
300 (probe- -1.2 NH3 decomposes at higher T
hole) N increases Φ
Mo(100) 200 -1.95
300 -1.1
Mo(211) 200 -1.9
300 -1.0
MO(111) 200 -1.55
300 -0.9
80S5 Ni(111) 200 SE edge III -1.7(2) sat. ARUPS, TDS
(UPS)
81F Pt(111) 100 SE edge III -3.0 sat. UPS, TDS
(UPS) ∆Φ corresponds to the sum of
α state (TD = 350 K) and
β state (TD = 150 K)
95K4 Pt(111) 100 Kelvin -3.0 LEED, AES, TDS, IRAS
97V3
96V2 Pt(111) 90 Kelvin III -0.29 IRAS
88R Re(0001) 80 Diode III -2.1 6L SHG
90R2 Re(0001) (80) Kelvin -2.3 sat. SHG
91A
96V Rh(111) SE edge III -2.3 θ = 0.25 (2 × 1) in LEED, a1 + a2 state
(E) µ0 = 1.9 D
83B5 Ru(0001) SE edge III -2.4 θ = 0.73 LEED, TDS, ESDIAD
(E) three states from TDS α, β, γ
α state: θ = 0.25, disordered
β state: bilayer formed through
hydrogen bonds
γ state: multilayer
µ0 = 1.9 D
see Fig. 22
91C Si(111) (300) PYS III -0.5 sat.
-(7 × 7)
91C2 Si(100) (300) PYS III -0.59 sat. LEED, AES
92C Si(111) 300 PYS III -0.6 sat. Authors conclude dissociation to
-(2 × 1) happen.
92R TiO2(110) 300 III -0.3 2L UPS

Table 24. PH3
Ref. PH3/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
89Z2 Ag(111) 105 SE edge III -1.4 TDS, UPS
(UPS)
98Y Au film 100 Kelvin -0.24 20 ppb under ambient conditions; rise
-0.32 50 ppb time of Kelvin probe signal was
-0.45 80 ppb 10 s; same behavior for AsH3.
85H Rh(100) 100 SE edge III -1.2 3L LEED, AES, TDS
(E) Bonding to surface via P conclu-
ded.
Table 25. PF3
Ref. PF3/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
(UPS)
Table 26. P(CH3)3
Ref. P(CH3)3/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
(UPS)
Table 27. AsH3
Ref. AsH3/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
98Y Au film 100 Kelvin -0.24 20 ppb under ambient conditions; rise
-0.32 50 ppb time of Kelvin probe signal was
-0.45 80 ppb 10 s; same behavior for AsH3.
4.2.4.7 H2O, D2O
Sass and Richardson [84S8] pointed out earlier that in studies of water adsorption on clean metal surfaces,
thermal desorption spectra, characteristically, show a two-peak behavior in the temperature range
150...200 K, although in certain cases a considerably more complex pattern is observed. In the usual
interpretation, the higher temperature peak (ca. 170...200 K) is attributed to molecular H2O in the first
monolayer at the surface, whereas the lower temperature peak (ca. 150...160 K) accompanies the onset of
multilayer ice formation. These temperatures can be correlated with binding energies of ca. 48...57 and
43...45 kJ mol-1, respectively. The latter corresponds, as expected, to the enthalpy of vaporization of ice
whilst the former lies in the upper part of the range generally considered to characterize physisorption.
With respect to the work-function changes induced by H2O adsorption there is always a decrease of
0.6 to 1.3 eV observed indicating that the lower half of the bilayer –pointing to the metal substrate –
interacts with the oxygen part. For higher exposures multilayer ice is condensed which does not
contribute very much to a further work-function decrease as the H2O dipoles are apparently randomly
oriented.
Figs. 23...25

Table 28. H2O, D2O
Ref. H2O, D2O/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
87B2 Ag(110) 80 (Kelvin) III -0.65 2L LEED, ESDIAD, TDS
no long-range order at 80 K
89M2 Al(100) 100 Kelvin III -0.95 12 L
93B3 Al(100) 100 Kelvin IV -1.2 2.5 L FT IR-RAS, NRA
-0.9 16 L at 100 K no dissociation of H2O
82H2 Co(0001) 100 Kelvin I -1.1 10 L UPS, TDS
Co(11 2 1) 100 Kelvin I -1.2 10 L H2O adsorption reversible below
300 K; ∆Φ > 0
94G Co(11 2 0) SE edge III -1.3 0.7 L XPS, UPS
(UPS)
82S Cu(110) 90 SE edge III -0.9 1L UPS, LEED, ELS
(UPS)
83B4 LEED, UPS, TDS
84B Cu(110) 110 Kelvin III -0.95 4L µ0 = 0.85 D
Cu(111) 110 Kelvin III -0.85 4L µ0 = 0.5 D
see Fig. 23
83P5 Cu(110) 350 * -0.09 *mirror electron microscopy
85S5 Cu(100) 80 SE edge -0.8 saturation UPS
(UPS)
93B2 Cu(100) 120 Kelvin III -0.9 10 L HREELS, TDS
defects stabilize H2O clusters
81W2 Ir(110) 140 Diode III -0.7 1L TDS, XPS
-(1 × 2)
81B Ni(110) 150 Kelvin III -0.7 1.2 L UPS, TDS, ELS
84P4 Ni(100) 100 SE edge -1.05 sat. UPS, XPS, TDS
(UPS)
87N Ni(111) 100 (Kelvin) III -0.65 2.5 L disordered layer
LEED, UPS
89P Ni(111) (100) SE edge III -1.1 θ = 0.66 ARUPS, LEED, XPS, TDS
(UPS) Authors propose bilayer model.
90C Ni(110) 130 Kelvin III -1.15 1.2 L LEED, TDS, NRA
θ § c(2 × 2) structure
92B2 Ni(665) 150 Kelvin III -0.7 θ = 0.75 LEED, TDS
H2O decorates the steps
Ni(221) 150 Kelvin III -1.4 (665): 11 (111) terraces +
1 (11 1 )step
(221): 3 (111) terraces +
1 (11 1 )step
92C2 Ni(110) 180 Kelvin III -0.6 LEED, ESDIAD, TDS, FTIR-RAS
c(2 × 2), H2O plane highly incli-
ned to surface normal
93M Ni(11 11 140 Kelvin III -1.05 LEED, TDS
9) (11 11 9): 10.5 (111) terraces +
1 (11 1 )step
µ0 = 1.2 D
Steps are decorated by H2O:

Ref. H2O, D2O/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
94M2 Ni(775) 150 Kelvin III -0.75 1.5 L LEED, AES
also: co-adsorption with Na
98R NiO(100) 120 ? -1.0 1 ML
90H4 Pd(110) 100 Kelvin III -0.73 θ = 0.5 LEED, TDS
86F3 Pt(110) 100 Kelvin III -1.0 5L ESDIAD, TDS
89R Pt(111) 90 SE edge III -1.15 UPS
(UPS) see Fig. 24
97V3 Pt(111) 90 Kelvin III -1.1 5L LEED, AES, IRAS
81T Ru(0001) 95 Diode III -0.6 2L LEED, HREELS, TDS
hydrogen bonded bilayer
(¥î¥5ÛVWUXFWXUHE\/(('
91P Ru(0001) 120 SE edge III -1.2 5L LEED, UPS, XPS
(UPS) see Fig. 25
95H Ru(0001) III -1.28 θ = 0.66 LEED, TDS, p(¥î¥
bilayer µ0 = 0.34 D
ȝ '0 = 0.65 D;
depolarization included with
two A states for the H2O bilayer
one A state for the D2O bilayer
96K2 Ru(0001) 400 Kelvin +0.20 0.25 ML LEED, HREELS, TDS
+0.75 0.5 ML similar result for
Ru(12(001) × (010))
+0.20 1.6 L similar result for
+0.77 6L Ru(12(001) × (010))
96L3 Ru(0001) 82 Kelvin III -1.3 bilayer at MDS, TDS
1.3 L
-1.7 3.5 L
97H Ru(0001) 120 Kelvin III -1.34 2L TDS: 2 states A1, A2 for the H2O
bilayer only one A state for D2O
94H2 TiO2(110) 90 SE edge III -1.1 θ* = 0.75 * θ = 1.0 refers to the saturation
(XPS) value for the 275 K TDS peak.
Band bending only 0.1 eV.
XPS, TDS
92M5 WSe2 100... ARUPS III -1.4 10 L UPS
(p-type) 140 band bending also determined
WSe2 III -0.7 6L
(n-type)
InSe III -0.9 10 L
GaSe III -0.9
(p-type)
96M2 WSe2 Kelvin III -0.2 3L UPS
(0001)
(p-type)
97B Zr(0001) 80 (Kelvin) III -1.1 1. layer LEED, TDS, NRA, FTIR-RAS
-1.3 2. layer
(θ = 0.75)

4.2.4.8 H2S
Table 29. H2S
Ref. H2S/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
79F Ru(11 2 0) 80 SE edge II 0.16 0.8 L H2S dissociates
(UPS) -0.36 / molecular adsorption
4.2.4.9 CO2, SO2, (CH3)2SO, (CH3)3PO3
Table 30. CO2
Ref. CO2/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
94B3 Cu(332) 95 Kelvin III -0.4 200 L LEED, AES, UPS, TDS
96H2 Cu(111) 100 Kelvin TDS, UPS, XPS
also with co-adsorbed K
86B3 Fe(111) 140 SE edge 1.25 1.5 L UPS
(UPS) unclear which species this is
69O Ni(100) 300 0.3 60 L LEED
dissociative adsorption
CO2 ĺ&22
87B Ni(110) 80 SE edge II 0.6 1L ARUPS, HREELS

(UPS) 0.5 2L CO2 parallel to surface ±20°
140 I 0.9 3L anionic bent species
69A W(100) 300 Therm 0.44
76H W(100) 300 Diode I 0.56 LEED, AES, TDS
Table 31. SO2
Ref. SO2/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
92A Cu(111) 80 Kelvin I -0.22 LEED, AES, TDS
200 III 0.24
88O TiO2(110) 300 SE edge 0.3 SO2 dissociates
(UPS)
SE edge
TiO2(441) 300 (UPS) 0.4 SO2 dissociates
85S4 Ti2O3 300 SE edge 1.3 LEED, UPS, XPS
(1012) (UPS) dissociative adsorption leading to
TiO2 and TiS2
Table 32. (CH3)2SO
Ref. (CH3)2SO / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
97S2 Au(100) 100 III -0.77 25 L TDS, XPS

Table 33. (CH3)3PO3
Ref. (CH3)3PO3/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
85H3 Rh(100) 100 SE edge -2.25 ML TDS, XPS, UPS
(UPS) -2.50 multilayer conclusion: PO points to the
surface: µ0 = 2.5 D
4.2.4.10 C2N2, HCN
Table 34. C2N2
Ref. C2N2/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
89R2 Pd(110) 300 SE edge I 1.0 sat. LEED, ARUPS, TDS, several
80 (UPS) ? 1.8 sat. LEED structures; above 200 K
C2N2 is believed to decompose
into 2 CN.
78N Pt(111) 300 SE edge I 0.5 sat. LEED, AES, TDS
el.
83G3 Ru(10 1 0) 300 I +0.8 2.5 L LEED, AES, TDS, UPS
Table 35. HCN
Ref. HCN/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
88H6 Pt(111) 90 Kelvin III -1.15 4L TDS, LEED

4.2.4.11 CH3CN, HCOOH, HNCO
Table 36. CH3CN (Acetonitrile)
Ref. CH3CN/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
83S2 Pt(111) 100 SE edge -1.5 ML XPS, TDS, HREELS
(UPS) -1.75 multilayer conclusion: CŁ1UHK\EULGL]HVWR
Cő1DQGFKHPLVRUEVQHDUO\
parallel to surface
92O2 Pt(111) III -1.4 2L LEED, AES, IRAS, TDS
-1.5 4L (multilayer)
97V3
Table 37. HCOOH (formic acid)
Ref. HCOOH/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
83M GaAs(110) 300 K III -0.5 sat. n-type, see Figs. and
-0.65 sat. p-type
88O TiO2(110) 300 SE edge -0.9 sat. molecularly adsorbed
(UPS)
SE edge
TiO2(441) 300 (UPS) -0.7 sat. molecularly adsorbed
Table 38. HNCO
Ref. HNCO/ T [K] Method Typ ∆Φ [eV] at θ1 Comments, interpretation

Substrate
83G3 Ru(10 1 0) 300 I +0.80 2.5 L LEED, AES, UPS, TDS
4.2.4.12 KOH, KCl, HCl, HBr
Table 39. KOH
Ref. KOH/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
95M Si(100) 300 Diode III -3.0 2 nm assumed intact KOH to be ad-
sorbed.
µ0 = 1 D
Table 40. KCl
Ref. KCl/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
86S Ag(111) 100 FEM III -1.1 sat. quartz microbalance, AES
670 III -0.35 sat.
89S Ag(110) 100 FEM III -1.0 sat. completely reversible
300 -0.9 sat.
670 -0.35 sat.

Table 41. HCl, HBr
Ref. HCl, HBr/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
78M Si(111) 300 SE edge 0.2 sat. both for HCl, HBr
both adsorb as molecular entities
4.2.5 Nonpolar hydrocarbons

Table 42. Methane (CH4)
Ref. CH4/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
96A Pt(111) 55 SE edge III -0.42 TDS, UPS
(UPS) µ0 = 0.54 D
96M Pt(111) 40 SE edge III -0.5 0.3 ML XPS, TDS
(XPS)
71Y W(100) 110 FEM I -0.34 sat.
72M3 W(111) 125 Diode III -0.30(5) TDS
78S W(100) 300 FEM IV -0.3 θ1 adsorbed species is probably CH2
0.2 3θ1
W(111) 300 FEM I 0.35 θ1 probably CH3 + H
Table 43. Propane (C3H8)
Ref. C3H8/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
71L Ni(111) 300 Diode III -0.3 LEED
Table 44. Ethylene (C2H4)

Substrate
86K3 Ag(110) 100...300 K III -0.7 2L LEED, UPS, TDS
86B -1.45 sat max. coverage < 0.5 at 100 K
C2H4 π-bonded to surface
c(2 × 2) structure
bonding via the O-atom
96H Ag(110) 90...750 K III -0.35 1L LEED, TDS, HREELS
conclusion: O interacts with Ag
surface; µ0 = 0.4 D
80K3 Al(100) 300 K II +0.24 θ1 LEED, AES
-0.4 θ2
84R2 Cu(110) 90 SE edge III -1.1 sat. UPS
(UPS)
97L2 Cu(111) 90 K III -0.9 1.8 L LEED, HREELS, TDS
conclusion: π-bond to surface ad-
sorption is reversible
74D2 Ni(111) 300 Diode III -0.3 sat. TDS


Substrate
75F Ni(111)*+ 80 FN II +0.13 θ1 *film
+
-0.44 θ2 dissociation at the beginning
Pd(111)*+ 80 FN II +0.08 θ1
-0.8 θ2
Pt(111)*+ 80 FN III -1.45 sat.
Cu(111)* 80 FN III +0.28 sat.
Au(111)* 80 FN III -0.46 sat.
Al(111)* 80 II +0.04 θ1
-0.06 θ2
79B2 Ni(111) 300 -0.3 sat. LEED, TDS, HREELS
conclusion: dehydrogenation to
C2H2
76G Pt(111) 300 Diode -1.5 1·10-8 torr LEED: diffuse (1/2 O) features
525 Diode -1.7 1·10-8 torr disordered
Pt(100) 300 Diode -1.2 1·10-8 torr LEED: substrate: (1 × 1)
-(5 × 1) 525 Diode -1.5 1·10-8 torr adsorbate: (¥î¥5Û
(1 × 1) disordered
78N Pt(111) 300 SE edge III -1.6 sat. LEED, AES, TDS
stepped (E)
79V Pt(111) 90 -1.4 sat.
210 FEM III -1.3 sat.
325 FN -0.7 sat.
Pt(533) 210 FN III -1.4 sat.
Pt(110) 210 FN III -1.2 sat.
Pt(210) 210 FN III -0.9 sat.
86A2 Pt(111) 300 Kelvin III -1.1
120 III -1.0
88Z Pt(111) 100 SE edge III -0.9 TDS, SIMS
320 (E) III -1.5 also other temperatures
88M2 Rh(111) 300 Diode III -1.2 6L
76E2 Re film 300 Diode II -0.18 1·1014 molecules cm-2
0.0 2.5·1014 molecules cm-2
-0.35 5.5·1014 molecules cm-2
84K Si(111) 330 K III -0.15 104 L TDS

74B W(100) 300 K III -0.5 sat.
W(111) 300 K III -0.45 sat.
W(211) 300 K III -0.45 sat.
W(110) 300 K III -1.1 sat.

Table 45. Acetylene (C2H2)

Substrate
74D2 Ni(111) 300 Diode III -0.6 at 4·10-9 mbar TDS
-1.0 at 1·10-8 mbar
77D2 Ni(111) 180 SE edge -1.2 saturation UPS
(UPS)
Pd(111) 180 SE edge -1.4 saturation
(UPS)
Pt(111) 180 SE edge -1.6 saturation
(UPS)
78B Ni(111) 300 III -1.3 6L LEED, TDS, HREELS
76G Pt(111) 300 Diode -1.5 LEED (2 × 2)
p = 1·10-8 torr
420 -1.65 after 10 min, disordered,
-1.8 1·10-8 torr, disordered
Pt(100) 300 Diode -1.65 LEED: substrate changes to (1 × 1)
-(5 × 1) Adsorbate structure (¥î¥5Û
420 -1.7 4·10-7 torr , no further change in
structure.
86A2 Pt(111) 300 Kelvin III -1.3
120 III -1.4
78R W(100) 300 Diode II +0.3 0.2 L AES, ELS
0.0 0.7 L
-0.6 5L
Table 46. Propylene (CH3CH:CH2)
Ref. CH3CH:CH2 T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

/Substrate
76G Pt(111) 300 Diode -1.3 LEED: (2 × 2)
-(1 × 1)
Pt(100) 300 Diode -1.2 LEED: ½ order streaks
-(5 × 1)
Table 47. Cyclopentane (C5H10)

Substrate
76G Pt(111) 300 Diode -1.0 7·10-9 torr LEED: (1 × 1)
-(1 × 1) low background
300 -0.7 4·10-7 torr disordered
Pt(100) 300 Diode -0.4 7·10-9 torr LEED: (5 × 1)
-(5 × 1) low background
-0.3 4·10-7 torr diffuse features at ½ order

Table 48. Pentadiene (C5H8)

Substrate
84A2 Pt(111) 90 Diode -1.5 sat. TDS, HREELS
conclusion: tilted C5-ring
Table 49. n-hexane (C6H14)

Substrate
76G Pt(111) 300 Diode -1.1 LEED: disordered
-(1 × 1)
Pt(100) 300 Diode -0.8 LEED: disordered
-(5 × 1)
Table 50. Cyclohexane (C6H12)

Substrate
76G Pt(111) 300 Diode -1.2 6·10-9 torr LEED: (1 × 1)
300 -0.7 4·10-7 torr very poorly ordered
420 -1.1 4·10-7 torr apparent (2 × 2)
573 -1.4 4·10-7 torr disordered
Pt(100)- 300 Diode -0.75 6·10-9 torr LEED: (5 × 1)
(5 × 1) 300 -0.4 4·10-7 torr LEED: (1 × 1) and diffuse strea-
ked (2 × 1) pattern
420 -1.2 4·10-7 torr LEED: (1 × 1) and diffuse strea-
ked (2 × 1) pattern
573 -1.5 4·10-7 torr LEED: (1 × 1) disordered
91E Pt(111) 130 SE edge III -0.89 at 1.2 L
(UPS)
97S Pt(111) 160... SE edge III -0.6 sat. TDS, HREELS
380 (UPS)
Table 51. Cyclohexene ()

Substrate
76G Pt(111) 300 Diode -1.7  2 2 
-(1 × 1) LEED: 
4 − 2
425 -1.6
LEED: apparent (2 × 2)
Pt(100) 300 Diode -1.6 LEED: (1 × 1)
-(5 × 1) diffuse (½ O) features
-1.5 LEED: (1 × 1)
streaked (2 × 1)

Table 52. 1,3 Cyclohexadiene (C6H8)

Substrate
76G Pt(111) 300 Diode -1.8 2·10-8 torr LEED: poorly ordered
-(1 × 1) -1.3 1h  4 − 2
-0.8 2·10-8 torr LEED:  0 4 
5h  
-8
2·10 torr  4 − 2
LEED:  
0 5 
Pt(100) 300 Diode -1.7 2·10-8 torr LEED: diffuse, ½ order streaks
-(5 × 1)
-1.6 1h LEED: diffuse, ½ order streaks
2·10-8 torr
-1.4 5h LEED: diffuse, ½ order streaks
2·10-8 torr
Table 53. Benzene (C6H6, C6D6)
Ref. C6H6, C6D6/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
90Z2 Ag(111) 100 SE edge I -0.7 1 ML TDS, XPS, UPS
98V2 Cu(111) 85 2PPE III -0.9 sat. LEED, 2PPE
Fig. 3
74D2 Ni(111) 300 Diode III -1.2 3.5 L TDS
-0.8 after pumping
88N3 Pd(110) 80 SE edge III -1.1 3L ARUPS, LEED, c(4 × 2), AES
(UPS) linear decrease of Φ
azimuthally oriented, tilted by
10 - 20º with respect to the surface
73G Pt(111) 300 ret. field IV -1.4 θ1 LEED, ordered structures
-0.7 θ2
Pt(100)- 300 ret. field IV -1.6 θ1 LEED, ordered structures
(5 × 1) -1.1 θ2
76G Pt(111) 300 Diode -1.8 4·10-7 torr, poorly ordered
300 -1.4  4 − 2
300 -0.7 5 min at 4·10-7 LEED:  
0 4 
 4 − 2
40 min at 4·10-7 LEED:  
Pt(100)- 300 Diode -1.6 0 5 
(5 × 1) LEED: substrate changes into
(1 × 1)
adsorbate: diffuse mig-like
½ order streakes
85A Pt(111) 300 Kelvin -1.5 saturation AES, HREELS, TDS
82R Pt(100)- 300 SE edge III -1.5 10 L ARUPS
(5 × 20) (UPS)
88M2 Rh(111) 300 Diode III -1.4 C6D6

Ref. C6H6, C6D6/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
88J2 Ru(0001) 120...25 K III -1.8 sat. LEED, HREELS
0 C6H6-mig parallel to surface
max. coverage: 0.14 molecule/Ru
atom; µ0 = 2.2 D
99W W(110) Kelvin III -1.5 2.5·1014 TDS, XPS
atoms cm-2
Table 54. Toluene (C6H5CH3)
Ref. C6H5CH3/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
74G Pt(111) 300 Diode -1.7 LEED: streaks at 1/3 order
-(1 × 1)
425 (4 × 2)
Pt(100) 300 Diode -1.5 LEED: (5 × 1), streaks at 1/3
-(5 × 1) order
425 (1 × 1) high background
85A Pt(111) 300 Kelvin -1.6 saturation AES, HREELS, TDS
Table 55. Ethylbenzene (C6H5C2H5)
Ref. C6H5C2H5/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
98R2 Pt(111) 135 SE edge III -1.8 0.5 ML UPS, TDS
(UPS)
Fe3O4(111) 135 SE edge III -1.2 1 ML
(UPS)
FeO(111) 135 SE edge III -0.2 1 ML
(UPS) -0.5 2 ML
Table 56. N-butylbenzene (C6H5C4H9)

Substrate
-(1 × 1)
Pt(100) 300 Diode - -1.5 LEED: (1 × 1) disordered
-(5 × 1)
Table 57. T-butylbenzene (C6H5C(CH3)3)
Ref. C6H5C(CH3)3 T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

/Substrate
-(1 × 1)
Pt(100) 300 Diode -1.8 LEED: (1 × 1) disordered
-(5 × 1)

Table 58. M-xylene (C6H4(CH3)2)
Ref. C6H4(CH3)2/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
74G Pt(111) 325 Diode -1.8 LEED: streaks at 1/2.6 order
-(1 × 1)
Pt(100) 325 Diode -1.7 LEED: (5 × 1) streaks at 1/3 order
-(5 × 1)
Table 59. Biphenyle (C6H5C6H5)

Substrate
74G Pt(111) 300 Diode -1.9 LEED: very poorly ordered
-(1 × 1)
-(5 × 1)
Table 60. Naphtalene (C10H8)

Substrate
73G Pt(100) 300 Diode III -1.7 sat. LEED
-(5 × 1)
76G Pt(111) 300 Diode -1.95 9·10-9 torr LEED: apparent (3 × 1)
425 Diode -2.0 9·10-9 torr LEED: (6 × 6)
Pt(100) 300 Diode -1.7 9·10-9 torr LEED: substrate: (1 × 1)
-(5 × 1) adsorbate: disordered
-1.65 9·10-9 torr LEED: substrate: (1 × 1)
adsorbate: disordered
Table 61. 2-Methylnaphtalene (C10H7CH3)
Ref. C10H7CH3/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
74G Pt(111) 300 Diode -2.0 LEED: very poorly ordered
-(1 × 1)
Pt(100) 300 Diode -1.6 LEED: disordered
-(5 × 1)

4.2.6 Polar hydrocarbons

Table 62. Methanol (CH3OH)
Ref. CH3OH / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
92S8 Cr(110) 90 SE edge III -2.2 UPS
(UPS)
77R2 Ni(111) 80 SE edge III -1.6 at 6 L TDS, UPS
(UPS)
85S6 Si(111) 80 Diode -1.2 at 80 L TDS, HREELS
-(7 × 7)
82C2 Pd(100) 77 Kelvin III -1.1 at 3 L TDS, UPS
95K4, Pt(111) 100 Kelvin -1.8 LEED, AES, TDS, IRAS
97V3
Table 63. Ethyleneoxide (C2H4O)
Ref. C2H4O / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
86K3, Ag(110) 100...300 Kelvin III -1.45 sat. LEED, UPS, TDS
86B c(2 × 2) structure
bonding via the O-atom
87B4 Fe(100) 100...300 SE edge IV -2.2 0.5 ML ARUPS
(UPS) -1.9 0.75 ML
87B4 Ni(111) 100...300 SE edge III -1.3 sat. ARUPS
(UPS)
90N Ni(111) 100 Kelvin III -1.6 2L TDS
co-adsorption with K
93W Ni(110) SE edge III -2.9 0.5 ML LEED, TDS, ARUPS
(UPS) c(2 × 2) structure
93W2 Pt(110) 140 SE edge III -2.1 0.5 ML LEED, TDS, ARUPS
-(1 × 2) (UPS) two differently oriented species
Table 64. Ethylenedioxide ((CH2)4O2)
Ref. (CH2)4O2/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
96H Ag(110) 90...750 Kelvin III -0.35 1L LEED, TDS, HREELS
conclusion: O interacts with Ag
surface; µ0 = 0.4 D
Table 65. Acetone (C3H6O)

Substrate
95K4, Pt(111) 100 Kelvin -1.6 LEED, AES, TDS, IRAS
97V3

Table 66. Furan (C4H4O)

Substrate
96O2 Pd(111) 175 SE edge III -1.5 XPS, UPS
(UPS)
Table 67. Benzenethiol (C6H5SH)
Ref. C6H5SH / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
99W2 Au(111) 300 ARUPS III -0.6 at 10 L LEED, HREELS, ARUPS, XPS
µ0 = 1.6·1030 Cm
82A Cu(111) 300 SE edge -1.0 saturation ARUPS
(UPS) at 10 L
Table 68. Pyridine (C6H5N)
Ref. C6H5N / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
88N2 Pd(110) 300 SE edge III -1.07 sat. (5 L) LEED, ARUPS
(UPS) c(4 × 2) structure
orientation parallel to surface
73G Pt(111) 300 Diode III -2.4 sat. LEED
Pt(100) 300 Diode III -2.4 sat. LEED
-(5 × 1)
76G Pt(111) 300 Diode -2.7 1·10-8 torr LEED: diffuse (1/2 O) features
-(1 × 1)
525 Diode -1.7 1·10-8 torr LEED: well defined streaks at 1/3,
2/3, 3/3 order
Pt(100) 300 Diode -2.4 1·10-8 torr LEED: (1 × 1) and disordered
-(5 × 1)
525 Diode 1·10-8 torr LEED: (1 × 1) plus (¥ × ¥5Û
Table 69. Aniline (C6H5NH2)
Ref. C6H5NH2/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
74G Pt(111) 300 Diode -1.8 LEED: streaks at 1/3 order
-(1 × 1)
-(5 × 1)
Table 70. Nitrobenzene (C6H5NO2)
Ref. C6H5NO2/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
74G Pt(111) 300 Diode -1.5 LEED: 1/3 order features
-(1 × 1)
-(5 × 1)

Table 71. Cyanobenzene (C6H5CN)
Ref. C6H5CN / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
74G Pt(111) 300 Diode -1.6 LEED: 1/3 order features
-(1 × 1)
-(5 × 1)
4.2.7 Halohydrocarbons
Table 72. Chloro-methane (ClCH3)
Ref. ClCH3/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
89Z Ag(111) 100 SE edge IV -0.8 0.9 ML XPS, UPS, TDS
(UPS) -0.6 1.3 ML 1 ML = 4.6(3)·1014 molecules cm-
2
97Y2 Al(111) 90 SE edge III -0.55 at 7 L UPS

(UPS)
90S2 Pd(100) 100 SE edge IV -0.9 3L UPS, TDS
(UPS) -0.75 12 L
99L Ru(0001) 100 Kelvin IV -1.9 min, 1.8 L
-1.5 3.5 L
-1.7 6L
97K4 Si(111) 100 K I 0.4 4L CH3Cl weakly bound at 100 K
does not react
Table 73. Chloro-ethane (ClC2H5)
Ref. ClC2H5/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
91Z3 Ag(111) 100 SE edge III -1.0 1 ML TDS, UPS, XPS
(UPS)
Table 74. Di-chloro-methane (Cl2CH2)
Ref. Cl2CH2/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
Table 75. Tri-chloro-methane (Cl3CH)
Ref. Cl3CH / T [K] Method Typ ∆Φ [eV] at θ1 Comments, interpretation

Substrate
84G1 Ag(111) 300 SE edge +1.0 LEED, UPS
(UPS)

Table 76. Tetra-chloro-methane (Cl4C)
Ref. Cl4C / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
79J3 Fe(100) 300 Diode 1.30 sat. mobile precursor
Table 77. Bromo-methane (BrCH3)
Ref. BrCH3/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
89Z Ag(111) 100 SE edge IV -1.0 0.9 ML XPS, UPS, TDS
(UPS) -0.7 1.4 ML 1 ML = 4.6(3)·1014 molecules cm-2
99L2 Ru(0001) 82 Kelvin IV -2.2 min, 3.5 L TDS, also with a ML of Cu
-1.85 6.5 L
Table 78. Di-bromo-methane (Br2CH2)
Ref. Br2CH2/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
(UPS)
Table 79. Tetra-bromo-methane (Br4C)
Ref. Br4C / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
79D3 Fe(100) 300 Diode I 0.95 sat. LEED, AES
CBr4 dissociates
Table 80. Iodo-methane (ICH3)
Ref. ICH3/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
(UPS)
95Y Au(100) 105 Diode -1.0 min at 5...15 L TDS, IRAS, HREELS
-0.8 30 L
93S8 Pd(100) 85 SE edge III -1.5 1.5 L UPS
(UPS)
Table 81. Iodo-ethane (IC2H5)
Ref. IC2H5/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
95Y Au(100) 105 Diode -0.85 min 7 L TDS, IRAS, HREELS
+0.1 25 L
Table 82. Chloro-tri-fluoro-methane (ClCF3)
Ref. ClCF3/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
92K Pt(111) 50 SE edge III -0.15 2.5 ML XPS, UPS, TDS
(UPS) CF3Cl does not react at 50 K

Table 83. 1,2-di-chloro-ethane (ClCH2CH2Cl)
Ref. ClCH2CH2Cl T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

/Substrate
92W2 Cu(111) 110 SE edge -0.55 at 1 ML UPS
Table 84. 1,2-di-chloro-ethene (ClCH:CHCl)
Ref. ClCH:CHCl / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
97Y Cu(100) 120 SE edge -0.25* NEXAFS
(E) -0.45** * CHClő&&O2
** cis-CHClő&+&O
Table 85. 1,2-chloro-bromo-ethane (ClCH2CH2Br)
Ref. ClCH2CH2Br T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

/Substrate
93K2 Cu(111) 111 SE edge I 0.8 sat. at 300 K Br/Cl adsorbate is
(E) formed and C2H4 desorbed
99T Cu(111) 100 SE edge -0.55 12 L LEED, AES, UPS
(UPS) -0.4 30 L
300 +0.75 10 L
Table 86. Iodo-benzene (IC6H5)
Ref. Substrate T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

92X Cu(111) 110 SE edge 0.6 2L AES, TDS, HREELS
(E)
Table 87. Chloro-benzene (ClC6H5)
Ref. ClC6H5/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
82R Pt(100)- 300 SE III -0.85 10 L ARUPS
(5 × 20) edge
(UPS)
4.2.8 Other hydrocarbons

Table 88. Di-ethyl-zink ((C2H5)2Zn)
Ref. (C2H5)2Zn / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
94K2 Pd(100) 90 SE edge IV -1.1 θ1 XPS, TDS
(UPS) -0.6 4θ1
99K4 Rh(111) 90 SE edge III -1.3 2L XPS, TDS, HREELS
(E)

Table 89. glycine (α-amino acetic acid) (H2NCH2CO2H)
Ref. H2NCH2 – T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

CO2H /
Substrate
89E3 Pt(111) 120 SE edge III -1.7 10·1014 LEED, TDS, UPS
(UPS) atoms cm-2
Table 90. Closo-1,2-di-carbado-decaborane (C2B10H12)
Ref. C2B10H12/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
94Z2 Cu(100) 150... SE edge I 2.0 sat.
400 (UPS)
Table 91. TCNQ (Tetra-cyano-quino-dimethane) (C12N4H4)
Ref. C12N4H4/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
86E2 Cu(111) 100 Diode I 0.8 at 1 ML HREELS supports negatively
1.36 at 2 ML charged layer
86E4 Cu(111) 100 Diode I 0.78 1. layer HREELS
1.28 2. layer
1.36 3. layer
4.2.9. Alkali metals

Table 92. Lithium (Li)
Ref. Li/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
86P2 Ag(111) 300 Kelvin IV -1.86 min
-1.76 ML
86P3 Ag(111) 300 Kelvin IV -1.9 min θLi = 0.5 AES
85P4 -1.8 ML θLi = 1.0
89H2 Al(111) 140 Kelvin III -1.20 1 1015 atoms cm-2
LEED, AES, TDS
µ0 = 2.1 D
95G3 CdTe(100) Diode III -1.8 ML LEED, AES, ELS
µ0 = 3.2 D
94M3 Cu(100) 180 SE edge IV -2.0 θLi = 0.55 LEED, AES
(E) -1.7 θLi = 0.8
96L Cu(111) 160 Diode IV -2.4 min ELS
-1.85 ML
87A4 GaAs(100) Kelvin -1.8 min
(IBA) -1.6 ML
79G2 Mo(211) 77 Diode III -1.5 ML
84K4 Mo(110) 5, 77, Diode IV -2.6 min θLi = 0.35
300 -1.7 ML θLi = 1


Substrate
88G3 Ni(100) 310 Diode IV -2.8 min RP
-2.5 ML
98M3 Ni(775) IV -2.4 µ0 = 1.5 D
-2.1
94J2 Ru(0001) SE edge IV -3.5 TDS, MDS
θLi = 0.46 α = 12.8 Å
3
(MDS) -2.8
96E Ru(0001) 200 Kelvin IV -3.6 min θLi = 0.45 NMR
-2.5 θLi = 1.0 µ changes from 4 to 0.5 D with
coverage
98E Ru(0001) Kelvin IV -3.5 min θLi = 0.5 µ0 = 4.9 D
-2.5
88N4 Si(111)- SE edge III -2.3 AES, MDS
(7 × 7) (UPS)
91C3 Si(111) IV -2.4 min NMR, TDS
-1.8
93F Si(111)- 300 SE edge III -1.9 1 ML AES, LEED
(7× 7) (E) -2.2 3 ML
94E2 Si(100) 360 Diode III -2.4 AES, TDS
95K3 n-type
p-type 360 Diode III -2.2
95K6 Si(100)- Diode III -1.8 1 ML
(2× 1) -2.4 2 ML
95K7 Si(100)- 300 III -2.3 AES, LEED, UPS
(2× 1) different Li induced super-
structures
66G W(211) 77 FEM III -1.5 ML
-1.8 2. layer
W(110) FEM FEM -3.0 5 1014 atoms cm-2
-2.4 12 1014 atoms cm-2
W(111) FEM III -1.7 5 1014 atoms cm-2
73M W(211) 77 Diode III -1.5 ML LEED
300 III -1.8 2. layer
-1.5 ML
-1.8 2. layer
74M5 W(110) 300 Diode IV -2.9 min 5 1014 cm-2
-1.9 ML 12 1014 cm-2
-2.3 2. layer 20 1014 cm-2
W(110) 77 Diode IV -2.8 min
-2.2 ML
W(110) 77 FEM IV -3.0 min
-2.4 ML
W(211) 300 Diode IV -1.5 1 min 5 1014 cm-2
-2.0 2 min 12 1014 cm-2
-1.9 16 1014 cm-2
W(100) 300 Diode III -1.4 ML 12 1014 cm-2
W(111) 300 Diode III -1.4 ML 12 1014 cm-2


Substrate
84K4 W(110) 5, 77, Diode IV -2.9 min θLi = 0.35 LEED
300 -2.0 ML θLi = 1
Mo(110) Diode IV -2.6 min θLi = 0.35
5, 77, -1.7 ML θLi = 1
300
Table 93. Sodium (Na)
Figs. 26 and 27
Ref. Na / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
77B4 Ag(110) SE edge III -2.0 θNa = 0.45 UPS, XPS
(UPS)
74P Al(111) 300 SE edge III -1.6 ML µ0 = 3.4 D
(E)
Al(100) 300 III -1.6 ML
87P2 Al(100) 100 SE edge IV -2.0 min µ0 = 3.2 D
(E) -1.6 ML
350 SE edge III -1.6 ML µ0 = 3.2 D
(E) linear decrease for
0.08 < θNa < 0.5 explained by
2D clustering. See Fig. 26.
89H2 Al(111) 140 Kelvin IV -1.5 θNa = 0.3 LEED, UPS, ELS
-1.4 µ0 = 1.8 D
Al(111) 300 Kelvin IV -1.7 θNa = 0.3 µ0 = 2.1 D
-1.4
95N2 Au(100) 130 Kelvin IV -2.7 min θNa = 0.22
-2.5 ML θNa = 0.45
300 III -2.5 ML θNa = 0.45, no minimum
observed
LEED, XPS, AES
lifting of (5 × 20)
reconstruction
95S5 Au(100) Kelvin -2.0 at θNa =0.1 XPS
-2.0 θNa = 0.25
-2.3 θNa = 0.55
80L Cu(111) 300 Diode IV -2.7 min θNa = 0.13, µ0 = 11.3 D
-2.3 ML θNa = 0.5, close-packed layer
LEED, AES, ELS, ARUPS
83W Cu(100) 100 Diode IV -2.1 min
-1.8 ML
91T Cu(111) 300 Diode IV -2.2 min θNa = 0.2
-2.0 ML θNa = 0.4
LEED, TDS
93S4 Cu(111) Diode IV -2.8 min θNa = 0.2, µ0 = 4.3 D, UPS
93S5 -2.3 ML θNa = 0.4


Substrate
93S6 Cu(110) Diode IV -2.1 min θNa = 0.5
93T2 SE edge -1.9 ML θNa = 1.0, µ0 = 2.7 D
(UPS) UPS
III -2.0 > θNa = 0.5 LEED, IPES
94F Cu(111) ARUPS IV -2.75 min, θNa =0.33 2PPE
(2PPE) -2.3 ML, θNa = 1
-2.4 2 ML
96L2 Cu(110) 100 ARUPS IV -2.2 min θNa = 0.3 AES, ARUPS
(370) -1.8 θNa = 0.7 ∆Φ is different after heating to
370 K
67P Ge(111) SE edge III -2.5 LEED
(E)
69W2 Ge(111) 300 Diode III -2.5
81B2 Ge(100) FEM IV -2.5 7·1014 atoms cm-2
-2.3 10·1014 atoms cm-2
Ge(111) FEM IV -2.4 7.5·1014 atoms cm-2
-2.3 10·1014 atoms cm-2
96K3 Ge(111) 40 SE edge III -2.5 UPS
(2 × 8) (UPS)
97N4 Ge(100)- Diode III -2.6 1 ML LEED, AES, ELS, TDS
(2 × 1)
80G Mo(211) 77 Diode IV -1.9 min LEED
-1.8 ML
70G Ni(111) 300 Kelvin IV -3.1 min θNa = 0.21, µ0 = 3.7 D
-2.2 ML θNa = 0.45
Ni(100) 300 Kelvin IV -3.1 min θNa = 0.26, µ0 = 3.6 D
-2.5 ML θNa = 0.5
Ni(110) 300 IV -2.1 min See Fig. 27
-2.0 ML
74A2 Ni(100) 300 Diode IV -3.3 min θNa = 0.23, µ0 = 3.4 D
-2.6 ML θNa = 0.45
88G3 Ni(100) 325 Diode IV -3.2 min
-2.4 ML
98M3 Ni(775) IV -2.9 µ0 = 4.3 D
-2.3
93S5 Ni(111) Diode IV -3.2 min θNa = 0.18
-2.6 ML θNa = 0.40
UPS
94B4 NiO 180 SE edge IV -2.2 min UPS, XPS
(UPS) -1.5 thick layer
88M2 Rh(111) 310 Diode IV -2.8 min, θNa = 0.25
-2.3 ML, θNa = 0.55
85K7 Ru(0001) 300 Diode IV -3.6 min µ0 = 3.4 D
-2.8 ML
87K2 Ru(10 1 0) 300 Diode IV -3.0 min, θNa = 0.5 TDS
-2.8 ML, θNa = 1.0 co-adsorption with CO
87R Ru(0001) 300 Diode IV -3.6 min θNa = 0.3
-2.9 ML θNa = 0.6, µ0 = 4.3 D
TDS, ELS


Substrate
91P6 Ru(0001) 120 SE edge IV -3.5 min, θNa = 0.30
(UPS) -3.0 ML, θNa = 0.44
94H3 Ru(0001) 50 Kelvin IV -3.7 min θNa = 0.2, µ0 = 5.0(5) D
-2.9 ML θNa = 0.55
LEED, TDS
69W2 Si(111) 300 Diode III -2.5
89G2 Si(001)- 430 SE edge III -2.9 LEED, AES
89G3 (2 × 1) (E)
91T2 Si(001)- 300 Diode III -3.0 at θNa = 1 LEED, AES, ELS
(2 × 1) clustering for θNa > 0.5
92R2 Si(111)- -2.7 min IPES
(2 × 1) -2.4
93H Si(100)- 100 SE edge IV -2.7 min UPS
(2 × 1) (UPS) -2.2 ML
93J Si(001)- ARUPS III -3.0 LEED, IPES
(2 × 1)
94O Si(111) 300 SE edge -2.5 min UPS
(UPS) -2.3 ML
97C2 Si(100)- 300 SE edge III -3.0 ARUPS
(2 × 1) (UPS)
67O W(100) FEM IV -2.45 min
W(110) FEM IV -3.90 min
W(111) FEM IV -2.0 min
W(112) FEM IV -2.35 min
Re(10 1 1) FEM IV -3.6 min
Re(1120) FEM IV -2.6 min
Re(10 2 2) FEM IV -2.9 min
68K W(110) FEM -3.6 min 5·1014 atoms cm-2
-2.9 10·1014 atoms cm-2
68K W(112) FEM -2.6 min 8·1014 atoms cm-2
-2.4 15·1014 atoms cm-2
W(100) FEM -2.5 min 7·1014 atoms cm-2
-2.2 10·1014 atoms cm-2
W(111) -2.1 7·1014 atoms cm-2
-2.0 10·1014 atoms cm-2
70M W(110) 77 Diode IV -3.4 min
-2.5 ML
-2.8 2. layer
W(110) 300 Diode IV -3.5
-2.5
71C5 W(112) 300 Diode III -2.0
73M3 W(112) 77 Diode IV -2.3 7·1014 atoms cm-2
-2.1 10·1014 atoms cm-2
200 K and 400 K similar
70C W(112) 300 Diode -2.0 at 0.5 ML LEED
W(112) + at θNa = 0.75
1 ML ML
oxygen


Substrate
85C W(100) 300 SE edge IV -3.0 LEED, AES, ARUPS
(UPS) -2.7
97O ZrC(100) SE edge IV -0.6 min θNa = 0.25, AES, UPS
(UPS) -0.1 θNa = 0.8
Table 94. Potassium (K)
Ref. K/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
82F2 Ag(111) Diode IV -2.9 min, θΚ = 0.15
-2.4 ML, θΚ = 0.33
88A2 Ag(111) Kelvin IV -2.8 θΚ = 0.55 LEED, AES
-2.1 θΚ = 1.5
89B4 Ag(111) 100 SE edge IV -3.5 min, θΚ = 0.5 UPS, XPS, ELS
(UPS) -2.8 ML, θΚ = 1.2
91O Ag(100) 325 SE edge III -2.2 θΚ = 1.2
140 (E) IV -2.4 min, θΚ = 0.2
-2.1 ML, θΚ = 0.4
86P2 Al(111) 300 SE edge III -2.2 AES
(E) or
Diode
87P2 Al(100) 100 SE edge IV -2.8 min LEED, AES, TDS
(E) -2.3 ML µ0 = 4.6
350 SE edge III -2.3 linear decrease for 0.05 <
(E) θΚ < 0.4 explained by 2D
clustering
89H2 Al(111) 140 Kelvin IV -2.2 min µ0 = 4.1 D
-1.7 ML
95N2 Au(100) 130 Kelvin IV -3.3 min, θΚ = 0.15 LEED, AES, XPS
-3.0 ML, θΚ = 0.4
300 Kelvin III -3.0 ML
95S4 Au(100) 130 Kelvin IV -3.3 θΚ = 0.15 LEED, XPS
-3.1 θΚ = 0.45 K-induced (5 × 20) ĺ
300 III -2.7 θΚ = 0.1 (1 × 1) “deconstruction”
-2.7 θΚ = 0.2
-3.1 θΚ = 0.45
99W3 Cr2O3(0001) 90 SE edge -3.0 θΚ = 0.5 LEED, XPS, Laser induced
(XPS) -2.9 θΚ = 1.0 desorption
87D2 Cu(100) 120 SE edge IV -3.6 min AES, TDS, ELS
(E) -2.3 ML
85W Cu(110) 300 SE edge IV -3.1 min MDS
(UPS) -2.3 ML
86A4 Cu(100) 330 SE edge IV -3.0 min, θΚ = 0.17 LEED, AES, ELS
(E) -2.5 θΚ = 0.3 µ = 16 D, goes to 3 D with
coverage
92A2 Cu(100) Kelvin IV -2.87 min, at θ1
-1.9 at 5θ1
95H3 Cu(111) 90 Kelvin IV -2.9 min, θΚ = 0.25 TDS
-2.4 θΚ = 0.6 CO-adsorption of CO


Substrate
98B Cu(332) 90 Kelvin IV -2.7 min, 0.8 ML LEED, AES, TDS, UPS
-2.3 2 ML
79B5 Fe(110) 300 SE edge IV -3.7 min, θΚ = 0.18 LEED, AES, UPS
(UPS) -2.8 ML, θΚ = 0.31 µ0 = 6.0 D
81L Fe(100) 300 Kelvin IV -2.4 min µ0 = 7.0 D
-2.1 ML
Fe(110) 300 Kelvin IV -3.5 min µ0 =4.4 D
-3.0 ML
Fe(111) 300 Kelvin IV -2.5 min µ0 = 3.8 D
-2.4 ML
92O GaAs(110)* 300 Kelvin III -2.8 LEED, AES
*prepared by ion bombard-
ment and annealing
GaAs(110)** 300 Kelvin III -3.5 1 ML **cleaved
p-type
n-type 300 Kelvin III -2.4 1 ML **cleaved
69W2 Ge(111) 300 Diode III -3.0
Ge(100) 300 Diode III -3.4
81B2 Ge(100) FEM IV -2.9 at 4.5·1014 atoms cm-2
-2.65 7.5·1014 atoms cm-2
Ge(111) FEM IV -2.8 at 4.5·1014 atoms cm-2
-2.65 7.5·1014 atoms cm-2
99O Graphite(0001) 160 SE edge III -2.2(1) θK = 0.35
85 (UPS)
Diode
76B4 Mo(100) 77 FEM IV -2.4 min, 5·1014
-2.1 atoms cm-2
ML, 9·1014
atoms cm-2
Mo(110) 77 FEM IV -3.1 min, 3·1014
-2.3 atoms cm-2
ML, 6·1014
atoms cm-2
Mo(211) 77 FEM IV -2.5 min, 4·1014
-2.1 atoms cm-2
ML, 8·1014
atoms cm-2
Mo(111) 77 FEM IV -2.1 min, 2.5·1014
-1.7 atoms cm-2
ML, 7.5·1014
atoms cm-2
91P5 MoS2 300 Diode III -1.1 0.2 ML LEED, AES, TDS
(basal) 2 D and 3 D clusters for
coverages θΚ > 0.2
96O NbC(100) SE edge III -2.0 θΚ = 0.5
(UPS)
NbC(111) SE edge IV -3.2 θΚ = 0.3 LEED, UPS
(UPS) -2.8 θΚ = 1.0
73A Ni(100) Diode -3.5 min, θΚ = 0.2 LEED
-2.9 ML, θΚ = 0.33 µ0 = 6.3 D


Substrate
74A2 Ni(100) 300 Diode IV -3.5 min, θΚ = 0.2 µ0 = 6.7 D
-2.8 ML, θΚ = 0.40
84S11 Ni(100) 120 SE edge IV -3.6 min, θΚ = 0.15
(UPS) -2.9 ML, θΚ = 0.33
88G3 Ni(100) 325 Diode IV -3.7 min
-3.3 ML
70G Ni(110) 300 Kelvin IV -2.7 min, θΚ = 0.38 µ0 = 5.3 D; see Fig. 27
-2.5 ML, θΚ = 0.5
85L2 Ni(111) SE edge III -4.1 MDS
(UPS)
86U Ni(111) 90 SE edge IV -4.0 min LEED, IRAS, TDS
(E) -3.5 ML µ0 = 3.7 D
90N Ni(111) 100 Kelvin IV -3.8 min, θΚ = 0.2 TDS
-3.1 θΚ = 0.7
91H2 Ni(100) 40 Kelvin IV -3.3 min
-2.5 ML
98M3 Ni(775) IV -3.5 µ0 = 6.3 D
-2.8
87B6 Pd(100) 300 IV -4.15 LEED, AES, TDS
-3.2 µ0 = 6.4 D
83K3 Pt(111) 300 SE edge IV -4.6 min, θΚ = 0.17 XPS, UPS
(UPS) -3.9 ML, θΚ = 0.33
85L Pt(111) 300 SE edge IV -4.6 µ0 = 9.4 D
(UPS) -4.0
88W Pt(111) SE edge IV -4.8 min, θΚ = 0.5 AES, TDS, UPS, HREELS
(E, UPS) -3.2 ML, θΚ = 1.0
96L2 Pt(111) 140 ARUPS IV -4.3 min, θΚ = 0.3 AES, TDS, UPS
-3.7 ML, θΚ = 0.5 incorporation of K
78L3 Re(10 1 0) 245 Diode IV -3.0 min 4.5·1014 atoms cm-2
-2.6 ML 7·1014 atoms cm-2
97V2 Re(0001) 105 Kelvin IV -4.3 min, θΚ = 0.45 TDS, SHG
-3.0 ML, θΚ = 1.0
92J2 Rh(111) 45 IV -3.8 min, θΚ = 0.35 UPS
-3.4 ML, θΚ = 1.0
85D3 Ru(0001) 80 Kelvin IV -4.3
-2.4
85M Ru(0001) 60 SE edge IV -4.0 min LEED, AES, UPS, TDS
(UPS) -3.3 ML µ0 = 3.6 D
86H4 Ru(10 1 0) 430 Diode IV -2.6 min µ0 = 3.9 D
-2.4 ML
87R Ru(0001) 300 Diode IV -3.9 min, θΚ = 0.17 TDS, ELS
-3.2 ML, θΚ = 0.35 µ0 = 7.8 D
88D Ru(0001) 450 Diode IV -3.7 min LEED, AES, TDS
-3.2
91P6 Ru(0001) 120 SE edge IV -3.8 min, θΚ = 0.2 XPS, UPS
(UPS) -3.0 ML, θΚ = 0.4


Substrate
69W2 Si(111) 300 Diode III -3.0 min
Si(100) 300 Diode IV -3.4
-3.1
83T2 Si(100)-(2 × 1) Diode III -2.1 θΚ = 0.5 LEED, AES, ELS
86O Si(100) 200 Kelvin IV -2.9 min AES
-2.6
Si(111) 300 Kelvin -3.1 min
-2.9
89E2 Si(100)-(2 × 1) ARUPS III -3.3
90M Si(111)-(7 × 7) 300 SE edge IV -3.2 min LEED, IPES, UPS
(UPS) -3.1
90N2 Si(100)-(2 × 1) SE edge IV -3.3 min, θΚ = 0.5
(UPS) -3.0 θΚ = 0.75
90R3 Si(100)-(2 × 1) 300 SE edge IV -3.45 min LEED, IPES, UPS
(UPS) -3.0 ML
92B4 Si(111) 300 Diode IV -3.1 min TDS, LEED, AES
-3.0 ML
92M3 Si(100)-(2 × 1) 300 -3.3 min LEED, AES, UPS, TDS
-2.5 ML includes band bending of
55 -3.3 min 0.3 eV at 300 K.
-2.5 ML
93F Si(111)-(7 × 7) 300 SE edge IV -3.4 min, θΚ = 0.5 LEED, AES
(E) -3.2 ML, θΚ
94W Si(111)-(7 × 7) 300 Diode III -3.0 LEED, AES, ARUPS
Si(111)
(¥î¥5Û% 300 Diode III -3.0 LEED, AES, ARUPS
97C3 Si(100)-(2 × 1) 300 SE edge III -3.5 min ARUPS
(UPS)
97N5 Si(111) 300 SE edge III -3.20 UPS
cleaved (UPS) (-3.56) second experiment
76B4 Ta(100) 77 FEM IV -2.3 min, 2.2·1014
-2.1 atoms cm-2
ML, 4·1014
atoms cm-2
Ta(110) 77 FEM IV -3.1 min, 2.3·1014
-2.2 atoms cm-2
ML, 4·1014
atoms cm-2
Ta(111) 77 FEM IV -1.6 min, 2.2·1014
-1.3 atoms cm-2
ML, 3.5·1014
atoms cm-2
Ta(211) 77 FEM IV -2.0 min, 3·1014
-1.8 atoms cm-2
ML, 4·1014
atoms cm-2
95H2 TiO2(110) ARUPS IV -3.8 min, θΚ = 0.4 LEED, ARUPS
-3.4 ML, θΚ = 0.7
65S W (averaged) FEM -2.6 min
-2.2


Substrate
66S W(100) 300 FEM IV -2.8 min, θΚ = 0.8 µ0 = 4.7 D
-2.4 ML, θΚ = 1.2
W(110) 300 FEM IV -2.8 min, θΚ = 0.85 µ0 = 7.8 D
-2.4 ML, θΚ = 1.1
W(111) 300 FEM IV -2.7 min, θΚ = 0.85 µ0 = 5.7 D
-2.4 ML, θΚ = 1.1
W(211) 300 FEM IV -2.8 min, θΚ = 0.85 µ0 = 6.8 D
-2.4 ML, θΚ = 1.1
67O2 W(100) FEM IV -3.0
-2.6
W(110) IV -4.3
-3.4
W(111) IV -2.5
-2.3
W(112) IV -3.2
-2.8
74M5 W(211) 245 IV -2.9 min,
-2.7 ML
74M7 W(112) 245 Diode -2.9 min 4·1014 atoms cm2
-2.2 2. layer 12·1014 atoms cm2
LEED
75B W(100) 77 FEM IV -3.0 min, 3.6·1014 µ0 = 4.8 D
-2.6 atoms cm-2
ML, 6.2·1014
atoms cm-2
W(110) 77 FEM IV -4.1 min, 2.8·1014
-3.2 atoms cm-2
ML, 4.6·1014
atoms cm-2
W(111) 77 FEM IV -2.5 min, 4·1014 µ0 = 4.1 D
-2.3 atoms cm-2
ML, 7·1014
atoms cm-2
W(211) 77 FEM IV -2.9 min, 3.5·1014 µ0 = 4.1 D
-2.7 atoms cm-2
ML, 6·1014
atoms cm-2
76B4 W(110) 77 FEM µ0 = 8.6 D
85C W(100) 300 SE edge -3.1 min LEED, AES, ARUPS
(UPS) -2.7 ML, θΚ = 0.6
91D W(112) 78 FEM IV -3.0 min
-2.7 ML

Table 95. Rubidium (Rb)
Fig. 28
Ref. Rb / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
89H2 Al(111) 140 Kelvin IV -2.3 min LEED, AES, UPS
-1.8 ML µ0 = 4.1 D; see Fig. 28
99S2 Cu(100) IV -2.8 min, θRb = 0.15 data of H. Schief, Diploma
-2.5 θRb = 0.3 Thesis, University Göttingen,
1990
97C3 Si(100) 300 SE edge III -3.5 min ARUPS
-(2 × 1) (UPS)
Table 96. Cesium (Cs)
Fig. 29
Ref. Cs / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
83H Ag(110) 300 SE edge IV -2.5 min LEED, AES
(UPS) -2.4 ML small amounts of alkali drive a
(1 × 2) reconstruction
86D Ag(110) 300 Kelvin IV -2.4 min θCs = 0.26
-2.2 ML θCs = 0.4
100 Kelvin -2.6 min
88A2 Ag(111) Kelvin IV -3.1 θCs = 0.6 LEED, AES
-2.7 θCs = 1.3
93S7 Ag(100) 80 Kelvin IV -2.9 min, θCs = 0.4 LEED, TDS
-2.3 ML,θCs> 0.9
86P2 Al(111) 300 SE edge IV -2.6 min AES
(E) -2.3 ML
87H Al(111) 140 Kelvin IV -2.4 min UPS, µ0 = 4.1 D
-1.8 ML
89H2 Al(111) 140 Kelvin IV -2.4 min LEED, AES, UPS
-1.8 ML µ0 = 4.1 D
94K3 Al(111) 85 Diode -2.57 min, θCs = 0.22 TDS, HREELS
-2.0 ML, θCs= 0.4
87T Be (polycr.) IV -2.4 2·1014 atoms AES
-1.6 cm2
94G3 CdTe(100) Diode III -1.7 θCs = 0.33 ML
LEED, AES
78L2 Cu(111) 300 Diode IV -3.4 min θCs = 0.16, µ0 = 9.6 D
80L -3.0 ML θCs = 0.26, p(2 × 2) close-
packed layer
LEED, AES, ELS, ARUPS
82P7 Cu(100) 300 Diode IV -3.0 min θCs = 0.14
-2.5 ML θCs = 0.27


Substrate
91S Cu(110) 100 Kelvin IV -2.8 min θCs = 0.16
-2.4 ML θCs = 0.28
260 IV -2.6 min θCs = 0.22
-2.4 ML θCs = 0.33
97A Cu(100) 300 Diode IV -3.1 min θCs = 0.45, IPE
-2.6 ML θCs = 1.0
71M GaAs(110) Diode III -4.0
(cleaved)
p-type
77D3 GaAs(110) Diode III -3.4 saturation LEED, AES
cleaved in
air
78C2 GaAs(110) 300 Kelvin III -3.3 θCs = 0.6
(cleaved)
n-type
Ge(111) 300 Kelvin III -3.3 θCs = 0.8
p-type
84R3 GaAS(111) Diode III -3.2 saturation
B
GaAs(100)
89M3 GaAs(110)* 300 SE edge III -3.7 *prepared by IBA
(UPS)
75D GaP(111) 80 Diode III -1.8(2) LEED: (1 × 1)
or 300
GaP( 1 1 1 )
69W2 Ge(111) 300 Diode IV -3.2 min
-3.0
Ge(100) 300 Diode IV -3.4 min
-3.1
86H5 Graphite Diode IV -2.4 min LEED:
(0001) 5·1014 atoms (¥î¥5ÛSDWWHUQ
cm2
81G Mo(211) 77 IV -2.8 min LEED
-2.7 ML
-2.3 2. layer
82S5 Mo(100) ? ? IV -3.6 min ELS
-3.4 ML
92E2 Mo(110) Diode IV -3.6 min
-2.9 ML
94G4 Mo(110) 77 Diode -2.5 3 1014 atoms cm−2
-1.9 15·1014 atoms cm-2
LEED, ELS
78P3 MoS2 300 Diode III -1.8
cleaved in 200 III -2.8
air
85K9 MoS2(0001) 300 Diode III -2.3 AES, TDS
85K10 170 III -3.0
78P2 NbSe2 200 Diode III -3.0 LEED
NbSe2 300 Diode III -0.6
70G Ni(110) 300 Kelvin IV -3.1 min θCs = 0.33; see Fig. 27


Substrate
75P2 Ni(100) 300 Diode IV -3.4 min LEED
-2.9 ML
77K4 Ni(100) ARUPS III -3.0 XPS
88G3 Ni(100) 325 Diode IV -3.8
-3.3
89D Ni(111) 100 SE edge IV -3.8 min, θCs = 0.5
(UPS) -3.2 θCs= 1.0
91K4 NiO(100) Diode III -3.0 TDS, also oxidation of Cs
89C Pt(111) 300 ARUPS IV -4.5 min, θCs = 0.25 LEED, ARUPS
-4.0 ML, θCs= 0.4
85H4 Ru(0001) 80 SE edge IV -4.1 min µ0 = 10.5 D
(E) -3.8 ML see Fig. 29
87R Ru(0001) 300 Diode IV -4.2 min θCs = 0.14
-3.5 ML θCs = 0.3
TDS, ELS; µ0 = 11 D
90D2 Ru(0001) 300 Diode IV -3.8 min LEED, TDS
-3.6 ML µ0 = 16.4 D
91P6 Ru(0001) 120 SE edge IV -4.0 min, θCs = 0.19 XPS, UPS
(UPS) -3.7 ML,θCs= 0.40
69W2 Si(111) 300 Diode IV -3.2 min
-2.9
Si(100) 300 Diode IV -3.6 min
-3.2
82T Si(100) SE edge IV -3.7 min LEED, AES, ELS, UPS
-(2 × 1) (UPS) -3.3
85I2 Si(100) IV -3.7 θCs = 0.7
-(2 × 1) -3.2 θCs = 1.0
87O2 Si(100) 200 Kelvin IV -3.4 min AES
-(2 × 1) -2.8 ML
89E2 Si(100) ARUPS IV -3.6 min
-(2 × 1) -3.1 ML
90M Si(111) 300 SE edge IV -3.25 min LEED, IPES, UPS
-(7 × 7) (UPS) -3.0 ML
94W3 Si(111) 300 Diode III -3.0 LEED, AES, ARUPS
-(7 × 7)
Si(111) 300 Diode III -3.0
-(¥î¥
R30Û%
67F Ta(110) Diode IV -3.1 min
-3.0 ML
97G2 TiO2(110) 130 SE edge III -2.2 1 ML µ0 = 6
(XPS) Band bending 0.3 eV D
67S W(110) FEM IV -3.9 min
-3.2 ML
W(100) IV -3.0 min
-2.8 ML
69M2 W(100) 300 SE edge IV -3.1 min, (2 × 2) LEED
(E) -2.3 ML


Substrate
69S W(110) FEM IV -3.6 min 1.8·1014 atoms cm-2
-3.4 ML 2.5·1014 atoms cm-2
W(100) IV -3.0
-2.8
W(211) III -3.2
W(111) III -2.0
W(115) III -2.6
W(103) III -2.8
70F W(110) 77 SE edge IV -3.7 min
(E) -3.2 ML
72V W(100) 300 Diode IV -3.1 min
-2.6 ML
71P2 W(211) 300 Diode IV -3.0 min θCs = 0.25, (2 × 2) LEED
-2.8 ML θCs = 0.43, close-packed layer
73P2 W(100) 300 Diode IV -3.1 min
-2.4 ML
80D2 W(110) 250 Kelvin IV -3.8 min 3.5·1014 atoms cm-2
-3.2 ML 5.5·1014 atoms cm-2
LEED, AES
87L WSe2* Diode III -3.1 6·1014 atoms AES, LEED, TDS
cm-2 *cleaved in air
97K5 WSe2 85 IV -4.1 min θCs = 0.4
-3.9 θCs = 0.8
AES, TDS
4.2.10 Noble metals

Besides the alkali metals, the noble metals (Cu, Ag, Au) are most thoroughly studied. The work-function
changes reflect a larger number of effects which may occur during adsorption. The most sensitive
coverage range is the monolayer, but some changes are also observed up to 10 ML. The work-function
changes are mainly affected by the growth mode: pseudomorphic or not in registry, distributed single
atoms or islands, cluster growth in three dimensions, layer-by-layer growth or clusters on a wetting layer
(the so-called Stranski-Krastanov growth mode). These different modes depend on atomic fluxes and
substrate temperature. Superimposed to these different growth modes, a change of the substrate
reconstruction may occur which also may influence Φ. Obviously, work-function measurements alone
can not discriminate all those different processes.
The high melting metal surfaces (W, Mo, Ta) have been preferred substrates from the beginning of
UHV technology in surface science, since they can easily be cleaned by high-temperature flashes. There
are some interesting reviews on this topic (e.g. [85K6]). Also Figs. 30 and 31 show the richness of the
observed Φ variations. As mentioned already in the introduction, Cu was selected to represent this class
of adsorbates and some more figures are added to the Cu table.

Table 97. Copper (Cu)
Figs. 32...41
Ref. Cu / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
87B7 Al(111) 300 ARUPS I 0.0 1 ML LEED, AES, ARUPS
+0.4 4 ML
Al(100) 300 I 0.0 1 ML
+0.2 4 ML
94H Ir(100) 380 FEM III -1.1+ 4...8 ML + average value
-1.4 1.5...4.5 ML Cu grows as Cu(100)
φ sat = 4.55 ± 0.02 eV
100
quartz crystal microbalance;

θ [ML] is given in relation to the
number of substrate atoms,
which is taken as 1.0×1015 Ir
atoms cm-2.
80S3 Mo(100) 300 Diode II +0.44 AES
-0.23 see Fig. 32
90T Mo(110) 300 Diode -0.52 min, θCu = 1 AES, LEED, TDS
-0.2 θCu = 3.5
87B5 Pd(111)* Kelvin III -0.70 2 ML * film on mica
88V
85P Pt(111) <475 ? IV -0.80 1 ML LEED, AES
T>475 K: alloy formation
θ = 1: p(1×1), pseudomorphic
95N Pt(111)
450 Kelvin -0.95 Figs. 33 and 34
350 -1.0
84B2 Ru(0001) 540 ? I 0.75 1 ML
1080 0.60 1 ML
86H4 Ru(0001) 100 SE edge III -0.8 θ ≥ 1* LEED, AES, TDS
(E) *from AES, annealed to 900 K
following to deposition
IV -1.0 θ=1 without annealing
-1.1 θ = 1.5
-0.9 θ = 2.3
-1.15 θ=9
87P Ru(0001)* 300 Diode IV -0.37 2 ML * thick Ru(0001) film on
Mo(110)
LEED, AES
growth mode: 2 D layer-by-
layer; see Fig. 35
88H2 Ru(0001) 85 SE edge -0.7 1 ML Cu MDS, IRAS, TDS
(E) -0.75 2.4 ML Cu
93W3 Ru(0001) 640 Kelvin -0.72 1 ML ∆Φ measured during Cu
-0.64 > 3 ML deposition: ∆Φ-oscillations
93S2 Ru(0001) 640 Kelvin III -0.7 1 ML Cu compresses oxygen on the
94S2 surface.
94S3


Substrate
85T2 Si(111) 300 ? -0.15 0.3 ML LEED, AES, first 2D alloy
formation then epitaxial growth
of Cu
97V V(100) SE edge II +0.44 1 ML LEED, AES, UPS, TDS
(UPS) +0.14 2 ML
+0.54 10 ML
65M W(110) <670 FEM II 0.25 2 ML
-0.32 >6 ML
69M W(110) 300 Kelvin IV -0.75 strained Cu(111) film
-0.33 Cu(111) film
73P W(110) 300* FEM IV -0.85 * plus annealing (T not given) to
-0.7 sat. spread the Cu over the tip face.
Φ
Cu(111)
W(100) FEM IV -0.65
-0.5 sat.
Φ
Cu(100)
W(111) FEM II 0.25
-0.3
-0.1
W(211) 300 FEM II 0.2
-0.7
-0.5
74B3 W(110) 300 SE edge IV -0.80 2.0·1015 cm-2 LEED, AES, TDS
(800) (E) -0.52 4.8·1015 cm-2
W(100) 300 SE edge II 0.15 0.8·1015 cm-2 LEED, AES, TDS
(E) -0.75 1.8·1015 cm-2
75C W(100) 77 FEM II +0.42 0.5·1015 cm-2* µ0 = 0.5 D

-0.20 1.2·1015 cm-2* * assignment of coverage by [77
R]
76M W(211) 300 Diode II 0.35 θ1
0.0 2 θ1
-0.42 3.5 θ1
-0.28 8 θ1
77J2 W(100) 400... FEM II Fig. 36
700
77J3 W(111) 500 FEM II +0.4 θ1
-0.3 4θ1
+0.2 7θ1
W(112) 600 FEM II +0.3 1.5θ1 W(310) similar to (112)
-0.9 3.5θ1
-0.5 5 θ1
W(110) 600 III -0.7 25·1014 atoms/cm2
77M3 W(112) 80...200 Diode II Fig. 37
77R W(100) 20 FEM II +0.42 0.5·1015 cm-2 Fig. 38
79R -0.32 1.2·1015 cm-2


Substrate
78B2 W(100) 78 FEM II +0.16 Fig. 39
-0.24
+0.20
81S W(100) 300... FEM II f(θ1,T) discussion of existing data
W(110) 930 Figs. 40 and 41
W(211)
W(111)
85K6 W(110) 800 Diode µ0 = 0.7 D at 800 K
86C2 W(110) 300* Kelvin III -0.65 1 ML LEED
-0.72 saturation *annealed to 850 K
87C W(110) 300 Kelvin III -0.67 θ = 1* LEED, AES, TDS
-0.72 θ=4 *from AES
-0.35 θ = 4** **annealed to 850 K
87A2 W(100) 300 SE edge II 0.25 0.5 LEED, AES, TDS
(E) -0.89 2.0 surface alloy formation
800 IV -0.45 0.5 reinterpretation of Bauer
0 1.0
98Y2 ZnO(0001) SE edge IV -0.15 θCu = 0.05 XPS, ISS
Zn (UPS) +0.42 θCu = 1.3
Table 98. Silver (Ag)
Figs. 42...47
Ref. Ag / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
91T3 Cu(110) 300 SE edge -0.1 θAg = 0.5 AES, LEED
(E) -0.05 θAg = 1.0
-0.40 θAg = 10
120 -0.35 θAg = 0.3
-0.22 θAg = 1.0
-0.53 θAg = 10
92M2 Cu(111) 300 SE edge IV -0.35 min
(E) -0.33 saturation
94N Cu(111) 300 Diode III -0.45 1 ML ML determination:
Auger and ∆ĭ
95W Cu(111) ARUPS III -0.3 1 ML
94H Ir(100) 78* FEM III -1.05+ 3...4 ML * spreaded at 442 K<T<640 K
-1.20¹ +
average ∆ĭ
¹ occurs only for θ > 2 ML
φ sat = 4.63 ± 0.02 eV

100
76J Mo(100) 300 Kelvin IV -0.12 1 ML AES

-0.08 >7 ML
80S3 Mo(100) 300 Diode II +0.08 0.7 ML AES
-0.10 3 ML also measured at 573, 863 K
90K Mo(110) 370 Diode III -0.05 0.1 ML only low coverages;
550 -0.07 0.1 ML diluted disordered layer
850 -0.14 0.1 ML see Fig. 42


Substrate
83S3 Pt(100) SE edge III -0.50 1 ML AES, UPS
(UPS)
Pt(997) SE edge III -0.54 1 ML
(UPS)
85P3 Pt(111) 310... SE edge III -1.2 1 ML AES, LEED, TDS
600 (E) -1.5 2.5 ML ML from TDS
Stranski-Krastanov-growth: φ of
the rough surface at θAg = 2
smaller than for the epitaxial ML.
82D2 Re* 300? FEM III -0.55 * The central plane of the tip is
Re( 10 1 0 ).
The final work function is
4.32 eV.
83A2 Re-tip 350... FEM IV -0.72 average ∆Φ
600 µ0 = (1.5±0.5) D
Re( 10 1 0 ) — -0.80* *jump of Φ during spreading of
Re( 10 1 1 ) — -1.00* Ag onto the indicated area
— -0.48*
Re( 10 2 0 ) — -0.78*
— -0.70*
— -0.55*
Re( 11 2 2 ) -1.00*
-0.90*
98S4 Re(0001) 300 Kelvin III -0.60 1 ML TDS, XPS
-0.75 2 ML
-0.70 4 ML
88P Ru(0001) 300 Diode ΙΙΙ −0.16 at 5 ML AES; layer by layer growth;
Ag(111); change in slope =
transition to next layer
95N3 Ru(0001) 350 Kelvin ΙΙΙ −0.33 θAg = 0.6 ∆Φ measurements during Ag
evaporation.
At higher T change in slope of
∆Φ.
95V V(100) 250... SE edge — 0.0±0.15 2 ML AES, UPS
900 layer growth for 2 ML
70S W(100) 920 FEM -0.55 0.7 ML
-0.35 1.5 ML
72J W(100) ? FEM II +0.15 1×1015 Ag atoms cm-2
-0.35 5×1015 Ag atoms cm-2
77K2 W(100) 300 Diode III -0.35 — Fig. 43
W(110) 300 Diode IV -0.87 —
-0.72 —
W(111) 300 Diode IV -0.45 —
-0.35 —
77B W(110) 300 Diode IV -0.75 2 ML LEED, AES, TDS
500 Diode -0.62 >3 ML
W(100) 300 Diode IV -0.30 2.5 ML Fig. 44
600 Diode -0.30 2.5 ML
800 Diode -0.25 >4 ML


Substrate
79S2 W(110) 300 FEM III -0.8 various changes at annealing
W(100) 300 III -0.15 temperatures up to 900 K
W(211) 300 III -0.7
W(111) 300 II +0.1
-0.3
79K W(110) var. Diode IV see µ0 = 1 D for surface gas
Fig. 45 µ0 = 0.1 D for strained Ag(111)
µ0 = 0.05 D for unstrained
Ag(111)
84K2 W(211) 300 Diode IV -0.65 1.2×1015 atoms cm-2, AES
900 -0.35 3 ×1015 atoms cm-2
85K6 W(110) 800 Diode — — — µ0 = 0.6 D at 800 K
W(211) 800 Diode — — — µ0 = 0.2 D at 800 K
93Z W(110) 90 Kelvin III -0.80 1 ML Fig. 46
300
700
95D W(110) 300 FEM see quartz crystal microbalance
Fig. 47 at Φsat: 5.25±0.25×1015 Ag
atoms cm-2
θ [ML] is given relative to the
number of substrate atoms which
is taken as 1.0×1015 Ir atoms cm-2
Table 99. Gold (Au)
Figs. 48...52
Ref. Au / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
95W Cu(111) ARUPS I +0.6 4 ML
94H Ir(100) 78* FEM — 0.10+ 1 ML quartz crystal microbalance
-0.20+ 2 ML DWĭsat:
±0.1 1...5 ML 2.25±0.18î1015 Au atoms cm-2
ɴ (ML) is given relative to the
number of substrate atoms, which
is taken as 1.0î1015 Ir atoms cm-2
* spreading temperature
445...520K
+ average value depending on
spreading temperature
83S3 Pt(100) SE edge IV -0.45 1 ML AES, UPS
(UPS) -0.4 3 ML
(UPS)
(UPS)


Substrate
77C Re tip with 600* FEM II 0.35 θ = 1+ * temperature of spreading the
[11 2 0] 0.20 evaporated Au
θ = 2.5
orientation + θ =1 is the amount of Au
required to reach maximum
coverage
average for the whole tip
see Fig. 48
77C Re(10 1 1 ) 550*... FEM — 0.20 θ<1 Topping model can be applied: Au-
850 Re dipole, α = 10 Å3
— -0.40 θ = 2...4 state 1, pseudomorphic film

— -0.10 θ>4 state 2, Au(111)
Re( 10 1 0 ) 380*... FEM — 0 θ < 2.5 adsorbate structure incorporating
940 Re
— 0.20 3<θ <8 Au(110)
— 0.40 θ>8 Au(111), Φ is too high due to field
reduction by the extension of the
flat plane
Re(11 2 2 ) 420*... FEM — most open surface studied here,
850 complicated behavior, surface alloy
formation concluded
Re(11 2 0) 350*... FEM — — θ<1 α = 22 Å3
250
II 0.40 θ=1
0.25 θ=2
0.60 θ>4 Au(111)
88P Ru(0001) 300 Diode II 0.01 0.7 ML AES, kinks
-0.06 1.5ML 2D pseudomorphic island
layer-by-layer growth
74Y W(111) ? FEM I 0.7
76J2 W(100) 77 FEM I 0.8 at: 30·1014 atoms/cm2, µ0 = 0.6 D
W(211) I 1.1 at: 25·1014 atoms/cm2, µ0 = 1.6 D
W(310) I 1.2 at: 40·1014 atoms/cm2, µ0 = 3 D
76R W(100) 20...330 FEM I 0.50 0.3 ML* Au-Au interaction starts at
θAu §0.25
*By comparing emission from
W(111) facet with literature data
76R2 W(110) 20 FEM I 0.55 — µ0 = 0.7 D
W(211) 20 FEM I 0.40 — µ0 = 0.3 D
77B W(110) 300... Diode I 0.12 1 ML AES, (see Fig. 49)
900
W(100) 300... Diode I 0.40 1 ML AES, (see Fig. 50)
900 superimposed are changes of ∆Φ
due to coverage and structure


Substrate
78B2 W(100) 78 FEM I 0.70 θ = 1 ML see Fig. 51
78J W(100) 78* FEM II 0.40 ș=1 ș = (6.7 ± 2.5)1014 atoms cm-2
0.25 ș = 2.2 ș = 2.7 θ(Au(100))
0.50 ș>3
W(211) 78* FEM qualitatively similar to W(100)
W(110) 78* FEM IV -0.40 ș = 0.6 *measurements are performed also
-0.17 ș=2 at higher temperatures
83P3 W(110) 300 Diode I +0.28 AES, ELS
W(100) 300 Diode I +0.65
W(211) 300 Diode I +0.25 θ1
+0.15 2θ1
+0.43 6θ1
84K2 W(211) 300... Diode II 0.50 0.7 ML AES
930 0.15 2 ML nearly no difference
0.63 4 ML between 300 and 930 K
85K6 W(110) 800 Diode — — — µ0 = 0.7 D at 800 K
W(211) 800 Diode µ0 = -0.3 D at 800 K
86M W 300 Diode see
Zylinder Fig. 52
4.2.11 3d transition metals

Table 100. Titanium (Ti)
Ref. Ti / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
74B2 W FEM -0.6
Table 101. Vanadium (V)
Ref. V/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
92Z3 TiO2(110) SE edge IV -0.3 min LEED, UPS, XPS
(UPS) +0.25 ML
+0.5 thicker layer

Table 102. Chromium (Cr)
Ref. Cr / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
93P TiO2(110) SE edge IV -1.5 min 1.8 Å LEED, XPS, LEIS
(He+) -0.9 >6Å
89B3 W(110) 100 SE edge III -1.3 ~0.5 ML Fig. 53
W(100) 1100 (SE) -0.5 1 ML pseudomorphic ML on both
substrates at 100 K
Table 103. Iron (Fe)
Ref. Fe / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
82S6 Ag(100) 300 ARUPS II 0.0 0.5 ML UPS
+0.75 1.0 ML Stranski-Krastanov growth mode
+0.2 3 ML
90T Mo(110) 300 Diode IV -0.55 min,θFe = 2 AES, LEED, TDS
-0.17 θFe > 4
85K4 MoS2 300 Diode III -0.45 θ1 Phase I: island formation
-1.0 2θ1 Phase II: reaction with substrate
LEED, AES
88H3 Re(0001) 980 Diode III -0.21 1 ML
-0.26 2 ML
99K3 Ru(0001) 300 Diode III -0.58 5 ML LEED, AES
93P TiO2(110) SE edge IV -1.3 min, 1 Å LEED, XPS, LEIS
(He+) -1.0 >4Å
78J2 W(001) 300 FEM IV -0.6 at 12×1014 atoms cm-2
600 -0.4 at 24×1014 atoms cm-2
1000 also deposited at 600 and 1000 K
without larger changes
97N2 W(110) 90 Kelvin III see extension of Ref. [97N3]
300 (IV) Fig. 54
300 +
600
97N3 W(110) 90 Kelvin IV see
≥ 300 Fig. 55
83G2 W(110) 300 Diode IV see AES kinks
W(112) Fig. 56. 1 ML = 1.4×1015 atoms cm-2
W(111) µ0 = 1.3 D (W(110))
W(001)
99K W(111) 300 Diode II +0.03 LEED, AES, TDS
-0.22 1 ML
-0.1 28 ML

Table 104. Cobalt (Co)
Ref. Co / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
95W Cu(111) ARUPS I +0.15 7 ML
90T Mo(110) 300 Diode IV -0.35 min, θCo = 0.8 AES, LEED, TDS
0.0 θCo = 1.3
+0.1 θCo = 1.5
+0.2 θCo = 3
91F Pt(110) SE edge III -0.8 1 ML LEED, AES
-(1 × 2) (UPS)
96S W(110) 300 IV -1.5 µ0 = 4.6 D
580 IV -0.45
W(100) 300 III -1.2 µ0 = 3.3 D
580 II -0.55
W(111) 300 IV -0.55 µ0 = 1.3 D
580 IV -0.55
89J W(110) SE IV see strained pseudomorphic ML
W(100) 1100 edge IV Fig. 57
(E)
Table 105. Nickel (Ni)
Ref. Ni / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
90T Mo(110) 300 Diode IV -0.35 min, θNi = 0.8 AES, LEED, TDS
0.0 θNi = 1.5
+0.23 θNi = 3.5
+0.20 θNi = 5
85P2 MoS2 80 IV -0.25
-0.05
300 -0.16
450 >0 interpretation: 2D islands
88B3 Ru(0001) 100* SE edge IV -0.4 θNi = 1.0 TDS
(UPS) -0.3 θNi = 1.6 *annealed to 700 K
99K3 Ru(0001) 300 Diode IV -0.24 1 ML LEED, AES
-0.12 2 ML
84K3 W(110) 300 Diode IV -0.75 reaction occurs for W(112) at
1100 cleaved temperatures
transition from pseudomorphic
to coincidence lattice below
1 ML
85K6 W(110) 800 Diode µ0 = 0.8 D at 800 K
W(211) 800 Diode µ0 = -0.02 D
94B W(110) IV -1.05
W(100) II +0.35
-0.4
W(111) — <±0.2
W(112) — <±0.2
94W4 W(110) Kelvin IV -0.75 θNi = 0.45 LEED
-0.15 3 ML

Ref. Ni / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
99K W(111) 300 Diode II +0.20 0.5 ML LEED, AES, TDS
+0.05 1 ML
+0.55 5 ML
+0.3 10 ML

Table 106. Zirconium (Zr)
Ref. Zr / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
71C2 (110) 295 FEM IV φsat = 4.45
(112) 295 FEM φsat = 3.92
(100) IV φsat = 3.87
(111) φsat = 3.88
(310) φsat = 3.65
80D W(100) 300 Diode IV -1.1 θ1 LEED, AES, TDS
-0.6 5θ1 pseudomorphic monolayer
1400 III -0.5 θZr= 0.5 c(2 × 2) structure
Table 107. Niobium (Nb)
Ref. Nb / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
79R W(100) 77 FEM IV -0.55 0.5
-0.4 1.0
90A Si(111) 300 SE edge +0.2 at 0.3 ML silicide
-(7 × 7) (UPS) +0.2 at 8 ML silicide
-0.3 at 20 ML Nb value
LEED, UPS
Table 108. Molybdenum (Mo)
Ref. Mo/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
95B Pt(111) 300 Diode -0.5 1 ML
-0.7 >1 ML
90A Si(111) 300 SE edge +0.15 at 1 ML LEED, UPS
-(7 × 7) (UPS) reaches W value abrupt interface
79R W(100) 77 FEM III -0.6 at 0.5 ML

Table 109. Rhodium (Rh)
Ref. Rh / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
99K3 Ru(0001) 200 Diode III -0.07 1 ML
300 III ~-0.01
91K2 W(110) var. Diode with LEED and ∆Φ transition
1 D – 2 D islands
94K W(110) 350 Diode IV -0.7 0.6 ML quasi Frank von der Moewe
+0.12 2 ML growth at low temperatures
830 Diode IV -0.55 0.8 ML Stranski-Krastonov or alloying at
-0.12 3 ML higher temperatures
1280 Diode IV -0.55 0.8 ML
-0.44 3 ML
96K W(110) 800...12 Diode III -0.4 at 0.4 ML
00
98F W(011) 200 Diode IV -0.90 min, θ = LEED
-0.25 0.35 metastable metal clusters
500 IV -0.50 θ = 1.1
-0.25 θ = 0.9
θ = 1.1
99K W(111) 300 Diode II +0.32 1 ML LEED, AES, TDS
+0.28 2 ML
+0.9 10 ML
Table 110. Palladium (Pd)
Figs. 58 and 59
Ref. Pd / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
82S2 Ag(100) 300 SE edge IV -0.3 0.5 ML Φ increases up to 8 ML
(UPS) ±0 1 ML Φ increases with coverage and
Ag(111) 300 SE edge I +0.4 1 ML reaches a saturation value of 5.6 eV
(UPS) at 8 ML which is equal to the bulk
value
88F2 Al(111) 300 ARUPS IV -0.1 1 ML very likely Pd diffusion into Al for
+1.8 > 10 ML the first 2 – 3 ML as con-cluded
later from ARUPS data
87B5 Cu(111) 420 Kelvin IV -0.25 0.3 ML coverage by quartz oszillator
film on +0.65 3.5 ML Φsaturation = bulk Pd(111)
mica Author: Similar curves found for
(100)Pd/(100)Ag; (111)Pd/(110)W;
(111)Pd/(110)Nb.
88V2 Cu(111) 300 Kelvin IV -0.25 0.2 ML comparison with other substrates
88V 300 nm +0.65 > 3 ML see Fig. 9
film on
mica
85P5 Mo(110) 300 Kelvin -0.18 θ1 LEED, AES, XPS
0.0 1.5 θ1
+0.55 2.5 θ1
+0.60 3 θ1

Ref. Pd / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
98S2 Mo(211) Diode I LEED, AES
100 I 0.2 1 ML* *from kinks in AES

0.52 sat. at 3 ML µ0 = 0.3 D
300 I 0.07 1 ML*
0.7 sat. >4 ML
800 I 0.08 1 ML*
0.48 sat. >4 ML
80W2 Nb(110) SE IV -0.2 1 ML UPS
(foil) edge +0.65 0/
(UPS)
88P Ru(0001) 300 Diode IV -0.03 ~0.5 ML Fig. 3
film on +0.12 ~3 ML 2-dim. pseudomorphic islands
Mo(110) later pseudomorphic Pd(111)
99K3 Ru(0001) 300 Diode I +0.04 1 ML LEED, AES
+0.15 3 ML
86N Si(111)- 300 SE edge (I) +0.12 1 ML θ = 1: 7.8·1014 atoms cm-2
(7 × 7) +0.32 2.5 ML
(quartz oscillator)
89R Ta(110) IV -0.35 θPd = 0.75 UPS
0.0 θPd = 1.1
+0.70 θPd = 0.5
80S4 W(110) 300 Diode IV -0.45 1 ML second layer metastable
830 IV -0.60 1 ML T > 700 K 3-dim. cluster
see Fig. 58
81P W(100) 300 Diode II 0.3 1 ML AES, ML from kinks in AES
0.17 2 ML Also annealed to 460, 510, 620,
0.5 4 ML and 1020 K resulting in gradual
changes. Behavior similar to other
fcc metals on W(100); see Fig. 59
85K6 W(110) 800 value from θ ĺ
µ0 = 0.74 D
90Z W(110) 900* Kelvin IV -0.54 1 ML** *annealed to 900 K
-0.38 1.8 ML*** **from TDS
***presumably cluster formation
98F W(011) 110 Diode IV -0.85 min,θ=0.35 LEED, metastable metal clusters
-0.40 θ = 1.2
800 III -0.55 1 ML
99K W(111) 300 Diode II +0.25 1 ML LEED, AES, TDS
+0.17 2 ML
+0.7 8 ML


Table 111. Lanthanum (La)
Ref. La / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
82L2 Mo(112) Diode IV -1.8 at 0.6 ML discussion of structures by LEED
-1.4 at 1.2 ML
77G2 W(100) 300 Diode IV -1.8 at 0.5 ML at higher T up to 1350 K the min-
-1.5 at 0.8 ML imum is more shallow on 0.3 eV
77V W(110) 300 Diode IV -2.5 4·1014 cm-2 LEED, AES; µ0 = 4.5 D
-1.8 8·1014 cm-2
Mo(110) 300 Diode IV -1.8 6·1014 cm-2 LEED, AES; µ0 = 3.9 D
-1.5 8·1014 cm-2
91B W(110)* FN III -2.8 at 1 ML also for (111) and (112) plans
(FEM)
Table 112. Hafnium (Hf)
Ref. Hf / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
94S W tip with 300* FEM IV -1.3** θ1 *measured at 300 K after sprea-
(111) center -0.5** 6θ1 ding of Hf at 1300 K
**average value
Table 113. Tantalum (Ta)
Ref. Ta / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
79R W(100) 77 FEM III -0.65 0.5 ML
90A Si(111) 300 SE edge +0.22 at 5 ML silicide
-(7 × 7) (UPS) +0.2 at 3 ML silicide
-0.45 at 30 ML Nb value
LEED, UPS
77K W(110) FEM µ0 = 0.5 D
Table 114. Tungsten (W)
Ref. W/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
86A Si(111) 300 SE edge +0.28 at 3 Å UPS, LEED
-(7 × 7) (UPS) thickness sharp interface at 300 K
90A Si(111) 300 SE edge +0.36 at 2 ML LEED, UPS
-(7 × 7) (UPS) reaches W value abrupt interface
75B2 W(110) Kelvin -0.6 θW = 0.5 This change of Φ decreases with
76B decreasing terrace width.
77K FEM µ0 = 0.2 D

Table 115. Rhenium (Re)
Ref. Re / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
96S6 Si(111)- 400 I +0.6 UPS, XPS
(7 × 7) sharp interface, µ0 = 0.11(5) D
77K W(110) FEM µ0 = 0.1 D
Table 116. Iridium (Ir)
Ref. Ir / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
79R W(100) 77 FEM I 0.8 0.5 ML
77K W(110) FEM µ0 = 0.0 D
91K2 W(110) var. Diode with LEED and ∆Φ transition
1 D – 2 D islands
350* Diode IV -0.55 0.25 ML *also annealed at 1250 K and
-0.2** 0.75 ML 1650 K
450* -0.3 0.35 ML **no saturation
-0.15** 1 ML
77K W(110) FEM µ0 = 0.0 D
96K W(110) 1100... Diode >-0.1 LEED
1500
Table 117. Platinum (Pt)
Ref. Pt / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
98S2 Mo(211) 300, Diode I 0.78 LEED, AES
1300
87A Re(0001) 350 PE-Kante IV -0.1 ML Pt grows epitaxially
+0.6 1 ML
77K W(110) FEM µ0 = 0.0 D
91K2 W(110) var. Diode LEED and ∆Φ indicate transition
from 1D to 2D islands
94 K W(110) 400 Diode IV -0.4 ML
+0.5 2 ML
96K W(110) 880... Diode III >-0.1 up to LEED
1240 1.5 ML

4.2.14 Rare-earth metals

Table 118. Neodymium (Nd)
Ref. Nd / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
87N2 Cu(100) 300 ? III -2.0 1.3 ML θ by kinks in Auger
different sub ML phases
Frank von der Marwe growth
550 III -1.7 1.3 ML alloy formation
800 III -1.4 1.3 ML alloy formation
88N5 Cu(111) 300 SE edge III -2.0 at 2.5 θ1 LEED, AES, ARUPS
900* (UPS) -1.7 at θ1 *annealed to
-1.7 at 2.5 θ1
92S2 Mo(112) 300 Diode IV -1.6 0.5 ML
300 -1.2 1.2 ML
600 -1.3 1.2 ML
900 -1.4 1.2 ML
92S5 Mo(110) 300 (Diode) IV -1.9 4·1014 cm-2
-1.25 7.5·1014
-1.45 cm-2
12·1014
cm-2
87G W(112) 300 Diode IV -1.8 0.5 LEED
-1.5 1.0
Table 119. Samarium (Sm)
Ref. Sm / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
89J3 Cu(111) 300 Diode III -1.9 θSm = 0.4 AES, LEED
-1.9 θSm = 1.0
-2.2 θSm = 2.0
87S2 Mo(110) 300 Diode IV* -2.4 0.2 ML *special: local maximum at 1 ML
-1.5 1.0 ML
-2.4 3 ML
88F Pd(100) Diode III -2.2 ? valence charge = 2.75 at surfaces
95R Ru(0001) 500 SE edge IV -2.4 0.3 ML UPS
(UPS) -2.2 0.8 ML
-2.4 3.0 ML
Table 120. Gadolinium (Gd)
Ref. Gd / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
97L Mo(112) 300 SE edge IV -1.4 1 ML LEED
(E) -0.8 2 ML
1100 -1.5 1 ML
-1.2 2 ML
76B5 W tip FEM -2.6 ? specific discussion for
W(111), (110), (121)

Ref. Gd / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
86K2 W(110) 300 Diode IV -2.5 0.33 ML Auger, LEED, TDS
-1.8 0.66 ML
1200 §
87G W(112) 300 Diode IV -1.6 0.5 ML linear chains of adatom
-1.4 1.0 ML for θ < 1
LEED, ordered structure
88G2 W(111) Diode -2.1 5·1014 cm-2
-1.5 7·1014 cm-2
91M2 W(100) 300 Diode IV -1.3 5·1014 cm-2 Typ IV ĺ,,,DWKLJK7
1200 -0.8 8·1014 cm-2
99S W(111) FEM IV -1.7 4.5·1014 atoms cm-2
-1.5 7.5·1014 atoms cm-2
-1.7 9 ·1014 atoms cm-2
Table 121. Terbium ()
Ref. Tb / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
92S5 Mo(110) 300 CPD IV -1.9 4·1014 cm-3 AES, LEED
-1.45 8·1014 cm-3 quartz microbalance
-1.55 13·1014 cm-3 Fig. 4
85K W(211) 300 Diode IV -2.9 0.5 ML Auger, LEED, TDS
up to -2.7 0.7 ML electropositive material
1050
86K2 W(110) 300 Diode IV -2.8 0.6 ML LEED, AES, TDS
-2.0 1.0 ML
88G2 W(111) 300 Diode -1.7 5·1014 cm-3 Typ IV ĺ,,,DW.
Ļ -1.5 7·1014 cm-3
1200
91M2 W(100) 300 Diode IV -1.4 5·1014 cm-3 Typ IV ĺ,,,DWKLJK7
Ļ -0.9 8·1014 cm-3
1200
Table 122. Dysprosium (Dy)
Ref. Dy / T [K] Method Type ∆Φ [eV] at θ1 Comments,

Substrate interpretation
91P4 Mo(110) 300 Kelvin -1.9 4·1014 atoms cm-2 LEED, AES
-1.2 7·1014 atoms cm-2 also at 850 K
-1.4 >12·1014 atoms cm-2
Table 123. Holmium (Ho)
Ref. Ho / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
89G W(112) 300 Diode? IV -1.9 0.5 ML LEED
-1.3 1.1 ML

Table 124. Erbium (Er)
Ref. Er / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
92S5 Mo(110) 300 CPD IV -1.85 4·1014 cm-2 µ0 = 1.9 D
-1.35 7·1014 cm-2
-1.45 12·1014 cm-2
95K α- 300 Kelvin III -1.6 5 Å Er
SiC(0001)
95S6 Si(100) 230 Kelvin III -1.1 1 ML XPS
-1.7 9 ML µ0 = 1.1(5) D
intermixing at higher T
Table 125. Thulium (Tm)
Ref. Tm / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
92N Mo(110) 300 Diode IV -1.7 0.8 ML
-1.55 ML
-2.0 2.5 ML
Table 126. Yterbium (Yb)
Ref. Yb / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
87S4 Mo(110) Diode IV -2.4 0.5 ML AES, LEED
also in -1.8 1 ML (1 ML: 0.55 substrate units)
87S3
97K2 Si(111) 300 Diode IV -1.75 0.6 ML AES, LEED
-1.65 1 ML
800 III -0.6 0.6 Si forms a step layer
4.2.15 Group IIa metals

Table 127. Beryllium (Be)
Ref. Be / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
79Z W(110) 300* Diode IV -0.75 at θ1 *measured also at higher T
-0.50 at 2 θ1
W(100) 300* I +0.28 saturation
91D W(112) 300 FEM II +0.4 1 ML
-0.6
0.0 saturation

Table 128. Strontium (Sr)
Ref. Sr / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
77V Mo(110) 300 Diode IV -2.6 0.25 ML LEED, AES
-2.0 1.0 ML µ0 = 5.1 D
W(110) 300 Diode IV -3.3 0.3 ML LEED, AES
µ0 = 5.1 D
-2.1 1.0 ML several ordered structures
µ0 = 6.6 D
79M Mo(112) Diode IV -2.1 4·1014 cm-2 LEED, structures in sub-ML
-1.8 7·1014 cm-2 regime discussed
= ML
73K W(110) 77, 300 FEM IV -2.9 0.3
-1.9 1.0
Table 129. Barium (Ba)
Ref. Ba / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
93V Ag(111) 300 Kelvin IV -2.3 4.5·1014 cm-2
<2.15 12·1014 cm-2
91L Cu(111) IV -3.0 min at θ1 UPS
-2.4 ML at 3θ1
70B Mo(110) 300 IV Φmin = 2.3 eV
Φsat = 2.7 eV
in russian language
81M Mo(112) Diode IV θmin = 2.3 eV coverages from LEED and
Re(10 1 0) θsat = 2.9 eV structures;
W(112) same result for all three
substrates
98G2 Mo(110) Diode IV -3.0 min 3·1014 atoms cm-2
-2.3 6·1014 atoms cm-2
LEED, ELS
95V2 Ni(110) Diode IV -3.2 at θ1 AES, LEED, TDS
-2.7 at 2θ1
82L3 Re(10 1 0) FEM? θmin = 2.0 eV
90H3 Si(100) 300 SE at XPS IV -2.8 2 ML ML: 6.8·1014 atoms cm-2
-2.6 4 ML
94V Si(100) Diode IV -2.5 1 ML
-(2 × 1) -2.2 2 ML
96W Si(111)- SE edge IV -2.9 2 ML LEED
(7 × 7) (E) -2.6 3 ML
98C Si(100) (SE edge) -2.3 0.6 ML Dimers remain in sub ML
-(2 × 1) become symmetric at 1 ML
and silicides start to form.
99K2 Si(100) 1140 SE edge III -1.9 θBa = 0.6 LEED, UPS
-(2 × 1) (UPS)
69F W(100) 300 ? IV -2.6 5·1014 cm-2 (θmin = 2.3 eV)
= 1 ML (θsat = 2.7 eV)
-2.1 > ML in Russian language

Ref. Ba / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
74G2 W(110) 300 ? LEED, linear branches in the
ĳFXUYH
IV -3.5 2.35·1014 cm-2 Φmin = 2.0 eV
-2.6 5.5·1014 cm-2 Φsat = 2.5 eV
75G W(110) 300 FEM IV -3.6 2.4·1014 cm-2 Φmin = 2.0 eV

-2.7 5.5·1014 cm-2 Φmax = 2.9 eV
interaction with co-adsorbed
Si
77G3 W(110) Diode IV -3.1 min 2.2·1014 cm-2 µ0 = 13.5 D, LEED
-2.5 ML 5.5·1014 cm-2
92L W(100) Diode -2.1 1 ML LEED, IPES
-1.7 >2 ML
73M2 W(112) 77 Diode IV -2.7 4·1014 cm-2 LEED
-2.4 6·1014 cm-2
4.2.16 Group IIIa metals

Table 130. Aluminum (Al)
Ref. Al / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
92P Ag(111) SE edge III -0.2 1 ML LEED, AES
(E) -0.3 2 ML
-0.38 4 ML
91K3 Mo(110) Diode IV -0.47 θ1
-0.44 >θ1
90D Pd(111) on Kelvin III -1.3 2 ML Stranski-Krastanov growth mode
mica for θ > 2 ML; µ0 = 0.29 D
98S Pd(100) 325 Kelvin III -1.3 2 ML At low θAl surface disordered.
Alloying for T at 750...950 K.
96P2 Re(10 1 0) 300 Kelvin III -1.2 1.3 ML AES, LEED, TDS
dips in ∆Φ at specific LEED
structures
96K4 Ru(0001) 300 Kelvin III -0.8 1 ML STM
-1.2 2.5 ML
84P3 Si(111) 300 PYS III -0.45 1 ML LEED: (2 × 1) ĺ¥3 × ¥
-(2 × 1) ĺ × 1) AES
Problem: 0xygen growth with
time and number of Al-doses.
74M2 W FEM IV -0.4* θ1 *average
-0.3* θ2 W(001) and W(111) show
complicated dependencies
74M8 W tip FEM IV -0.2 at 2 θ1
-0.15 at 3 θ1

Table 131. Gallium (Ga)
Ref. Ga / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
85K5 W(100) 700...1600 FEM nearly constant at 4.5 eV (?)
Table 132. Indium (In)
Ref. In / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
96R Au(111) 300 SE edge III* -0.7 LEED, AES
(E) A disordered AuIn2 compound is
formed. *from Ref. [ ]
4.2.17 Group IVa elements

For Carbon (C) see Table 6 and 7.
Table 133. Silicon (Si)
Ref. Si / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
71C3 W(100) 295 FEM II +0.55 θ1
+0.2 5θ1
73B3 W(110) 300 Diode III LEED
Table 134. Germanium (Ge)
Ref. Ge / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
85K2 InP(110) 300 Kelvin IV -1.1 0.4 ML n- and p-type
-1.0 >2 ML
92B Nb tip 300 FEM IV -0.5 θGe = 1
(110) center probe hole -0.45 θGe = 2
92S4 Si(100) Diode IV -0.10 1 ML LEED, AES
-(2 × 1) -0.08 3 ML
73B3 W(110) 300 Diode III -0.3 >2 ML LEED
73Z W average 900* FEM I +0.65 *spreading temperature
final value: Φ = 5.2 ± 0.1
Mo average 900* FEM I +0.85 *spreading temperature
final value: Φ = 5.2 ± 0.1
83Z W 500 FEM I +0.28

Table 135. Tin (Sn)
Ref. Sn / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
91Z Au(111) 300 SE edge III -0.9 1 ML AES
AuSn forms which grows laterally
as a double layer
88T Mo(110) 350 Diode IV -0.2 0.2ML AES, LEED, TDS
-0.9 0/ Stranski-Krastanov growth after 2
Fig. 7 ML alloying at 600 K, repulsive
interaction in ML.
85T4 Si(111) 300 PYS +0.5 1 ML AES, LEED
-(2 × 1)
87A3 Si(100) 300 PYS III -0.25 2 ML LEED, AES, PYS
-(2 × 1) layer growth till 2 ML, then
Stranski-Krastanov growth.
Between θGe = 0.5...1.0 ML
a (2 × 1) ĺ × 1) structure
transition occurs.
Table 136. Lead (Pb)
Ref. Pb / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
80T Ag(111) SE edge III -0.48 2 ML LEED
(E)
84A Cu(111) 300 III -0.6 1 ML LEED, AES
Cu(100) -0.45 1 ML
88T Mo(110) 300 Diode IV -0.4 0.7 LEED, AES
-0.36 1.0
-0.78 2.5
92M Pt(111) 300 Kelvin I -1.5 1 ML After ML formation inter-
mixed region occurs at the
Pb/Pt interface
77J W(211) 526 FEM II +0.15 3·1014 atoms cm-2
-0.3 22·1014 atoms cm-2
W(100) 463 FEM IV -0.13 3·1014 atoms cm-2
0 Â14 atoms cm-2
843 FEM IV -0.2 3·1014 atoms cm-2
-0.1 10·1014 atoms cm-2
W(110) 290 FEM IV -0.45 5·1014 atoms cm-2
-0.40 8·1014 atoms cm-2
78J2 W(100) 300* FEM IV -0.15 6·1014 atoms cm-2 surface reconstruction at
0.0 Â14 atoms cm-2 800 K
800* IV -0.17 3·1014 atoms cm-2 *deposition temperature
-0.13 10·1014 atoms cm-2

4.2.18 Group Va elements

Table 137. Antimon (Sb)
Ref. Sb / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
93M2 Au(111) 300 IV -0.8 θ1
-0.7 >2θ1
92E GaAs(110) Kelvin control by electric field induced
cleaved Raman spectroscopy from which
band bending is derived
p-type 300 I +0.5 1 ML no dipole contribution, only band
bending
n-type 300 I +0.6 0.4 ML no dipole contribution , only band
bending
+0.75 5 ML 0.55 dipole contribution
p-type 90 I +0.5 1 ML 0.25 dipole contribution
+0.66 10ML 0.3 dipole contribution
n-type 90 I +0.6 1 ML 0.3 dipole contribution
+0.7 4 ML 0.45 dipole contribution
Table 138. Bismuth (Bi)
Ref. Bi / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
90P Au(111) SE edge III -1.5 1 ML LEED, AES
(E) Bi forms monolayer followed of
Bi-Au compound at the interface
82C4 Bi(0001) SE edge -1.0 3 ML AES
(E) linear decrease of ∆Φ ĺ
subsurface O
86P Pt(111) 640 IV -2.05 0.75 ML* *adsorbate
-1.98 1 ML* LEED, AES, TDS
93G Pt(110) 150 III -1.2
(1 × 2)

4.2.19 Other elements

Table 139. Mercury (Hg)
Ref. Hg / T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
68S Mo tip with FEM II +0.4 θHg = 0.2
(110) center +0.4 θHg = 0.6
+0.1 θHg = 1.8
90S3 Ni(111) SE edge III -0.37 12 L LEED, UPS
(UPS)
68S W tip with FEM II +0.4 θHg = 0.3
(110) center +0.3 θHg = 0.75
78J3 W(100) 295 Diode II +0.12(2) θHg = 0.75 LEED, AES
0.0 θHg = 1.0
92Z4 W(110) Kelvin IV -0.75 4 ML LEED, TDS
-0.65 > 5 ML
Table 140. Uranium (U)
Ref. U/ T [K] Method Type ∆Φ [eV] at θ1 Comments, interpretation

Substrate
68C W 300* FEM IV -1.3 min *annealed to T > 1040 K
-1.1 ML
71C W(100) 300* FEM IV -1.0 θ1 *deposition temperature
probe hole -0.75 6θ1
W(110) IV -1.20 θ1
-1.15 2θ1
W(111) IV -1.25 θ1
-0.77 6θ1
W(112) IV -1.75 θ1
-1.15 3θ1
W(113) IV -1.1 θ1
-0.9 3θ1
W(116) IV -0.95 θ1
-0.7 2θ1

Figures for 4.2
0.5
Pd(110)Xe Ni(110)D 2
0
0.4
Work − function change ∆Φ [eV]

− 0.2
0.3
a b
− 0.4
c 0.2
− 0.6
0.1
−0.8
0 1 2 3 4 5 6 7 0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6

Xe exposure L [Langmuir] D2 coverage θ [ML]
Fig. 2. Xe adsorption on Pd(110) at 77 K. (a) Fig. 3. Work-function change ∆Φ vs. coverage θ

work-function change, (b) Xe Auger peak-to-peak for D2 adsorption on Ni(110). T = 175 K,
amplitude, (c) Xe overlayer LEED beam intensity θ = 1 ML Ł·1015 atoms cm-2. From [87J]
vs. Xe exposure. From [71P].
0.8 8 0.20
Ni(110)D 2
0.7 Ni(111)H
0.6 6 0.15
D2 pressure p [arb.units]
0.5
0.4 4 0.10
β2
0.3
α β1
0.2 2 0.05
0.1
0 0
190 230 270 310 350 390 0 0.2 0.4 0.6 0.8 1.0
Temperature T [K] H coverage θ [ML]
Fig. 4. Thermal desorption spectrum and work-function Fig. 5. Work-function change caused by H2 adsorption
change for desorption of D2 from Ni(110). Initial at 150 K on Ni(111) as a function of the absolute
coverage = 1.5 monolayer; adsorption temperature = coverage θ. From [79C2].
175 K; heating rate 0.5 K s-1.From [87J].

0.25 0.24
Pd(100)H Pd(100)H
0.20
0.20

0.16
0.15
0.12
0.10
0.08
0.05
0.04
0 0.5 1.0 1.5 2.0 0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
H coverage θ [ML] H coverage θ [ML]
Fig. 6. Hydrogen adsorption on Pd(100). Calculated Fig. 7: Work-function change for H on Pd(100) with
coverage dependence of work-function change (filled coverage θ. From [80B4].
circles) and experimental results (crosses) from Ref.
[80B4]. The work functions were calculated for ordered
structures where the hydrogen occupies surface hollow
sites up to θ = 1 followed by an occupation of
subsurface (Oh) sites by the additional hydrogen atoms.
From [94W], [94W2].
0.4 1.0
Pt(100)H2 W :H 2
Tad = 100K 0.8
0.3 W(100)
0.6
W(211)
0.2
H 2 desorption rate
0.4
0.1 0.2
a1 a2 b
W(111)
0
0
− 0.2
− 0.1 W(110)
− 0.4
− 0.2 − 0.6
100 200 300 400 500 0 0.2 0.4 0.6 0.8 1.0
Temperature T [K] H 2 coverage θ [ML]
Fig. 8. Thermal desorption spectra (upper curve) and Fig. 9. Work-function change vs. coverage for H2 on
work-function change (lower curve) for 5 L H2 W(110), W(100), W(211), and W(111). From [74B].
adsorbed on the (1 × 1)-like structure of Pt(100) at
100 K. The most prominent peaks are labeled a1, a2,
and b, respectively. No hydrogen desorption below
100 K could be detected. A work-function change of
0 eV corresponds to the work function of the clean hex-
rot surface (Φ = 5.75 eV). From [91P3].

0 5.3 0 5.3
W(110)H 2
−0.1 5.2 −0.1 5.2

Work function [eV]
Work function [eV]

− 0.2 5.1 − 0.2 5.1
− 0.3 5.0 − 0.3 5.0
− 0.4 4.9 − 0.4 4.9
− 0.5 4.8 − 0.5 4.8

0 5 10 15 20 25 30 35 40 0 40 80 120 160 200
a H 2 exposure L [L] b H 2 exposure L [L]
Fig. 10. Work function and work-function change vs. exposure in Langmuir of H2 for hydrogen adsorption on clean
W(110) at 90 K. (a) shows the region from 0 to 40 L and (b) the entire curve. From [97N].
1.0 0.6
Au(111)0 Pt(111)0
0.5
0.8
0.4
0.6
0.3
0.4
0.2
0.2
0.1
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 0 0.2 0.4 0.6 0.8 1.0
O coverage θ [ML] O coverage θ [ML]
Fig. 11. Work-function change measured as a function Fig. 12. Work-function change of Pt(111) plotted as a
of oxygen coverage. The solid curve is a fit for the data function of oxygen coverage. The plot exhibits no
using equation (7’). The authors consider that the first change in slope for the entire range of oxygen coverage
steep increase in Φ could be due to lifting of the clean studied. The surface is exposed to NO2 at 400 K. From
Au(111) surface reconstruction. The remainder range [89P2].
0.1<θ0<1 ML is than nearly linear with a dipole
moment of 0.12 D similar to the value for Pt(111) of µ
= 0.115 D [89P2]. From [98S3].
3.77 ⋅ 10−15θµ
Equation (7’): ∆Φ =
1 + 9αθ 3 / 2

100 70
Pd(111)Cl 0.6
Pt(111)Cl
60 (3×3) 0.4
80
50

0.5

AUGER signal I [arb.units]
0.3
AUGER signal I [arb.units]

40
60 0.4
30 0.2
0.3
40 20
0.1
0.2 10
20 (√3×√3)R30° 0 0
0.1
0 0 − 0.1
0 1 2 3 0 1 2 3
Cl exposure L [L] Cl exposure L [L]
Fig. 13. Work-function change (solid line) and chlorine Fig. 14. Work-function change (solid line) and chlorine
AES signal at 181 eV (dashed line) as a function of Cl AES signal at 181 eV (dashed line) as a function of Cl
exposure in L units of the Pd(111) surface at 300 K. exposure in L units of the Pd(111) surface at 300 K.
LEED structure indicated. From [80E]. LEED structure indicated. From [80E].
6.50 1500 Ni(110)CO

Ni(110) c d
6.25 CO
1000
6.00
Work − function Φ[eV]
5.75 500
O
5.50
0
5.25 1.0 1.0
Relative sticking coefficient s/s0

a b
Coverage θ [ML]
5.00
4.75 N2 0.5 0.5
4.50
0 1.0 2.0 3.0 4.0 5.0
Exposure L [L] 0 0
0 1 2 3 4 5 0 0.5 1.0
Fig. 15. Work function vs. exposure for CO, O2, and CO exposure L [L] CO coverage θ [ML]
N2 on Ni(110) at 20 K. The values are taken from
the secondary electron threshold of the UP Fig. 16. CO adsorption on Ni(110) at 130 K. (a)
spectra. The arrows indicate first appearance of Exposure-coverage calibration; (b) relative sticking
physisorbed species in the UP spectra. From coefficient s/s0 as f(coverage); (c) ∆Φ as f(exposure);
(d) ∆Φ as f(coverage). From [85B3].
[82H].

1.5
90 K
Ni(111) CO
1.0
288 K
cooling experiments
at θCO = constant
0.5
Fig. 17. Work-function changes obtained following CO
adsorption on Ni(111) at 90 K and 288 K, respectively.
The open circles show the initial and final ∆Φ value
obtained upon cooling the CO overlayer from 288 to
0 90 K at constant coverage. From [88S2].
0 0.2 0.4 0.6
CO coverage θ [ML]
620 Pt(110)CO
]
T [K
Fig. 18. Work-function change of the Pt(110)

ure
580
erat
surface vs. CO pressure and T at constant oxygen

pressure of 5.2·10-4 Torr. Vertical bars indicate
p
Tem
540 the maximum amplitude of oscillations obtained

at the respective temperature. Temporal
oscillations in the catalytic CO oxidation on
500 Pt(110) under isothermal conditions in a flow
reactor were detected and recorded by means of
620 work function measurements between 440 and

0 590 K and in a pressure range between about 10-5
600
and 10-3 Torr. A large variety of oscillation
580 forms, including well-defined transitions from
− 0.2
]
T [K
560 periodic to irregular oscillations, was found,

depending on the choice of partial pressures and
ure
540
− 0.4
erat
temperature. LEED studies demonstrated that the

520 oscillations occur near the completion of the CO
p
Tem
500 induced 1×2 and 1×1 structural transformation of

− 0.6 the surface. Slight variation of the parameters led
480 to period doubling and transition to irregular
behavior. From [86E].
1 2 3
CO pressure p [10 −4 Torr]

0.6 1.4
(210) Pt :CO Rh :CO (430)
1.3

0.5
(321)
(741) (210) (531)
1.2
(430) (320)
0.4 (321)
(320)
(520) 1.1
(520) (310)
0.3 (310)
1.0
0.2 0.9
5.10 5.15 5.20 5.25 5.30 5.35 5.40 4.60 4.65 4.70 4.75 4.80
a Work function of clean surface Φ [eV] b Work function of clean surface Φ [eV]
Fig. 19. Work-function change ∆ΦCO after saturated CO adsorption at 300 K. ∆ΦCO vs. work function of
corresponding clean surface area {hkl}. Symbols indicate terrace structure. Dashed line represents linear regression
line. (a) Platinum. Intercept, A0 = 5.2 ± 0.2 eV; slope, A1= -0.92 ± 0.04; r = 0.997, without {210} and {320}. (b)
Rhodium. Intercept, A0 = 6.9 ± 0.9 eV; slope, A1= -1.2 ± 0.2; r = 0.97, without {430} and {321}. From [90L].
1.6 0.8
X :CO
Ru(0001) CO
Rh X = Rh FEM tip average
1.2 0.6
Pd
CO coverage θ [ML]
0.8 0.4
Ir Pt
Pt
Pt 0.2
0.4
0
4.60 4.80 5.00 5.20 5.40 0 0.2 0.4 0.6 0.8
Work function of clean surface Φ [eV] Work − function change ∆Φ [eV]
Fig. 20. Work-function change after saturated CO Fig. 21. Calibration of the work-function change
adsorption at 300 K for different fcc metals vs. work induced by CO adsorption of Ru(0001) vs. coverage at
function of corresponding clean surface. The plotted 200 K; relative coverage taken from integration of TPD
values represent measurements in which the {210} traces; absolute calibration at θ = 0.33 by comparison
([90L] and [81N3]) directions dominate (only for clean with LEED. From [83P2].
Pd was a general average value used). Dashed line
represents linear regression line: intercept,
A0 = 8 ± 1 eV; slope, A1= -1.4 ± 0.2; r = 0.97. From
[90L].

0 0
Ru(0001) NH 3
− 0.5

−1.0
Cu(111) H2 O
− 0.5
−1.5
−2.0 Cu(110) H2 O
−2.5 −1.0
0 0.2 0.4 0.6 0.8 0 1 2 3 4
NH3 coverage θ [ML] H2O exposure L [L]
Fig. 22. Work-function change for NH3 on Ru(0001) at Fig. 23. Work-function decrease due to water
80 K as function of NH3 coverage. From [83B5]. adsorption on Cu(110) and Cu(111). The initial dipole
moments are 0.85 and 0.5 Debye, respectively. From
[83B4].
Exposure L [1015 impacts cm−2]

0
0 3 6 9 12 15 Ru(0001) H2O
2−
O2 T = (90 K)
Pt(110)X
0.5 − 0.4
O (90→300 K)
0
− 0.8
NO (90 K) O2 (20 K)
− 0.5
−1.2
NO (20 K) 0 1 2 3 4 5
−1.0 H2O exposure L [10− 6 mbar s]
H2O (90 K)
Fig. 25. Work-function change upon H2O adsorption
0 5 10
Exposure L [MLE] on Ru(0001) at 120 K. From [91P].
Fig. 24. Work-function change upon exposure for O2,

H2O, and NO on Pt(111) at low temperature. The single
points O 22 - (90 K) and O (90ĺ K) are for a
saturated O 22 - layer at 90 K, and after annealing it to
300 K. An exposure of 1 MLE corresponds to 1.5·1015
impacts per cm2. From [89R].

0 0
Al(100) Na Ni(110) Na, K, Cs
T = 300K

−1
−1
Cs Na
3.2D −2
K
−2 ionic “ML”
−3
−3 −4
0 0.1 0.2 0.3 0.4 0.5 1 2 0 0.2 0.4 0.6 0.8 1.0 1.2 1.4
Na coverage θ [ML] Coverage θ [1015 atoms cm−2 ]
Fig. 26. Sodium induced work-function changes. Fig. 27. Work-function change vs. coverage for Na
Circles represent data points for an unannealed (open circles), K (open triangles), and Cs (open
overlayer and triangles values after annealing or high squares) on Ni(110) at 300 K. From [70G].
temperature adsorption. Porteus data (diamonds) were
obtained at room temperature [74P]. 3.2 D is calculated
from a least square fit in the ionic regime. θNa = 0.50,
c(2 × 2), is defined as monolayer coverage “ML”. The
sodium coverage is calculated from the integrated
thermal desorption spectra. From [87P2].
0 0 ring
Al(111) Rb p(2 × 2)
T = 140 K
− 0.5 compressed
−1
and mixed
(√3 × √3) R30°
−1.0 −2
(√3 × √3) R30°
Ru(0001) Cs
−1.5 (2 × 2) −3 T = 80 K
Φ max
−2.0 −4
Φ min
−2.5 −5
0 2 4 6 8 10 0 1 2 3 4 5 6 7 multilayer
Rb coverage θ [1014 atoms cm−2 ] Cs coverage θ [1014 atoms cm−2 ]
Fig. 28. Work-function change for different amounts of Fig. 29. Work-function change for Cs on Ru(0001) at
Rb adsorbed on Al(111) at 140 K. From [89H2]. 80 K with increasing Cs coverage. The observed LEED
structures are indicated. From [85H4].

0.2 0.6
W(110) X X = Au
W(100) X X = Au
0 0.4
Ni

Pd
− 0.2 0.2
Pd
−0.4 0
Co
−0.6 Ag − 0.2
−0.8 Cu
−0.4
Cu
−1.0 −0.6 Fe
0 5 10 15 20 25 30 35 0 1 2 3 4
Atomic density N [1014 atoms cm−2 ] Coverage θ [ML]
Fig. 30. Work-function change of a W(110) surface as Fig. 31. Relative work function of annealed surfaces of
a function of coverage (in 1014 atoms cm-2) induced by Au (900 K), Pd (1020 K), Co (1100 K), Cu(800 K), and
various metals deposited at 300 K. The atomic density Fe (1000 K) on W(100) as a function of coverage. The
of the W(110) surface is 14.12·1014 atoms cm-2.From Au, Pd, Cu, and Fe curves were reproduced from Refs.
[85K6]. [77B], [81P], [74B3], and [78J2], respectively. From
[89J].
0.5 0
Mo(100) Cu Start Cu deposition Pt(111) Cu
0.4
− 0.2
T = 300 K
0.3
573 K − 0.4
0.2
965 K
0.1 − 0.6
1 ML Cu (111)
0
− 0.8
T = 350 K T = 450 K
− 0.1
− 1.0
− 0.2
−0.3 − 1.2
0 1 2 3 4 0 200 400 600 800
Cu coverage θ [monolayers] Deposition time t [s]
Fig. 32. Work-function change of Mo(100) with Cu Fig. 33. Work-function change measured in situ during
coverage for depositions at 300 K (full dots), at 573 K Cu deposition on Pt(111) at two different temperatures
(open triangles) and 965 K (open circles). From [80S3]. T. Cu deposition starts at 0 s. At 145 s one monolayer
of Cu is accumulated. The curve for T = 450 K shows a
characteristic minimum-to-maximum structure at a
coverage near 1 ML (1 ML defined as one Cu(111)
layer). The slope of the curve for T = 350 K is more
rounded, according to a less ideal layer growth. From
[95N].

0 Cu Pt(110) Cu T = 420 K
R = 0.66 ML/min
a
− 0.02
T = 400 K
0
R = 0.7 ML/min
− 0.02
b
0
T = 370 K
R = 0.66 ML/min Fig. 34. Work-function change during deposition of Cu
− 0.02 onto Cu (the substrate of the Cu layers is Pt(111)).
Temperature dependence of the observed oscillations at
c almost identical deposition rates: (a) 420 K; (b) 400 K;
− 0.04 (c) 370 K; (d) 340 K. Upon lowering the deposition
0 T = 340 K
R = 0.66 ML/min temperature from 420 K, where besides an initial
decrease no periodic variation is found, to 340 K an
− 0.02 oscillatory behavior sets in and the amplitude of the
work-function-change oscillations increases. This
experiment nicely demonstrates the influence of surface
− 0.04 roughness on work function (Smoluchowski effect).
d From [95N].
0 100 200 300
Deposition time t [s]
0 5.0
Ru(0001) Cu W(100) Cu
− 0.1 T = 78 K 600 K
Work − function Φ [eV]
− 0.2 4.5
− 0.3
− 0.4 4.0
0 1 2 3 4 0 5 10 15 20
Cu coverage θ [ML] Copper atom density N [1014 atoms cm−2 ]
Fig. 35. Work-function change of Ru(0001) at 300 K Fig. 36. Work function vs. coverage produced by
with Cu coverage. From [87P]. incremental doses of Cu condensed onto W(100) at
78 K and after spreading each dose at 600 K. From
[77J2].

0.1
∆Φ max
0

− 0.1 ∆Φ max
∆Φsat
− 0.2 ∆Φsat
W(112)Cu
− 0.3
∆Φmin
−0.4
∆Φmin
− 0.5
−0.6
0 100 200 300 400
a Temperature T [K] b Cu coverage θ
Fig. 37. Work-function changes induced by Cu adsorption on the W(112) face as a function of the substrate
temperature. Open circles: ∆ϕmax, full circles: ∆ϕsat, crosses: ∆ϕmin. From [77M3].
0.6 4.8
W(100) Cu W(100) Cu
[78B2] ,T = 78 K
0.4
4.6
0.2
4.4
0
4.2
− 0.2 [74B3] ,T = 800 K
[77R] ,T = 20 K
[75R] 77 K
[74B3] 300 K 4.0
− 0.4
[74B3] ,T = 300 K
− 0.6 3.8
0 2 4 6 8 10 12 14 0 1 2 3
14 −2
Cu coverage θ [10 atoms cm ] Number of monolayers
Fig. 38. Work-function change vs. coverage of Cu Fig. 39. Work function of W(100) with Cu coverage:
adsorbed on W(100). [77R] adsorption at 20 K (open full circles at 78 K from [78B2]; open circles at 800 K
squares); [75C] adsorption at 77 K (open circles); from [74B3]; crosses at 300 K from [74B3]. From
[74B3] adsorption at 300 K, Cu axis rescaled (open [78B2].
triangles). From [77R].

5.3 5.3
W(100) Cu
5.1 5.1

4.9 4.9
4.7 4.7
1 2 4 3
1
4.5 4.5
2
3
4
4.3 4.3
0 5 10 15 20 25 30 0 5 10 15 20 25 30
a Deposition time t [min] b Deposition time t [min]
Fig. 40. Average work function vs. deposition-time plots for Cu on W(100) at various substrate temperatures: (a)
Curve 1, 400 K; curve 2, 450 K; curve 3, 500 K; curve 4, 550 K; (b) curve 1, 600 K; curve 2, 650 K; curve 3, 680 K,
curve 4, 800 K. From [ 81S].
For Fig. 41, see next page
0 5.3
Mo(110)Ag
5.1
a
4.9
− 0.05
b 4.7
W(110)Ag
4.5
−0.10
c 4.3
W(100)Ag
4.1
W(111)Ag
− 0.15
0 0.025 0.050 0.075 0.100 4.0
Ag coverage θ [ML] 0 1 2 3 4
Deposition time t [min]
Fig. 42. Work-function change as a function of silver
coverage θ on the Mo(110) face (a) at 370 K, (b) at 550 Fig. 43. Work function caused by silver adsorption on
K, and (c) at 850 K. In (a) the Ag atoms form 2D low index tungsten planes by constant deposition rate.
islands with a constant dipole moment per atom in the From [77K2].
island. In (b) and (c) the adsorbed Ag atoms form a 2D
gas. Obviously, the dipole moment per atom depends
somewhat on temperature. From [90K].

4.7 5.3
W(111) Cu W(211) Cu
4.6
5.1

4.5
1
4.9
4.4 2
2
4.7 1
4.3
3 3
4 4
4.5
4.2
5 5
4.0 4.3
0 5 10 15 20 25 30 35 0 5 10 15 20 25 30 35
a Deposition time t [min] b Deposition time t [min]
6.2
W(110) Cu
6.0
5.8
5.6
3
5.4
2
5.2
4
5
5.0
4.8 1
0 1 2 3 4 5 6 7
c Deposition time t [min]
Fig. 41. Average work function vs. Cu deposition-time plots for (a) the W(111) plane, (b) the W(211) plane and (c)
the W(110) plane at various substrate temperatures: curves 1, 300 K; curves 2, 500 K; curves 3, 680 K; curves 4, 800
K; curves 5, 930 K. From [ 81S].

0 0
W(110)Ag W(110)Ag
− 0.2

− 0.2
T = 300 K d
T = 500 K − 0.4
− 0.4
c b
− 0.6
b
− 0.6
− 0.8
c
a
maximum drift
− 0.8 −1.0
0 1 2 3 4 5 0 1 2 3 4 5 6 7 8 9
Ag coverage θ [units of Na ] Deposition time t [min]
Fig. 44. Work-function change of a W{110} surface Fig. 45. Work-function changes vs. time of Ag
with Ag coverage. Coverage in units of Na = 12.89·1014 deposition at (a) 78 K, (b) 300 K, (c) 770 K, (d) 1000
K. Flux density is 5.27·1012 atoms/s cm2 (determined
atoms cm-2. The maximum drift during the experiment by the quartz oscillator). From [79K].
is the difference between the work function after
flashing off the Ag at the end of the experiment and the
work function before the experiment. From [77B].
0.4 5.6
W(110)Ag unannealed,T = 90 K W(110)Ag
unannealed,T = 300 K
annealed at 700 K
0 5.2
− 0.4 4.8
− 0.8 4.4
− 1.0 4.0
0 1 2 3 4 0 1 2 3
Ag coverage θ [ML] Ag exposure L [ML]
Fig. 46. Work-function changes vs. coverage in Fig. 47. Work function of the (110) facet of a tungsten
monolayers for Ag deposition on W(110) at 90 and field emitter at 300 K as a function of silver exposure.
300 K, and 300 K annealed for 120 s at 700 K. All The authors interpret this data as follows: Below an
measurements were carried out at 90 K. From [93Z]. exposure treshold of about one ML, Ag adatoms
migrate to the high-index facets that surround the
W(110) plane, and the emission properties are
indistinguishable from those of the bare substrate. At
1 ML the adatoms invade the (110) plane, modifying
the surface density of electron states and bringing about
an abrupt increase in electron emission. Above 2 ML
the additionally evaporated Ag atoms migrate again to
the surrounding facets. From [95D].

5.4 0.25
Re:Au W(110)Au
T = 900 K
0.20
5.2

300 K
0.15
5.0
W:Au
0.10
4.8
0.05
4.6
0 maximum drift
4.4 −0.05
0 1 2 3 4 5 6 7 0 1 2 3 4 5
Au coverage θ [ML] Au coverage θ [ML]
Fig. 48. Comparison of changes in average work Fig. 49. Work-function change of a W(110) surface
function with average coverage for gold spread at with Au coverage at 300 and 900 K deposition
600 K on tungsten and rhenium. From [77C]. temperature. From [77B].
0.6 5.4
W(100)Au W(100)Au
T = 900 K
300 K
0.4 5.2
0.2 5.0
0 4.8
[78B2],T = 78 K
maximum drift [76R],T = 20 K
−0.2 4.6
0 1 2 3 0 1 2 3
Au coverage θ [ML] Au coverage θ [ML]
Fig. 50. Work-function change of a W(100) surface Fig. 51. Work-function changes with Au coverage on
with Au coverage at 300 and 900 K. From [77B]. W(100). Filled dots 78 K [78B2], open dots 20 K
[76R]. From [78B2].

1.0 0
W:Au W(110) W(110)Cr

0.8 after T = 1100 K annealed
− 0.50
W(001)
0.6
W(112) W(115)
−1.00
0.4
deposited at 1000 K
0.2
W(111) −1.50
0 0.5 1.0 1.5 2.0 2.5
Cr coverage θ [ML]
0
Fig. 53. Work-function change for Cr overlayers on
W(110) at 100 K (open circles) and after a brief 1100 K
anneal (solid circles). Chromium coverage is
− 0.2 determined by TPD peak area. No change was observed
0 1 2 3 4
for the AES and LEED data. Therefore, the ∆Φ
Au coverage θ [1015 atoms cm−2 ] difference is assigned to a difference in adatom
mobility and two-dimensional ordering during the
Fig. 52. Work-function changes as a function of Au formation of a pseudomorphic monolayer for
coverage of selected low-index faces of a W cylindrical 0 < θCr < 1. From [89B3].
crystal surface. The work function of the clean W(001)
surface was taken as zero. Au coverage scale was
calibrated by assuming that the first maximum for
W(112) appears at 6.3·1014 atoms cm-2 as reported in
Ref. [84K2]. From [86M].
0.2 5.5 Fig. 54. Work-function change and work function vs.
W(110)Fe T = 90 K Fe coverage on W(110) for deposition at various
150 K temperatures, as indicated on the figure. Deposition
0 175 K 5.3 was carried out at a rate of 0.1 monolayers per 90 s.

200 K
250 K After each dose the crystal was cooled to 90 K for
− 0.2 300 K 5.1 work-function measurements and then reheated for the
600 K next dose, and so on. Conversion of Fe from the low to
the high temperature form is governed by diffusion and
−0.4 4.9 aggregation into islands at T ≥ 160 K, with an
activation energy of diffusion ~ 10 kcal mol-1. Direct
− 0.6 conversion of isolated Fe atoms does not occur below
4.7
220 K and may not in fact play a significant role in the
conversion of Fe(I) to Fe(II), which may exist only in
− 0.8 4.5 close-packed patches. For high coverages conversion
occurs already at 300 K. These findings suggest that
−1.0 Fe-Fe interactions contribute to conversion and that the
4.3
0 0.2 0.4 0.6 0.8 1.0 1.2 rate limiting step for conversion may mainly be
Fe coverage θ [ML] diffusion except at very high coverages. From [97N2].

0.2 5.5 5.4

W(110)Fe T = 90 K W:Fe
300 K
0 300K /600 K 5.3

5.2

− 0.2 5.1
Fe(110)
−0.4 4.9 5.0

W(110)
Fe(111)
− 0.6 4.7
Fe(100) 4.8
W(112)
− 0.8 4.5
Fe(poly film)
4.6 W(111)
−1.0 4.3
0 0.5 1.0 1.5 2.0 2.5 3.0 3.5
Fe coverage θ [ML]
4.4
Fig. 55. Work function and work-function change vs.
Fe coverage in monolayers on clean W(110) for various W(001)
deposition temperatures. The curve marked
300 K/600 K refers to deposition at 300 K with 60 s 4.2
anneal at 600 K after each dose. From [97N3]. 0 1 2 3 4 5 6
Fe coverage θ [1015 atoms cm−2 ]
Fig. 56. Work function during continuous room

temperature deposition as a function of the iron
coverage for the W(110), W(112), W(111), and W(001)
surfaces. From [83G2].
0.2 0.4
W(110)Co unannealed W(100)Co unannealed
annealed annealed
0 0.3
− 0.2 0.2
− 0.4 0.1
− 0.6 0
− 0.8 − 0.1
−1.0 − 0.2
0 1 2 3 0 1 2 3
a Co coverage θ [ML] b Co coverage θ [ML]
Fig. 57. Work-function change of the unannealed (100 K) and annealed (1100 K) surfaces of (a) Co/W(110); and (b)
Co/W(100) as a function of Co coverage. From [89J].

0.4 0.6
W(110)Pd T = 300 K
W(100)Pd
0.2 0.5

0.4
0
1 T = 460 K
2 0.3
3
− 0.2
0.2
− 0.4
0.1
− 0.6
0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 0 1 2 3 4 5
Pd coverage θ [ML] Pd coverage θ [ML]
Fig. 58. Work-function change of a W(110) surface vs. Fig. 59. Work-function change of a W(100) surface vs.
Pd coverage at various deposition rates and substrate Pd coverage evaporated and measured at 300 K. Filled
temperatures. Open circles: 17·1012 cm-2 s-1, 300 K, circles as deposited at 300 K; crosses after anneal at
2 min anneals at 830 K for θ < 1; filled circles: 28·1012 460 K. From [81P].
cm-2 s-1, 300 K, 2 min anneals at 830 K for all θ; open
triangles: 17·1012 cm-2 s-1, 300 K. From [80S4].

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76D Dahlberg, S.C.: Surf. Sci. 59 (1976) 83.
76E Engelhardt, H.A., Menzel, D.: Surf. Sci. 57 (1976) 591.
76E2 Ehrhardt, J.-J., Fusy, J., Cassuto, A.: J. Microsc. Spectrosc. Electron. 1 (1976) 415.
76E3 Evans, St., Pielaszek, J., Thomas, J.M.: Surf. Sci. 56 (1976 ) 644.
76G Gland, J.L., Somorja, G.A.: Adv. Colloid Interface Sci. 5 (1976) 205.
76H Hopkins, B.J., Jones, A.R., Winton, R.I.: Surf. Sci. 57 (1976) 266.
76I Ivanov, V.P., Boreskov, G.K., Savchenko. V.I.. Egelhoff, W.F., Weinberg, W.H.: Surf. Sci.
61 (1976) 207.
76J Jaschinski, W., Niedermayer, R.: Thin Solid Films 32 (1976) 181.
76J2 Jones, J.P., Jones, N.T.: Thin Solid Films 35 (1976) 83.
76K Krishnan, N.G., Delgass, W.N., Robertson, W.D.: Surf. Sci. 57 (1976) 1.
76M Mroz, A., Sidorski, Z.: Acta Phys. Pol. A 49 (1976) 437.
76M2 McElhiney, G., Pritchard, J.: Surf. Sci. 60 (1976) 397.
76M3 McElhiney, G., Papp, H., Pritchard, J.: Surf. Sci. 54 (1976) 617.
76N Nieuwenhuys, B.E.: Surf. Sci.59 (1976) 430.
76P Polanski, J., Sidorski, Z., Zuber, S.: Acta Phys. Pol. A 49 (1976) 299.
76R Richter, L., Gomer, R.: Phys. Rev. Lett. 37 (1976) 763.
76R2 Richter, L., Gomer, R.: Surf. Sci. 59 (1976) 575.
76R3 Roberts, R.H., Pritchard, J.: Surf. Sci. 54 (1976) 687.
76T Taylor, T.N., Colmenares, C.A., Smith, R.L., Somorjai, G.A.: Surf. Sci. 54 (1976) 317.
76Y Yates, J.T.Jr., Klein, R., Madey, T.E.: Surf. Sci. 58 (1976) 469.
77A Abon, M., Bergeret, G., Tardy, B.: Surf. Sci. 68 (1977) 305.
77B Bauer, E., Poppa, H., Todd, G., Davis, P.R.: J. Appl. Phys. 48 (1977) 3773.
77B2 Bozso, F., Ertl, G., Grunze, M., Weiss, M.: Appl. Surf. Sci. 1 (1977) 103.
77B3 Butz, R., Wagner, H.: Surf. Sci. 63 (1977) 448.
77B4 Briggs, D., Marbrow, R.A., Lambert, R.M.: Surf. Sci. 65 (1977) 314.
77B5 Bradshaw, A.M., Hofmann, P., Wyrobisch, W.: Surf. Sci. 68 (1977) 269.
77B6 Bonzel, H.P., Pirug, G.: Surf. Sci. 62 (1977) 45.
77C Coles, S.J.T., Jones, J.P.: Surf. Sci. 68 (1977) 312.
77C2 Collins, R.A., Kiwanga, C.A.: Surf. Sci. 64 (1977) 778.
77D Derochette, J.-M., Marien, J.: Phys. Status Solidi A 39 (1977) 281.
77D2 Demuth, J.E.: Chem. Phys. Lett. 45 (1977) 12.
77D3 Derrien, J., Arnaud d’avitaya, F.: Surf. Sci. 65 (1977) 668.
77D4 Demuth, J.E.: Surf. Sci. 65 (1977) 369.

77E Erley, W., Wagner, H.: Surf. Sci. 66 (1977) 371.

77E2 Ertl, G., Neumann, M., Streit, K.M.: Surf. Sci. 64 (1977) 393.
77E3 Engel, T., Von dem Hagen, T., Bauer, E.: Surf. Sci. 62 (1977) 361.
77F Fischer, T.E., Kelemen, S.R.: Surf. Sci. 69 (1977) 1.
77G Goddard, P.J., Lambert, R.M.: Surf. Sci. 67 (1977) 180.
77G2 Gupalo, M.S., Medvedev, V.K., Smereka, T.P., Babkin, G.V., Palyukh, B.M.: Fiz. Tverd.
Tela 19 (1977) 2955; Sov. Phys. Solid State (English Transl.) 19 (1977) 1731.
77G3 Gorodetsky, D.A., Melnik, Yu.P.: Surf. Sci. 62 (1977) 647.
77G4 Gartland, P.O.: Surf. Sci. 62 (1977) 183.
77J Jones, J.P., Roberts, E.W.: Surf. Sci. 62 (1977) 415.
77J2 Jones, J.P., Roberts, E.W.: Surf. Sci. 64 (1977) 355.
77K Kellog, G.L., Tsong, T.T.: Surf. Sci. 62 (1977) 343.
77K2 Kolaczkiewicz, J., Sidorski, Z.: Surf. Sci. 63 (1977) 501.
77K3 Kessler, J., Thieme, F.: Surf. Sci. 67 (1977) 405.
77K4 Krishnan, N.G., Delgass, W.N., Robertson, W.D.: J. Phys. F 7 (1977) 2623.
77K5 Klein, R., Shik, A.: Surf. Sci. 69 (1977) 403.
77L Leung, C., Vass, M., Gomer, R.: Surf. Sci. 66 (1977) 67.
77M Marien, J.: Phys. Status Solidi A 38 (1977) 513.
77M3 Mróz, S., Mróz, A., Sidorski, Z., in: Proc. 7th Intern. Vacuum Congr. and 3rd Intern. Conf. on
Solid Surfaces, Vienna, 1977, p. 1125.
77M4 Marbrow, R.A., Lambert, R.M.: Surf. Sci. 67 (1977) 489.
77P Pantel, R., Bujor, M., Bardolle, J.: Surf. Sci. 62 (1977) 589.
77R Richter, L., Gomer, R.: Appl. Phys. 13 (1977) 303.
77R2 Rubloff, G.W., Demuth, J.E.: J. Vac. Sci. Technol. 14 (1977) 419.
77S Sébenne, C.A.: Nuovo Cimento 39B (1977) 768.
77V Vedula, Yu.S., Gonchar, V.V., Naumovets, A.G., Fedorus, A.G.: Fiz. Tverd. Tela 19 (1977)
1569; Sov. Phys. Solid State (English Transl.) 19 (1977) 1505.
78B Bertolini, J.-C., Massardier, J., Dalmai-Imelik, G.: J. Chem. Soc. Faraday Trans. 74 (1978)
1720.
78B2 Billington, R.L., Rhodin, T.N.: Phys. Rev. Lett. 41 (1978) 1602.
78B3 Brodén, G., Pirug, G., Bonzel, H.P.: Surf. Sci. 72 (1978) 45.
78B4 Bauer, E., Engel, T.: Surf. Sci. 71 (1978) 695.
78C Collins, R.A., Kiwanga, C.A., Surf. Sci. 71 (1978) 185.
78C2 Clemens, H.J., Wienskowski, J., Mönch, W.: Surf. Sci. 78 (1978) 648.
78F Felter, T.E., Estrup, P.J.: Surf. Sci. 76 (1978) 464.
78G Gewinner, G., Peruchetti, J.C., Jaegle, A., Kalt, A.: Surf. Sci. 78 (1978) 439.
78G2 Goddard, P.J., Schwaha, K., Lambert, R.M.: Surf. Sci. 71 (1978) 351.
78G3 Grunze, M., Boszo, F., Ertl, G., Weiss, M.: Appl. Surf. Sci. 1 (1978) 241.
78G4 Goldstein, B., Szostak, D.J.: Surf. Sci. 74 (1978) 461.
78G5 Green, A.K., Bauer, E.: Surf. Sci. 74 (1978) 676.
78H Hofmann, P., Unwin, R., Wyrobisch, W., Bradshaw, A.M.: Surf. Sci. 72 (1978) 635.
78J Jones, J.P., Roberts, E.W.: Thin Solid Films 48 (1978) 215.
78J3 Jones, R.G., Perry, D.L.: Surf. Sci. 71 (1978) 59.
78L2 Lindgren, S.A., Walldén, L.: Solid State Commun. 25 (1978) 13.
78L3 Lakh, Kh.I., Stasyuk, Z.V.: Fiz. Tverd. Tela 20 (1978) 1989; Sov. Phys. Solid State (English
Transl.) 20 (1981) 1149.
78M Miyamura, M., Sakisaka, Y., Nishijima, M., Onchi, M.: Surf. Sci. 72 (1978) 243.
78M2 Marbrow, R.A., Lambert, R.M.: Surf. Sci. 71 (1978) 107.
78N Netzer, F.P., Wille, R.A: Surf. Sci. 74 (1978) 547.
78P Peralta, L., Margot, E., Berthier, Y., Oudar, J.: J. Microsc. Spectrosc. Electron. 3 (1978) 151.
78P2 Papageorgopoulos, C.A.: J. Phys. C 11 (1978) L15.
78P3 Papageorgopoulos, C.A.: Surf. Sci. 75 (1978) 17.

78P4 Prior, K.A., Schwaha, K., Lambert, R.M.: Surf. Sci 77 (1978) 193.
78R Rawlings, K.J., Hopkins, B.J., Foulias, S.D.: Surf. Sci. 77 (1978) 561.
78S Shigeishi, R.A.: Surf. Sci. 72 (1978) 61.
78T Taylor, J.L., Weinberg, W.H.: J. Vac. Sci. Technol. 15 (1978) 1811.
78T2 Taylor, J.L., Ibbotson, D.E., Weinberg, W.H.: J. Chem. Phys. 69 (1978) 4298.
78W Wang, C., Gomer, R.: Surf. Sci. 74 (1978) 389.
79A Akimoto, K., Sakisaka, Y., Nishijima, M., Onchi, M.: Surf. Sci. 82 (1979) 349.
79A2 Akimoto, K., Sakisaka, Y., Nishijima, M., Onchi, M.: Surf. Sci. 88 (1979) 109.
79B Bertel, E., Schwaha, K., Netzer, F.P.: Surf. Sci. 83 (1979) 439.
79B2 Bertolini, J.C., Rousseau, J.: Surf. Sci. 83 (1979) 531.
79B3 Bauer, E., Poppa, H.: Surf. Sci. 88 (1979) 31.
79B4 Bhattacharya, A.K., Broughton, J.Q., Perry, D.L.: Faraday Trans. I 75 (1979) 850.
79B5 Brodén, G., Bonzel, H.P.: Surf. Sci. 84 (1979) 106.
79C Chandler, P.E., Taylor, P.A., Hopkins, B.J.: Surf. Sci. 82 (1979) 500.
79C2 Christmann, K., Behm, R.J., Ertl, G., Van Hove, M.A., Weinberg, W.H.: J. Chem. Phys. 70
(1979) 4168.
79D Dowben, P.A., Jones, R.G.: Surf. Sci. 84 (1979) 449.
79D2 Dowben, P.A., Jones, R.G.: Surf. Sci. 88 (1979) 348.
79D3 Dowben, P.A., Jones, R.G.: Surf. Sci. 89 (1979) 114.
79F Fisher, G.B.: Surf. Sci. 87 (1979) 215.
79G Grunze, M., Driscoll, R.K., Burland, G.N., Cornish, J.C.L., Pritchard, J.: Surf. Sci. 89 (1979)
381.
79G2 Gupalo, M.S., Medvedev, V.K., Palyukh, B.M., Smereka, T.P.: Fiz. Tverd. Tela 21 (1979)
79H Habraken, F.H.P.M., Bootsma, G.A., Hofmann, P., Hachicha, S., Bradshaw, A.M.: Surf. Sci.
88 (1979) 285.
79H2 Hofmann, P., Horn, K., Bradshaw, A.M., Jacobi, K.: Surf. Sci. 82 (1979) L610.
79H3 Hölzl, J., Schulte, F.K.: Work function of metals, Springer Tracts of Modern Physics,
Vol. 85, Höhler, G., Niekisch, E.A. (eds.), Berlin: Springer, 1979, p. 1.
79H4 Hofmann, P., Wyrobisch, W., Bradshaw, A.M.: Surf. Sci. 80 (1979) 344.
79H5 Hollins, P., Pritchard, J.: Surf. Sci. 89 (1979) 486.
79J Jupille, J., Bigeard, B., Fusy, J., Cassuto, A.: Surf. Sci. 84 (1979) 190.
79J2 Jones, R.G., Perry, D.L.: Surf. Sci. 88 (1979) 331.
79J3 Jones, R.G.: Surf. Sci. 88 (1979) 367.
79K Kolaczkiewicz, J.: Surf. Sci. 84 (1979) 475.
79K2 Küppers, J., Nitschke, F., Wandelt, K., Ertl, G.: Surf. Sci. 87 (1979) 295.
79K3 Küpers, J., Wandelt, K., Ertl, G.: Phys. Rev. Lett. 43 (1979) 928.
79M Medvedev, V.K., Yakovkin, I.N.: Fiz. Tverd. Tela 21 (1979) 313; Sov. Phys. Solid State
79N Norton, P.R., Goodale, J.W., Selkirk, E.B.: Surf. Sci. 83 (1979) 189.
79N2 Norton, P.R., Goodale, J.W.: Solid State Commun. 31 (1979) 223.
79P Peruchetti, J.C., Gewinner, G., Jaegle, A.: Surf. Sci. 88 (1979) 479.
79R Richter, L., Gomer, R.: Surf. Sci. 83 (1979) 93.
79S Sidorski, Z., Zuber, S., Polanski, J.: Surf. Sci. 80 (1979) 626.
79S2 Sidorski, Z., Szelwicki, T., Dworecki, Z.: Thin Solid Films 61 (1979) 203.
79S3 Schwaha, K., Spencer, N.D., Lambert, R.M.: Surf. Sci. 81 (1979) 273.
79T Taylor, J.L., Ibbotson, D.E., Weinberg, W.H.: Surf. Sci. 79 (1979) 349.
79V Van Strien, A.J., Nieuwenhuys, B.E.: Surf. Sci. 80 (1979) 226.
79W Weiss, M., Ertl, G., Nitschke, F.: Appl. Surf. Sci. 2 (1979) 614.
79W2 Wang, C., Gomer, R.: Surf. Sci. 90 (1979) 10.
79Z Zuber, S., Sidorski, Z., Polanski, J.: Surf. Sci. 87 (1979) 375.
80B Bonczek, F., Engel, T., Bauer, E.: Surf. Sci. 97 (1980) 595.
80B2 Behm, R.J., Christmann, K., Ertl, G.: J. Chem. Phys. 73 (1980) 2984.
80B3 Bertel, E., Netzer, F.P.: Surf. Sci. 97 (1980) 409.

80B4 Behm, R.J., Christmann, K., Ertl, G.: Surf. Sci. 99 (1980) 320.
80B5 Benndorf, C., Egert, B., Nöbl, C., Seidel, H., Thieme, F.: Surf. Sci. 92 (1980) 636.
80C Chen, J.-R., Gomer, R.: Surf. Sci. 94 (1980) 456.
80C2 Chiang, T.-C., Kaindl, G., Eastman, D.E.: Solid State Commun. 36 (1980) 25.
80D Davis, P.R.: Surf. Sci. 91 (1980) 385.
80D2 Desplat, J.-L., Papageorgopoulos, C.A.: Surf. Sci. 92 (1980) 97.
80E Erley, W.: Surf. Sci. 94 (1980) 281.
80F Foord, J.S., Goddard, P.J., Lambert, R.M.: Surf. Sci. 94 (1980) 339.
80F2 Feulner, P., Kulkarni, S., Umbach, E., Menzel, D.: Surf. Sci. 99 (1980) 489.
80G Gupalo, M.S., Medvedev, V.K., Palyukh, B.M., Smereka, T.P.: Fiz. Tverd. Tela 22 (1980)
80G2 Gerenser, L.J., Baetzold, R.C.: Surf. Sci. 99 (1980) 259.
80H Habraken, F.H.P.M., Mesters, C.M.A.M., Bootsma, G.A.: Surf. Sci. 97 (1980) 264.
80H2 Hölzl, J., Porsch, G., Schrammen, P.: Surf. Sci. 97 (1980) 529.
80I Ibbotson, D.E., Wittrig, T.S., Weinberg, W.H.: Surf. Sci. 97 (1980) 297.
80K Kaindl, G., Chiang, T.-C., Eastman, D.E., Himpsel, F.J.: Phys. Rev. Lett. 45 (1980) 1808.
80K2 Kitson, M., Lambert, R.M.: Surf. Sci. 100 (1980) 368.
80K3 Khonde, K., Darville, J., Donnelly, S.E.: Appl. Surf. Sci. 6 (1980) 297.
80L Lindgren, S.ǖ:DOOGpQ/3K\V5HY%22 (1980) 5967.
80M Michel, R., Gastaldi, J., Allaria, C., Jourdan, C., Derrien, J.: Surf. Sci. 95 (19080) 297.
80N Nishitani, R., Kawai, S., Iwasaki, H., Nakamura, S., Aono, M., Tanaka, T.: Surf. Sci. 92
(1980) 191.
80O Oudar, J.: Catal. Rev. Sci. Eng. 22 (1980) 171.
80O2 Oudar, J.: Proc. ICOSS-4 and ECOSS-3, Cannes (1980) 645.
80P Purtell, R.J., Merrill, R.P., Seabury, C.W., Rhodin, T.N.: Phys. Rev. Lett. 44 (1980) 1279.
80R Rawlings, K.J.: Surf. Sci. 99 (1980) 507.
80S Sakisaka, Y., Miyamura, M., Tamaki, J., Nishijima, M., Onchi, M.: Surf. Sci. 93 (1980) 327.
80S2 Schlenk, W., Bauer, E.: Surf. Sci. 94 (1980) 528.
80S3 Soria, F., Hoppa, H.: J. Vac. Sci. Technol. 17 (1980) 449.
80S4 Schlenk, W., Bauer, E.: Surf. Sci. 93 (1980) 9.
80S5 Seabury, C.W., Rhodin, T.N., Purtell, R.J., Merrill, R.P.: Surf. Sci. 93 (1980) 117.
80T Takayanagi, K., Kolb, D.M., Kambe, K., Lehmpfuhl, G.: Surf. Sci. 100 (1980) 407.
80W Wang, C., Gomer, R.: Surf. Sci. 91 (1980) 533.
80W2 Weng, S.L., El-Batanouny, M.: Phys. Rev. Lett. 44 (1980) 612.
81B Benndorf, C., Nobl, C., Rusenberg, M., Thieme, F.: Surf. Sci. 111 (1981) 87.
81B2 Bigun, G.I., Nabitovich, I. D., Sukhorskii, Yu.S.: Fiz. Tverd. Tela 23 (1981) 2128; Sov. Phys.
81C Campuzano, J.C., Dus, R., Greenler, R.G.: Surf. Sci. 102 (1981)172.
81E Ertl, G., Lee, S.B., Weiss, M.: Surf. Sci. 111 (1981) L711.
81F Fisher, G.B.: Chem. Phys. Lett. 79 (1981) 452.
81G Gupalo, M.S., Medvedev, V.K., Palyukh, B.M., Smereka, T.P.: Fiz. Tverd. Tela 23 (1981)
81H Hayden, B.E., Schweizer, E., Kotz, R., Bradshaw, A.M.: Surf. Sci. 111 (1981) 26.
81I Ibbotson, D.E., Wittrig, T.S., Weinberg, W.H.: Surf. Sci. 110 (1981) 294.
81K Kramer, H.M., Bauer, E.: Surf. Sci. 107 (1981) 1.
81L Lee, S.B., Weiss, M., Ertl, G.: Surf. Sci. 108 (1981) 357.
81M Medvedev, V.K., Yakovkin, I.N.: Fiz. Tverd. Tela 23 (1981) 669; Sov. Phys. Solid State
81M2 Melamed B.Ya., Silant'ev, V.I., Shevchenko, N.A.: Fiz. Tverd. Tela 23 (1981) 2424; Sov.
Phys. Solid State (English Transl.) 23 (1981) 1416.
81N Nishijima, M., Masuda, S., Sakisaka, Y., Onchi, M.: Surf. Sci. 107 (1981) 31.
81N2 Namba, H., Darville, J., Gilles, J.M.: Surf. Sci. 108 (1981) 446.
81N3 Nieuwenhuys, B.E: Surf. Sci. 105 (1981) 505.
81P Prigge, S., Roux, H., Bauer, E.: Surf. Sci. 107 (1981) 101.

81S Sidorski, Z., Szelwicki, T., Dworecki, Z.: Thin Solid Films 75 (1981) 87.
81S2 Schmeisser, D., Jacobi, K.: Surf. Sci. 108 (1981) 421.
81T Thiel, P.A., Hoffmann, F.M., Weinberg, W.H.: J. Chem. Phys. 75 (1981) 5556.
81W Wandelt, K., Hulse, J., Küppers, J.: Surf. Sci. 104 (1981) 212.
81W2 Wittrig, T.S., Ibbotson, D.E., Weinberg, W.H.: Surf. Sci. 102 (1981) 506.
82A Agron, P.A., Carlson, T.A.: J. Vac. Sci. Technol. 20 (1982) 815.
82C Christmann, K., Demuth, J.E.: Surf. Sci. 120 (1982) 291.
82C2 Campbell, C.T., Taylor, T.N.: Surf. Sci. 122 (1982) 119.
82C2 Christmann, K., Demuth, J.E.: J. Chem. Phys. 76 (1982) 6308.
82C3 Castro, G.R., Küppers, J.: Surf. Sci. 123 (1982) 456.
82C4 Campbell, C.T., Taylor, T.N.: Surf. Sci. 118 (1982) 401.
82D Derochette, J.-M.: Phys. Status Solidi A 71 (1982) K99.
82D2 Derochette, J.-M.: Bull. Soc. R. Sci. Liege 51 (1982) 136.
82D3 Derochette, J.-M.: Bull. Soc. R. Sci. Liege 51 (1982) 147.
82E Ertl, G., Lee, S.B., Weiss, M.: Surf. Sci. 114 (1982) 515.
82E2 Erley, W.: Surf. Sci. 114 (1982) 47.
82F Foord, J.S., Lambert, R.M.: Surf. Sci. 115 (1982) 141.
82F2 Faldt, A.: Surf. Sci. 114 (1982) 311.
82H Hsu, Y., Jacobi, K., Rotermund., H.H.: Surf. Sci. 117 (1982) 581.
82H2 Heras, J.M., Papp, H., Spiess, W.: Surf. Sci. 117 (1982) 590.
82J Jacobi, K., Rotermund H.H.: Surf. Sci. 116 (1982) 435.
82K Khonde, K., Darville, J., Gilles, J.M.: J. Vac. Sci. Technol. 20 (1982) 834.
82K2 Kato, H., Sakisaka, Y., Miyano, T., Kamel, K., Nishijima, M., Onchi, M.: Surf. Sci. 144
(1982) 96.
82L Lindgren, S.A., Paul, J., Wallden, L.: Surf. Sci. 117 (1982) 426.
82L2 Lozovyi, Ya., B., Medvedev, V.K., Smereka, T.P., Palyukh, B.M., Babkin, G.V.: Fiz. Tverd.
82L3 Lakh, Kh.I., Stasyuk, Z.V.: Zh. Tekh. Fiz. 52 (1982) 1397.
82L4 Lang, N.D., Williams, A.R., Himpsel, F.J., Reihl, B., Eastman, D.E.: Phys. Rev. B 26 (1982)
1728.
82L5 Lange, P., Grider, D., Neff, H., Sass, J.K., Unwin, R.: Surf. Sci. 118 (1982) L257.
82M Murayama, Z., Kojima, I., Miyazaki, E., Yasumori, I.: Surf. Sci. 118 (1982) L281.
82M2 Mariani, C., Horn, K., Bradshaw, A.M.: Phys. Rev. B 25 (1982) 7798.
82N Nishitani, R., Oshima, C., Aono, M., Tanaka, T., Kawai, S., Iwasaki, H., Nakamura S.: Surf.
Sci. 115 (1982) 48.
82N2 Nakanishi, S., Kanno, M., Horiguchi, T.: Jpn. J. Appl. Phys. Part 2 - Letters 21 (1982) L419.
82P Park, C., Kramer, H.M., Bauer, E.: Surf. Sci. 115 (1982) 1.
82P2 Park, C., Kramer, H.M., Bauer, E.: Surf. Sci. 116 (1982) 456.
82P3 Park, C., Cramer, H.M., Bauer, E.: Surf. Sci. 116 (1982) 467.
82P4 Popov, G. Bauer, E.: Surf. Sci. 122 (1982) 433.
82P5 Poelsema, B., Palmer, R.L., Comsa, G.: Surf. Sci. 123 (1982) 152.
82P6 Popov, G. Bauer, E: Surf. Sci. 123 (1982) 165.
82P7 Papageorgopoulos, C.A.: Phys. Rev. B 25 (1982) 3740.
82R Richardson, N.V., Palmer, N.R.: Surf. Sci. 114 (1982) L1.
82S Spitzer, A., Lüth, H.: Surf. Sci. 120 (1982) 376.
82S2 Smith, G.C., Norris, C., Binns, C., Padmore, H.A.: J. Phys. C: Solid State Phys. 15 (1982)
6481.
82S3 Spitzer, A., Lüth, H.: Surf. Sci. 118 (1982) 121.
82S4 Spitzer, A., Lüth, H.: Surf. Sci. 118 (1982) 136.
82S5 Soukiassian, P., Riwan, R., Borenzstein, Y.: Solid State Commun. 44 (1982) 1375.
82S6 Smith, G.C., Padmore, H.A., Norris, C.: Surf. Sci. 119 (1982) L287.
82S7 Sakisaka, Y., Kato, H., Onchi, M.: Surf. Sci. 120 (1982) 150.
82T Tochihara, H., Murata, Y.: J. Phys. Soc. Jpn. 51 (1982) 2920.
82T2 Tysoe, W.T., Lambert, R.M.: Surf. Sci. 115 (1982) 37.

83A Andersson, S., Harris, J.: Phys. Rev. B 27 (1983) 9.

83A2 Al-Rawi, O.Z., Jones, J.P.: Surf. Sci. 124 (1983) 220.
83A3 Artamonov, O.M., Smirnov, O.M., Terekhov, A.N.: Poverkhnost Fizika Khimiya Mekhanika
(1983); Phys. Chem. Mech. Surfaces (English Transl.) 2 (1985) 2281.
83B Behm, R.J., Thiel, P.A., Norton, P.R., Ertl., G.: J. Chem. Phys. 78 (1983) 7437.
83B3 Blaszczyszyn, M., Blaszczyszyn, R., Meclewski, R., Melmed, A.J., Madey, T.E.: Surf. Sci.
131 (1983) 433.
83B4 Bange, K., Döhl, R., Grider, D.E., Sass, J.K.: Vacuum 33 (1983) 757.
83B5 Benndorf, C., Madey, T.E.: Surf. Sci. 135 (1983) 164.
83C Cattania, M.G., Penka, V., Behm, R.J., Christmann, K., Ertl, G.: Surf. Sci. 126 (1983) 382.
83G Gudde, N.J., Lambert, R.M.: Surf. Sci. 134 (1983) 703.
83G2 Gardiner, T.M.: Thin Solid Films 105 (1983) 213.
83G3 Gudde, N.J., Lambert, R.M.: Surf. Sci. 124 (1983) 372.
83H Hayden, B.E., Prince, K.C., Davie, P.J., Paolucci, G., Bradshaw, A.M.: Solid State Commun.
48 (1983) 325.
83J Jackman, T.E., Griffiths, K., Davies, J.A., Norton, P.R.: J. Chem. Phys. 79 (1983) 3529.
83K Koel, B.E., Peebles, D.E., White, J.M.: Surf. Sci. 125 (1983) 709.
83K2 Khonde, K., Darville, J., Gilles, J.M.: Surf. Sci. 126 (1983) 414.
83K3 Kiskinova, M., Pirug, G., Bonzel, H.P.: Surf. Sci. 133 (1983) 321.
83M Mattern-Klosson, M., Ding, X.M., Lüth, H., Spitzer, A.: Surf. Sci. 129 (1983) 1.
83M2 Miranda, R., Daiser, S., Wandelt, K., Ertl, G.: Surf. Sci. 131 (1983) 61.
83N Nakanishi, S., Horiguchi, T.: Surf. Sci. 125 (1983) 605.
83N2 Niehus, H.: Surf. Sci. 130 (1983) 41.
83N3 Nakanishi, S., Horiguchi, T.: Surf. Sci. 133 (1983) 605.
83O Okano, T.: Jpn. J. Appl. Phys. 22 (1983) 1496.
83P Pradier, C.M., Berthier, Y., Margot, E., Oudar, J.: J. Microsc. Spectrosc. Electron. 8 (1983) 269.
83P2 Pfnür, H., Menzel, D.: J. Chem. Phys. 79 (1983) 2400.
83P3 Polanski, J., Sidorski, Z., Zuber, S.: Acta Phys. Pol. A 64 (1983) 377.
83P4 Papp, H.: Surf. Sci. 129 (1983) 205.
83P5 Phu, S.U., Bardolle, J., Bujor, M.: Surf. Sci. 129 (1983) 219.
83R Reed, A.P.C., Lambert, R.M., Foord, J.S.: Surf. Sci. 134 (1983) 689.
83R2 Rotermund, H.H., Jacobi, K.: Surf. Sci. 126 (1983) 32.
83S Stott, Z.T., Hughes, H.P.: Surf. Sci. 126 (1983) 455.
83S2 Sexton, B.A., Avery, N.R.: Surf. Sci. 129 (1983) 21.
83S3 Salmerón, M., Ferrer, S., Jazzar, M., Somorjai, G.A.: Phys. Rev. B 28 (1983) 6758.
83T Taylor, T.N., Campbell, C.T., Rogers, J.W.Jr., Ellis, W.P., White, J.M.: Surf. Sci. 134 (1983)
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83T2 Tochihara, H.: Surf. Sci. 126 (1983) 523.
83W Walldén, L.: Surf. Sci. 134 (1983) L513.
83W2 Wimmer, E., Freeman, A.J., Hiskes, J.R., Karo, A.M.: Phys. Rev. B 28 (1983) 3074.
83Z Zubenko, Yu.V., Ishmukhametov, M.B.: Fiz. Tverd. Tela 25 (1983) 1239 (Sov. Phys. Solid
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84A Argile, C., Barthes-Labrousse, M.-G., Rhead, G.E.: Surf. Sci. 138 (1984) 181.
84A2 Avery, N.R.: Surf. Sci. 146 (1984) 363.
84B Bange, K., Grider, D.E., Madey, T.E., Sass, J.K.: Surf. Sci. 137 (1984) 38.
84B2 Brown, A., Vickerman, J.C.: Surf. Sci. 140 (1984) 261.
84B3 Bozso, F., Arias, J., Hanrahan, C.P., Yates, J.T. Jr., Martin, R.M., Metiu, H.: Surf. Sci. 141
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84B4 Billy, J., Abon, M.: Surf. Sci. 146 (1984) L525.
84C Chen, Y.C., Cunningham, J.E., Flynn, C.P.: Phys. Rev. B 30 (1984) 7317.
84F Foord, J.S., Lambert, R.M.: Surf. Sci. 138 (1984) 258.
84G Godowski, P., Mroz, S.: Thin Solid Films 111 (1984) 129.
84G2 Griffiths, K., Jackman, T.E., Davies, J.A., Norton, P.R.: Surf. Sci. 138 (1984) 113.
84H Ho, P., White, J.M.: Surf. Sci. 137 (1984) 103.

84H2 Ho, P., White, J.M.: Surf. Sci. 137 (1984) 117.
84H3 Hrbek, J., dePaola, R.A., Hoffmann, F.M.: J. Chem. Phys. 81 (1984) 2818.
84H5 Horlacher, A., Smith R.A., Barker, R.A., Estrup, P.J.: Surf. Sci. 136 (1984) 327.
84K Klimesh, P., Meyer, G., Henzler, M.: Surf. Sci. 137 (1984) 79.
84K2 Kolaczkiewicz, J., Bauer, E.: Surf. Sci. 144 (1984) 477.
84K4 Kanash, O.V., Fedorus, A.G.: Zh. Eksp. Teor. Fiz. 86 (1984) 223; Sov. Phys. JETP (English
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84K5 Kiskinova, M., Pirug, G., Bonzel, H.P.: Surf. Sci. 136 (1984) 285.
84M Moog, E.R., Webb, M.B.: Surf. Sci. 148 (1984) 338.
84M2 Maurice, V., Peralta, L., Berthier, Y., Oudar, J.: Surf. Sci. 148 (1984) 623.
84N Norton, P.R., Griffiths, K., Bindner, P.E.: Surf. Sci. 138 (1984) 125.
84P Peebles, D.E., Peebles, H.C., White, J.M.: Surf. Sci. 136 (1984) 463.
84P3 Ping, C., Bolmont, D., Sebenne, C.A.: J. Phys. C: Solid State Phys. 17 (1984) 4897.
84P4 Peebles D.E., White, J.M.: Surf. Sci. 144 (1984) 512.
84P5 Peebles, D.E., White, J.M.: Surf. Sci. 148 (1984) 656.
84P6 Peebles, D.E., Peebles, H.C., White, J.M.: Surf. Sci. 136 (1984) 463.
84R Ruette, F., Blyholder, G., Head, J.D.: Surf. Sci. 137 (1984) 491.
84R2 Ritz, A., Spitzer, A., Lüth, H.: Appl. Phys. A 34 (1984) 31.
84R3 Rodway, D.: Surf. Sci. 147 (1984) 103.
84S Surnev, L., Tikhov, M.: Surf. Sci. 138 (1984) 40.
84S2 Seip, U., Tsai, M.-C., Christmann, K., Küppers, J., Ertl, G.: Surf. Sci. 139 (1984) 29.
84S3 Surnev, L., Bliznakov, G., Kiskinova, M.: Surf. Sci. 140 (1984) 249.
84S4 Sass, J.K., Bange, K., Dohl, R., Piltz, E., Unwin, R.: Ber. Bunsen-Ges. Phys. Chem. 88
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84S5 Shayegan, M., Cavallo, J.M., Glover, R.E., Park, R.L.: Phys. Rev. Lett. 53 (1984) 1578.
84S6 Spitzer, A., Lüth, H.: Phys. Rev. B 30 (1984) 3098.
84S7 Schaefer, J.E.: Surf. Sci. 148 (1984) 581.
84S8 Sass, J.K., Richardson, N.V.: Surf. Sci. 139 (1984) L204.
84S9 Sidorski, Z.: Appl. Phys. A 33 (1984) 213.
84S10 Sakisaka, Y., Miyano, T., Onchi, M.: Phys. Rev. B 30 (1984) 6849.
84S11 Sun, Y.-M., Luftman, H.S., White, J.M.: Surf. Sci. 139 (1984) 379.
84W Wandelt, K., Hulse, J.E.: J. Chem. Phys. 80 (1984) 1340.
85A Abon, M., Bertolini, J.C., Billy, J., Massardier, J., Tardy, B.: Surf. Sci. 162 (1985) 395.
85B Benndorf, C., Krüger, B.: Surf. Sci. 151 (1985) 271.
85B3 Behm, R.J., Ertl, G., Penka, V.: Surf. Sci. 160 (1985) 387.
85B4 Baldinger, T., Bechtold, E.: Surf. Sci. 159 (1985) 406.
85C Cousty, J., Riwan, R., Soukiassian, P.: J. Phys. (Paris) 46 (1985) 1693.
85D Derry, G.N., Ross, P.N.: J. Chem. Phys. 82 (1985) 2772.
85D2 Dolle, P., Alnot, M., Ehrhardt, J.J., Thomy, A., Cassuto, A.: Surf. Sci. 152-153 (1985) 620.
85D3 de Paola, R.A., Hrbek, J., Hoffmann, F.M.: J. Chem. Phys. 82 (1985) 2484.
85E Eyink, K.G., Lamartine, B.C., Haas, T.W.: Appl. Surf. Sci. 21 (1985) 29.
85F Feulner, P., Menzel, D.: Surf. Sci. 154 (1985) 465.
85F2 Foord, J.S., Lambert, R.M.: Surf. Sci. 161 (1985) 513.
85G Griffiths, K., Norton, P.R., Davies, J.A., Unertl, W.N., Jackman, T.E.: Surf. Sci. 152/153
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85H Hegde, R.I., Tobin, J., White, J.M.: J. Vac. Sci. Technol. A 3 (1985) 339.
85H2 Hochst, H., Colavita E., Fisher, G.B.: J. Vac. Sci. Technol. A 3 (1985) 1554.
85H3 Hegde, R.I., Greenlief, C.M., White, J.M.: J. Phys. Chem. 89 (1985) 2886.
85H4 Hrbek, J.: Surf. Sci. 164 (1985) 139.
85I Ismail, A., Ben Brahim, A., Palau, J.M., Lassabatere, L.: Surf. Sci. 162 (1985) 195.
85I2 Ishida, H., Shima, N., Tsukada, M.: Surf. Sci. 158 (1985) 438.
85K Kolaczkiewicz, J., Bauer, E.: Surf. Sci. 154 (1985) 357.
85K2 Koenders, L., Bartels, F., Ullrich, H., Mönch, W.: J. Vac. Sci. Technol. B 3 (1985) 1107.

85K3 Kojima, I., Orita, M., Miyazaki, E., Otani, S.: Surf. Sci. 160 (1985) 153.
85K4 Kamaratos, M., Papageorgopoulos, C.A.: Surf. Sci. 160 (1985) 451.
85K5 Kim, H., Okuno, K.: J. Vac. Sci. Technol. A 3 (1985) 2215.
85K7 Kiskinova, M., Rangelov, G., Surnev, L.: Surf. Sci. 150 (1985) 339.
85K9 Kennou, S., Ladas, S., Papageorgopoulos, C.: Surf. Sci. 164 (1985) 290.
85K10 Kennou, S., Ladas, S., Papageorgopoulos, C.: Surf. Sci. 152/153 (1985) 1213.
85L Lackey, D., Surman, M., Jacobs, S., Grider, D., King, D.A.: Surf. Sci. 152/153 (1985) 513.
85L2 Lee, J., Hanrahan, C.P., Arias, J., Martin, R.M., Metiu, H.: Surf. Sci. 161 (1985) L543.
85M Markert, K., Wandelt, K.: Surf. Sci. 159 (1985) 24.
85P Paffett, M.T., Campbell, C.T., Taylor, T.N., Srinivasan, S.: Surf. Sci. 154 (1985) 284.
85P2 Papageorgopoulos, C., Kamaratos, M.: Surf. Sci. 164 (1985) 353.
85P3 Paffett, M.T., Campbell, C.T., Taylor, T.N.: Langmuir 1 (1985) 741.
85P4 Parker, S.D.: Surf. Sci. 157 (1985) 261.
85P5 Park, Ch., Bauer, E., Poppa, H.: Surf. Sci. 154 (1985) 371.
85S Shayegan, M., Williams, E.D., Glover, R.E.III, Park, R.L.: Surf. Sci. 154 (1985) L239.
85S2 Strasser, G., Grunze, M., Golze, M.: J. Vac. Sci. Technol. A 3 (1985) 1562.
85S3 Sporken, R., Thiry, P.A., Pireaux, J.J., Caudano, R., Adnot, A.: Surf. Sci. 160 (1985) 443.
85S4 Smith, K.E., Henrich, V.E.: Phys. Rev. B 32 (1985) 5384.
85S5 Spitzer, A., Ritz, A., Lüth, H.: Surf. Sci. 152/153 (1985) 543.
85S6 Stroscio, J.A., Bare, S.R., Ho, W.: Surf. Sci. 154 (1985) 35.
85S7 Surnev, L., Rangelov, G., Bliznakov, G.: Surf. Sci. 159 (1985) 299.
85T Tatarenko, S., Alnot, M., Ehrhardt, J.J., Ducros, R.: Surf. Sci. 152-153 (1985) 471.
85T2 Taleb-Ibrahimi, A., Mercier, V., Sebenne, C.A., Bolmont, D., Chen, P.: Surf. Sci. 152-153
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85T3 Tatarenko, S., Alnot, M., Ducros, R.: Surf. Sci. 163 (1985) 249.
85T4 Taleb-Ibrahimi, A., Sebenne, C.A., Proix, F., Maigne, P.: Surf. Sci. 163 (1985) 478.
85W Woratschek, B., Sesselmann, W., Küppers, J., Ertl, G., Haberland, H.: Phys. Rev. Lett. 55
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86A Azizan, M., Nguyen Tan, T.A., Ciut, R., Baptist, R., Chauvet, G.: Surf. Sci. 178 (1986) 17.
86A2 Abon, M., Billy, J., Bertolini, J.C.: Surf. Sci. 171 (1986) L387.
86A3 Abon, M., Billy, J., Bertolini, J.C., Tardy, B.: Surf. Sci. 167 (1986) 1.
86A4 Aruge, T., Tochihara, H., Murata, Y.: Phys. Rev. B 34 (1986) 8237.
86B Benndorf, C., Nieber, B.: J. Vac. Sci. Technol. A 4 (1986) 1355.
86B2 Baier H.-U., Koenders, L., Mönch, W.: J. Vac. Sci. Technol. B 4 (1986) 1095.
86B3 Behner, H., Spiess, W., Wedler, G., Borgmann, D.: Surf. Sci. 175 (1986) 276.
86B4 Breitschafter, M.J., Umbach, E., Menzel, D.: Surf. Sci. 178 (1986) 725.
86B5 Behm, R.J., Brundle, C.R., Wandelt, K.: J. Chem. Phys. 85 (1986) 1061.
86C Chrzanowski, E., Bauer, E.: Surf. Sci. 173 (1986) 106.
86C2 Chelvayohan, M., Gomer, R.: Surf. Sci. 172 (1986) 337.
86D Döhl-Oelze, R., Stuve, E.M., Sass, J.K.: Solid State Commun. 57 (1986) 323.
86E Eiswirth, M., Ertl., G.: Surf. Sci. 177 (1986) 90.
86E2 Erley, W., Ibach, H.: Surf. Sci. 178 (1986) 565.
86E3 Eder, S., Markert, Jablonski, A., Wandelt, K.: Ber. Bunsenges. Phys. Chem. 90 (1986) 225.
86E4 Erley, W., Ibach, H.: Surf. Sci. 178 (1986) 565.
86F Feyer, N., Kiskinova, M., Pirug, G., Bonzel, H.P.: Appl. Phys. A 39 (1986) 209.
86F2 Freyer, N., Kiskinova, M., Pirug, G., Bonzel, H.P.: Surf. Sci. 166 (1986) 206.
86F3 Fusy, J., Ducros, R.: Surf. Sci. 176 (1986) 157.
86F4 Foord, J.S., Lambert, R.M.: Surf. Sci. 169 (1986) 327.
86H Hendrickx, H.A.C.M., Nieuwenhuys, B.E.: Surf. Sci. 175 (1986) 185.
86H2 Herlt, H.-J., Bauer, E.: Surf. Sci. 175 (1986) 336.
86H3 Hrbek, J.: J. Phys. Chem. 90 (1986) 6217.
86H4 Harrison, K., Lambert, R.M., Prince, R.H.: Surf. Sci. 176 (1986) 530.

86H5 Hu, Z.P., Wu, N.J., Ignatiev, A.: Surf. Sci. 177 (1986) L956.
86H6 Hardegree, E.L., Ho, P., White, J.M.: Surf. Sci. 165 (1986) 488.
86I Inoue, M., Ueda, K.: Jpn. J. Appl. Phys. Part 1, 25 (1986) 802.
86I2 Ismail, A., Palau, J.M., Lassabatere L.: J. Appl. Phys. 60 (1986) 1730.
86J3 Jablonski, A., Eder, S., Markert, K., Wandelt, K.: J. Vac. Sci. Technol. A 4 (1986) 1510.
86K Kirstein, W., Kruger, B., Thieme, F.: Surf. Sci. 176 (1986) 505.
86K2 Kolaczkiewicz, J.. Bauer, E.: Surf. Sci. 175 (1986) 487.
86K3 Krüger, B., Benndorf, C.: Surf. Sci. 178 (1986) 704.
86M Mroz, S., Bauer, E.: Surf. Sci. 169 (1986) 394.
86M2 Mullins, D.R., White, J.M., Luftman, H.S.: Surf. Sci. 167 (1986) 39.
86M3 Miyano, T., Sakisaka, Y., Komeda, T., Onchi, M.: Surf. Sci. 169 (1986) 197.
86N Nishigaki, S., Komatsu, T., Arimoto, M., Sugihara, M.: Surf. Sci. 167 (1986) 27.
86N2 Norton, P.R., Bindner, P.E., Jackman, T.E.: Surf. Sci. 175 (1986) 313.
86N3 Norton, P.R., Bindner, P.E.: Surf. Sci. 169 (1986) L259.
86O Oellig, E.M., Miranda, R.: Surf. Sci. 177 (1986) L947.
86P Paffett, M.T., Campbell, C.T., Taylor, T.N.: J. Chem. Phys. 85 (1986) 6176.
86P2 Parker, S.D., Dobson, P.J.: Surf. Sci. 171 (1986) 267.
86P3 Parker, S.D., Rhead, G.E.: Surf. Sci. 167 (1986) 271.
86S Sendecki, S.: Surf. Sci. 165 (1986) 402.
86S2 Schönhense, G.: Appl. Phys. A 41 (1986) 39.
86U Uram, K.J., Ng, L., Yates Jr., J.T.: Surf. Sci. 177 (1986) 253.
86V Vladimirov, G.G., Rump, G.A.: Poverkhnost N10 (1986) 61.
87A Alnot, M., Gorodetskii, V., Cassuto, A., Ehrhardt, J.J.: Thin Solid Films 151 (1987) 251.
87A2 Attard, G.A., King, D.A.: Surf. Sci. 188 (1987) 589.
87A3 Andriamanantenaosa, I., Lacharme, J.P., Sebenne, C.A.: Surf. Sci. 189-190 (1987) 563.
87A4 Argile, C., Rhead, G.E.: Thin Solid Films 152 (1987) 546.
87B Bartos, B., Freund, H.-J., Kuhlenbeck, H., Neumann, M., Lindner, H., Müller, K.: Surf. Sci.
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87B2 Bange, K., Madey, T.E., Sass, J.K., Stuve, E.M.: Surf. Sci. 183 (1987) 334.
87B3 Bonnet, J., Soonckindt, L., Ismail, A., Lassabatere, L.: Thin Solid Films 151 (1987) 103.
87B4 Benndorf, C., Nieber, B., Krüger, B.: Surf. Sci. 189-190 (1987) 511.
87B5 Bucci, J.V., Swirbel, T.J., Vook, R.W., Schwarz, J.A.: Scanning Microscopy 1 (1987) 1001.
87B6 Berkó, A., Solymosi, F.: Surf. Sci. 187 (1987) 359.
87B7 Barnes, C.J., Asonen, H., Salokatve, A., Pessa, M.: Surf. Sci. 184 (1987) 163.
87C Chelvayohan, M., Gomer, R.: Surf. Sci. 186 (1987) 412.
87C2 Christmann, K., Ehsasi, M.: Appl. Phys. A 44 (1987) 87.
87D de Paola, R.A., Hoffmann, F.M., Heskett, D., Plummer, E.W.: Phys. Rev. B 35 (1987) 4236.
87D2 Dubois, L.H., Zegarski, B.R., Luftman, H.S.: J. Chem. Phys. 87 (1987) 1367.
87E Engstrom, J.R., Tsai, W., Weinberg, W.H.: J. Chem. Phys. 87 (1987) 3104.
87F Foord, J.S., Lambert, R.M.: Surf. Sci. 185 (1987) L483.
87G Gonchar, F.M., Medvedev, V.K., Smereka, T.P., Lozovyi, Ya.B., Babkin, G.V.: Fiz. Tverd.
87H Hohlfeld, A., Sunjic, M., Horn, K.: J. Vac. Sci. Technol. A 5 (1987) 679.
87I Inoue, M.: Jpn. J. Appl. Phys. Part 1, 26 (1987) 300.
87J Jackman, T.E., Griffiths, K., Unertl, W.N., Davies, J.A., Gürtler K.H., Harrington, D.A.,
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87J2 Jacobi, K.: Surf. Sci. 192 (1987) 499.
87K Kalis, T., Belyaeva, M.E., Sergeev, S.I.: Elektrokhimiya 23 (1987) 126. (Sov.
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87K2 Kiskinova, M.: Surf. Sci. 182 (1987) 150.
87L Ladas, S., Kennou, S., Kamaratos, M., Foulias, S.D., Papageorgopoulos, C.: Surf. Sci.
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87N Nöbl, C., Benndorf, C.: Surf. Sci. 182 (1987) 499.
87N2 Nix, R.M., Lambert, R.M.: Surf. Sci. 186 (1987) 163.

87O Onellion, M., Eskine, J.L.: Phys. Rev. B 36 (1987) 4495.

87O2 Ortega, J.E., Oellig, E.M., Ferron, J., Miranda, R.: Phys. Rev. B 36 (1987) 6213.
87P Park, C., Bauer, E., Poppa, H.: Surf. Sci. 187 (1987) 86.
87P2 Paul, J.: J. Vac. Sci. Technol. A 5 (1987) 664.
87P3 Patterson, C.H., Lambert, R.M.: Surf. Sci. 187 (1987) 339.
87R Rangelov, G., Surnev, L.: Surf. Sci. 185 (1987) 457.
87S Surnev, L.,Rangelov, G., Kiskinova, M.: Surf. Sci. 179 (1987) 283.
87S2 Stenborg, A., Bauer, E.: Surf. Sci. 185 (1987) 394.
87S3 Stenborg, A., Bauer, E.: Surf. Sci. 189-190 (1987) 570.
87S4 Stenborg, A., Bauer, E.: Phys. Rev. B 36 (1987) 5840.
87S5 Steinberger, I.T., Wandelt, K.: Phys. Rev. Lett. 58 (1987) 2494.
87T Tompa, G.S., Seidl, M., Ermler, W.C., Carr, W.E.: Surf. Sci. 185 (1987) L453.
87W Wandelt, K., in: Wißmann, P. (ed.), “Chemisorption on metal films”, Elsevier, 1990, p. 280.
88A Astaldi, C., Jacobi, K.: Surf. Sci. 200 (1988) 15.
88A2 Argile, C., Rhead, G.E.: Surf. Sci. 203 (1988) 175.
88B Beckerle, J.D., Yang, Q.Y., Johnson A.D., Ceyer, S.T.: Surf. Sci. 195 (1988) 77.
88B2 Bourgeois, S., Poirault, R., Plociennik J.-M., Randriamanivo, A.: J. Microsc. Spectrosc.
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88B3 Berlowitz, P.J., Houston, J.E., White, J.M., Goodman, D.W.: Surf. Sci. 205 (1988) 1.
88D Duszak, R., Prince, R.H.: Surf. Sci. 205 (1988) 143.
88E Ehsasi, M., Christmann. K.: Surf. Sci. 194 (1988) 172.
88F Faldt, A., Kristensson, D.K., Myers, H.P.: Phys. Rev. B 37 (1988) 2682.
88F2 Frick, B., Jacobi, K.: Phys. Rev. B 37 (1988) 4408.
88G Griffiths, K.: J. Vac. Sci. Technol. A 6 (1988) 210.
88G2 Gonchar, F.M., Smereka, T.P., Stepanovskii, S.I., Babkin, G.V.: Fiz. Tverd. Tela 30 (1988)
88G3 Gidley, D.W., Koymen, A.R., Capehart, T.W.: Phys. Rev. B 37 (1988) 2465.
88H Harrington, D.A., Norton, P.R.: Surf. Sci. 195 (1988) L135.
88H2 Hoffmann, F.M., Rocker, G., Tochihara, H., Martin, R.M., Metiu, H.: Surf. Sci. 205 (1988) 397.
88H3 Haase, G., Asscher, M., Linke, U.: Appl. Surf. Sci. 35 (1988) 1.
88H4 He, J.-W., Harrington, D.A., Griffiths K., Norton, P.R.: Surf. Sci. 198 (1988) 413.
88H5 He, J.-W., Memmert, U., Griffiths, K., Lennard, W.N., Norton, P.R.: Surf. Sci. 202 (1988)
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88H6 Hagaus, P.L., Guo, X., Chorkendorff, I., Winkler, A., Siddiqui, H., Yates, J.T.: Surf. Sci. 203
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88I Imbihl R., Ladas, S., Ertl, G.: Surf. Sci. 206 (1988) L903.
88J Jacobi, K.: Phys. Rev. B 38 (1988) 5869.
88J2 Jakob, P., Menzel, D.: Surf. Sci. 201 (1988) 503.
88J3 Jaegermann, W.: Ber. Bunsen-Ges. Phys. Chem. 92 (1988) 537.
88J4 Jacobi, K.: Phys. Rev. B 38 (1988) 6291.
88K Kiskinova, M., Tikhov, M., Bliznakov, G.: Surf. Sci. 204 (1988) 35.
88K2 Kiskinova, M., Szabo, A., Yates Jr., J.T.: J. Chem. Phys. 89 (1988) 7599.
88L Lin, J.C., Shamir, N., Gomer, R.: Surf. Sci. 206 (1988) 61.
88M Memmert, U., Norton, P.R.: Surf. Sci. 203 (1988) L689.
88M2 Mate, C.M., Kao, Ch.-T., Somorjai, G.A.: Surf. Sci. 206 (1988) 145.
88N Nakanishi, S., Sasaki, K.: Surf. Sci. 194 (1988) 245.
88N2 Netzer, F.P., Rangelov, G., Rosina, G., Saalfeld, H.B.: J. Chem. Phys. 89 (1988) 3331.
88N3 Netzer, F.P., Rangelov, G., Rosina, G., Saalfeld, H.B., Neumann, M., Lloyd, D.R.: Phys.
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88N4 Nishigaki, S., Ohara, M., Murakami, A., Fukui, S., Matsuda, S.: Appl. Surf. Sci. 35 (1988)
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88N5 Nix, R.M., Judd, R.W., Lambert, R.M.: Surf. Sci. 203 (1988)307.
88O Onishi, H., Aruga, T., Egawa, C., Iwasawa, Y.: Surf. Sci. 193 (1988) 33.
88P Park, C.: Surf. Sci. 203 (1988) 395.

88P2 Packard, W.E., Webb, M.B.: Surf. Sci. 195 (1988) 371.
88R Rosenzweig, Z., Asscher, M.: Surf. Sci. 204 (1988) L732.
88R2 Rump, G.A., Vladimirov, G.G., Magkoev, T.T.: Poverkhnost N3 (1988) 54.
88S Silvestre, C., Shayegan, M.: Phys. Rev. B 37 (1988) 10432.
88S2 Surnev, L., Xu, Z., Yates Jr., J.T.: Surf. Sci. 201 (1988) 14.
88T Tikhov, M., Bauer, E.: Surf. Sci. 203 (1988) 423.
88T2 Tysoe, W.T., Lambert, R.M.: Surf. Sci. 199 (1988) 1.
88U Ueda, K., Mega, T.: Jpn. J. Appl. Phys. Part 1, 27 (1988) 2227.
88V Vook, R.W., Swirbel, T.J., Bucci, J.V.: J. Vac. Sci. Technol. A 6 (1988) 1710.
88V2 Vook, R.W., Swirbel, T.J., Chao, S.S.: Appl. Surf. Sci. 33-34 (1988) 220.
88W Windham, R.G., Bartram, M.E., Koel, B.E.: J. Chem. Phys. 92 (1988) 2862.
88X Xu, Y. : Proceedings of the Chinese-Japanese Joint Seminar on Vacuum and Surface
Analysis (VASA-85). Vacuum and Surface Analysis. Vol. 1. World Scientific. (1988) 192.
88Z Zhou, X.-L., Zhu, X.-Y., White, J.M.: Surf. Sci. 193 (1988) 387.
89A Alnot, M., Ehrhardt, J.J., Barnard J.A.: Surf. Sci. 208 (1989) 285.
89B Bermudez, V.M., Glass, A.S.: J. Vac. Sci. Technol. A 7 (1989) 1961.
89B2 Bermudez, V.M.: J. Appl. Phys. 66 (1989) 6084.
89B3 Berlowitz, P.J., Shinn, N.D.: Surf. Sci. 209 (1989) 345.
89B4 Blass, P.M., Zhou, X.-L., White, J.M.: Surf. Sci. 215 (1989) 74.
89C Cousty, J., Papageorgopoulos, C.A., Riwan, R.: Surf. Sci. 223 (1989) 479.
89D Dolle, P., Tommasini, M., Jupille, J.: Surf. Sci. 211/212 (1989) 904.
89E Ernst-Vidalis, M.-L., Bauer, E.: Surf. Sci. 215 (1989) 378.
89E2 Enta, Y., Kinoshita, T., Suzuki, S., Kono, S.: Phys. Rev. B 39 (1989) 1125.
89E3 Ernst, K.H., Christmann, K.: Surf. Sci. 224 (1989) 277.
89F Fusy, J., Ducros, R.: Surf. Sci. 214 (1989) 337.
89G Gonchar, F.M., Medvedev, V.K., Smereka, T.P., Savichev, V.V.: Fiz. Tverd. Tela 31 (1989)
89G2 Glander, G.S., Webb, M.B.: Surf. Sci. 222 (1989) 64.
89G3 Glander, G.S., Webb, M.B.: Surf. Sci. 224 (1989) 60.
89H He, J.-W., Memmert, U., Norton, P.R.: J. Chem. Phys. 90 (1989) 5088.
89H2 Hohlfeld, A., Horn, K.: Surf. Sci. 211/212 (1989) 844.
89J Johnson, B.G., Berlowitz, P.J., Goodman, W.D., Bartholomew, C.H.: Surf. Sci. 217 (1989) 13.
89J2 Jacobi, K., Astaldi, C., Geng, P., Bertolo, M.: Surf. Sci. 223 (1989) 569.
89J3 Jaffey, D.M., Gellman, A.J., Lambert, R.M.: Surf. Sci. 214 (1989) 407.
89K Kiss, J., Klivenyi, G., Revesz, K., Solymosi, F.: Surf. Sci. 223 (1989) 551.
89L Lauth, G., Solomun, T., Hirschwald, W., Christmann, K.: Surf. Sci. 210 (1989) 201.
89L2 Lauth, G., Schwarz, E., Christmann, K.: J. Chem. Phys. 91 (1989) 3729.
89M Memmert, U., He, J.-W., Griffiths, K., Lennard, W.N., Norton, P.R., Richardson N.V.,
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89M2 Memmert, U., Bushby, S.J., Norton, P.R.: Surf. Sci. 219 (1989) 327.
89M3 Maeda Wong, T., Heskett, D., Dinardo, N.J., Plummer, E.W.: Surf. Sci. 208 (1989) L1.
89O Oral, B., Kothari, R., Vook, R.W.: J. Vac. Sci. Technol. A 7 (1989) 2020.
89P Pache, T., Steinruck, H.-P., Huber, W., Menzel, D.: Surf. Sci. 224 (1989) 195.
89P2 Parker, D.H., Bartram, M.E., Koel, B.E.: Surf. Sci. 217 (1989) 489.
89R Ruckman, M.W., Jiang, L.Q., Strongin, M.: Surf. Sci. 221 (1989) 144.
89R2 Ramsey, M.G., Rosina, G., Netzer, F.P., Saalfeld, H.B., Lloyd, D.R.: Surf. Sci. 217 (1989)
140.
89S Sendecki, S.: Surf. Sci. 213 (1989) 430.
89S2 Shamir, N., Lin, J.C., Gomer, R.: Surf. Sci. 214 (1989) 74.
89S3 Shamir, N., Gomer, R.: Surf. Sci. 216 (1989) 49.
89Y Ying, Z.C., Ho, W.: J. Chem. Phys. 91 (1989) 5050.
89Z Zhou, X.-L., Solymosi, F., Blass, P.M., Cannon, K.C., White, J.M.: Surf. Sci. 219 (1989)
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89Z2 Zhou, X.-L., White, J.M.: Surf. Sci. 221 (1989) 534.

89Z3 Zhou, X.-L., White, J.M., Koel, B.E.: Surf. Sci. 218 (1989) 201.
90A Azizan, M., Nguyen Tan, T.A., Veuillen, J.Y.: Vacuum 41 (1990) 1132.
90B Bertolo, M., Jacobi, K.: Surf. Sci. 226 (1990) 207.
90C Callen, B.W., Griffiths, K., Memmert, U., Harrington, D.A., Bushby, S.J., Norton P.R.: Surf.
Sci. 230 (1990) 159.
90D Domenicucci, A., Vook, R.W.: Thin Solid Films 193-194 (1990) 227.
90D2 Duszak, R., Prince, R.H.: Surf. Sci. 226 (1990) 33.
90E Ehsasi, M., Rezaie-Serej, S., Block, J.H., Christmann, K.: J. Chem. Phys. 92 (1990) 7596.
90H Höchst, H., Engelhardt, M.A.: Proc. SPIE Int. Soc. Opt. Eng. 1190 (1990) 17.
90H2 He, J.-W., Norton, P.R.: Surf. Sci. 230 (1990) 150.
90H3 Hollering, R.W.J., Dijkamp, D., Lindelauf, H.W.L., van der Heide, P.A.M., Krijn, M.P.C.M.:
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90H4 He, J.-W., Norton, P.R.: Surf. Sci. 238 (1990) 95.
90K Kolaczkiewicz, J.: Surf. Sci. 231 (1990) 103.
90K2 Kolaczkiewicz, J., Hochól, M., Zuber, S.: Surf. Sci. 247 (1991) 284.
90L Li, X.Q.D., Vanselow, R.: Surf. Sci. 236 (1990) L369.
90M Magnusson, K.O., Reihl, B.: Phys. Rev. B 41 (1990) 12071.
90N Nieber, B., Benndorf, C.: Surf. Sci. 235 (1990) 129.
90N2 Nishigaki, S., Matsuda, S., Sasaki, T., Kawanishi, N., Ikeda, Y., Takeda, H.: Surf. Sci. 231
(1990) 271.
90P Puckrin, E., Slavin, A.J.: Phys. Rev. B 41 (1990) 4970.
90R Ray, K.B., Hannon, J.B., Plummer, E.W.: Chem. Phys. Lett. 171 (1990) 469.
90R2 Rosenzweig, Z., Asscher, M., Wittenzellner, C.: Surf. Sci. 240 (1990) L583.
90R3 Reihl, B., Magnusson, K.O.: Phys. Rev. B 42 (1990) 11839.
90S Shinn, N.D.: Phys. Rev. B 41 (1990) 9771.
90S2 Solymosi, F., Berko, A., Revesz, K.: Surf. Sci. 240 (1990) 50.
90S3 Singh, N.K., Jones, R.G.: Surf. Sci. 232 (1990) 229.
90T Tikhov, M., Bauer, E.: Surf. Sci. 232 (1990) 73.
90Z Zhao, Y.B., Gomer, R.: Surf. Sci. 239 (1990) 189.
90Z2 Zhou, X.-L., Castro, M.E., White, J.M.: Surf. Sci. 238 (1990) 215.
91A Asscher, M., Rosenzweig, Z.: J. Vac. Sci. Technol. A 9 (1991) 1913.
91B Bhave, A.S., Kanitkar, P.L.: J. Phys. D - Appl. Phys. 24 (1991) 454.
91B2 Borgmann, D., Kiessling, W., Stadelmann, M., Wedler, G.: Surf. Sci. 251-252 (1991) 831.
91B4 Bugyi, L., Solymosi, F.: Surf. Sci. 258 (1991) 55.
91C Cherif, S.M., Lacharme, J.-P., Sebenne, C.A.: Surf. Sci. 243 (1991) 113.
91C2 Cherif, S.M., Lacharme, J.-P., Sebenne, C.A.: Surf. Sci. 251-252 (1991) 737.
91C3 Chrost, J., Fick, D.: Surf. Sci. 251-252 (1991) 78.
91D Dworecki, Z.: Surf. Sci. 247 (1991) 279.
91E Ernst, K.H., Campbell, C.T.: Surf. Sci. 259 (1991) L736.
91F Fusy, J., Alnot, M., Abouelaziz, H., Ehrhardt, J.J.: Surf. Sci. 252/252 (1991) 573.
91H Hansen, W.: Thesis, TU Berlin, Germany (1991).
91H2 Hölzl, J., Fritsche, L.: Surf. Sci. 247 (1991) 226.
91H3 Houston, J.E.: Surf. Sci. 255 (1991) 303.
91K Kleint, C., Halim, S.M.A.E.: Surf. Sci. 247 (1991) 375.
91K2 Kolaczkiewicz, J., Bauer, E.: Phys. Rev. B 44 (1991) 5779.
91K3 Kolaczkiewicz, J., Hochól, M., Zuber, S.: Surf. Sci. 247 (1991) 284.
91K4 Kennou, S., Kamaratos M., Papageorgopoulos, C.A.: Surf. Sci. 256 (1991) 312.
91L Lindgren, S.A., Walldén, L.: Surf. Sci. 257 (1991) L619.
91M2 Medvedev, V.K., Smereka, T.P., Stepanovskii, S.I., Gonchar, F.M., Kamenetskii, R.R.: Fiz.
Tverd. Tela 33 (1991) 3603; Sov. Phys. Solid State (English Transl.) 33 (1991) 2028.
91N Nichtl-Pecher, W., Stammler, W., Heinz, K., Müller, K.: Phys. Rev. B 43 (1991) 6946.
91O Okada, M., Tochihara, H., Murata, Y.: Surf. Sci. 245 (1991) 380.
91P Pirug, G., Ritke, C., Bonzel, H.P.: Surf. Sci. 241 (1991) 289.
91P2 Pennemann, B., Oster, K., Wandelt, K.: Surf. Sci. 249 (1991) 35.

91P3 Pennemann, B., Oster, K., Wandelt, K.: Surf. Sci. 251-252 (1991) 877.
91P4 Pleshkov, V.A., Shakirova, S.A., Rump, G.A.: Poverkhnost Fizika Khimiya Mekhanika
(Phys. Chem. Mech. Surfaces (English Transl.) 6 (1991) 2384).
91P5 Papageorgopoulos, C.A., Kamaratos, M., Kennou, S., Vlachos, D.: Surf. Sci. 251-252 (1991)
1057.
91P6 Pirug, G., Ritke, C., Bonzel, H.P.: Surf. Sci. 257 (1991) 50.
91P7 Pope, T.D., Bushby, S.J., Griffiths, K., Norton, P.R.: Surf. Sci. 258 (1991) 101.
91S Sass, J.K., Lackey, D., Schott, J., Straehler, B.: Surf. Sci. 247 (1991) 239.
91S2 Sokolowski, M., Koch, T., Pfnür, H.: Surf. Sci. 243 (1991) 261.
91T Tang, D., McIlroy, D., Shi, X., Su, C., Heskett, D.: Surf. Sci. 255 (1991) L497.
91T2 Tikhov, M., Boishin, G., Surnev, L.: Surf. Sci. 241 (1991) 103.
91T3 Taylor, T.N., Muenchhausen, R.E., Hoffbauer, M.A.: Surf. Sci. 243 (1991) 65.
91Z Zhang, Y., Slavin, A.J.: J. Vac. Sci. Technol. A 9 (1991) 1784.
91Z2 Zhuang Sh., Ji, M., Wu, J., Wandelt, K.: Surf. Sci. 251-252 (1991) 759.
91Z3 Zhou, X.-L., White, J.M.: Surf. Sci. 241 (1991) 244.
91Z4 Zhang, C.-S., Flinn, B.J., Mitchell, I.V., Norton, P.R.: Surf. Sci. 245 (1991) 373.
92A Ahner, J., Effendy, A., Wassmuth, H.-W.: Surf. Sci. 269-270 (1992) 372.
92A2 Argile, C., Rhead, G.E.: Surf. Sci. 279 (1992) 244.
92B Bakhtizin, R.Z., Suvorov, A.L., Zaripov, R.F.: Acta Phys. Pol. A 81 (1992) 247.
92B2 Benndorf, C., Mundt, C.: J. Vac. Sci. Technol. A 10 (1992) 3026.
92B3 Bertolo, M., Jacobi, K.: Surf. Sci. 265 (1992) 1.
92B4 Boishin, G., Surnev, L.: Surf. Sci. 273 (1992) 301.
92C Cherif, S.M., Lacharme, J.-P., Sebenne, C.A.: Surf. Sci. 274 (1992) 257.
92C2 Callen, B.W., Griffiths, K., Kasza, R.V., Jensen, M.B., Thiel, P.A., Norton, P.R.: J. Chem.
Phys. 97 (1992) 3760.
92E Esser, N., Benne, I., Srama, R., Richter, W.: Surf. Sci. 269-270 (1992) 1037.
92E2 Ernst-Vidalis, M.-L., Papageorgopoulos, C., Stawinski, U., Bauer, E.: Phys. Rev. B 45 (1992)
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92J Jo, S.K., White, J.M.: Surf. Sci. 261 (1992) 111.
92J2 Janssens, T., Castro, G.R., Busse, H., Schneider, U., Wandelt, K.: Surf. Sci. 269/270 (1992)
664.
92K Kiss, J., Alberas, D.J., White, J.M.: Surf. Sci. 275 (1992) 82.
92L Lamouri, A., Krainsky, I.L.: Surf. Sci. 278 (1992) 286.
92M Mazina-Ngokoudi, M., Argile, C.: Surf. Sci. 262 (1992) 307.
92M2 Mroz, S., Stachnik, B.: Acta Phys. Pol. A 81 (1992) 233.
92M3 Michel, E.G., Pervan, P., Castro, G.R., Miranda, R., Wandelt, K.: Phys. Rev. B 45 (1992)
11811.
92M4 Mullins, D.R., Lyman, P.F., Overbury, S.H.: Surf. Sci. 277 (1992) 64.
92M5 Mayer, T., Klein, A., Lang, O., Pettenkofer, C., Jaegermann, W.: Surf. Sci. 269/270 (1992)
909.
92N Nicklin, C.L., Binns, C., Norris, C., McCluskey, P., Barthes-Labrousse, M.-G.: Surf. Sci.
269-270 (1992) 700.
92O Ortega, J.E., Miranda, R.: Appl. Surf. Sci. 56-58 (1992) 211.
92O2 Ou, E.C., Young, P.A., Norton, P.R.: Surf. Sci. 277 (1992) 123.
92P Polanski, G., Toennies, J.P.: Surf. Sci. 260 (1992) 250.
92R Roman, E.L., de Segovia, J.L., Kurtz, R.L., Stockbauer, R., Madey, T.E.: Surf. Sci. 273
(1992) 40.
92R2 Reihl, B., Sorensen, S.L., Dudde, R., Magnusson, K.O.: Surf. Sci. 269/270 (1992) 1005.
92S Shern, C.S.: Surf. Sci. 264 (1992) 171.
92S2 Sander, M., Imbihl, R., Schuster, R., Barth, J.V., Ertl, G.: Surf. Sci. 271 (1992) 159.
92S3 Shen, G.L., Casanova, R., Thornton, G.: Vacuum 43 (1992) 1129.
92S4 Surnev, S.: Surf. Sci. 278 (1992) 375.
92S5 Shakirova, S.A., Pleshkov, V.A., Rump, G.A.: Surf. Sci. 279 (1992) 113.
92S6 Shern, C.S.: Chinese J. Phys. 30 (1992) 841.

92S7 Shi, H., Jacobi, K.: Surf. Sci. 278 (1992) 281.
92S8 Shinn, N.D.: Surf. Sci. 278 (1992) 157.
92W Wu, K. et al.: Surf. Sci. 264 (1992) 249.
92W2 Walter, W.K., Jones, R.G.: Surf. Sci. 264 (1992) 391.
92X Xi, M., Bent, B.E.: Surf. Sci. 278 (1992) 19.
92Y Gong, Y.-M., Leng, R.-H.: Solid State Commun. 84 (1992) 1085.
92Z2 Zadorozhnyl, L.P., Medvedev, V.K., Smereka, T.P., Gonchar, F.M.: Fiz. Tverd. Tela 34
(1992) 1051; Sov. Phys. Solid State (English Transl.) 34 (1992) 561.
92Z3 Zhang, Z., Henrich, V.E.: Surf. Sci. 277 (1992) 263.
92Z4 Zhao, Y.B., Gomer, R.: Surf. Sci. 271 (1992) 85.
93A Atli, A., Abon, M., Bertolini, J.C.: Surf. Sci. 287/288 (1993) 110.
93B2 Brosseau, R., Brustein, M.R., Ellis, T.H.: Surf. Sci. 294 (1993) 243.
93B3 Bushby, S.J., Callen, B.W., Griffiths, K., Esposto, F.J., Timsit, R.S., Norton, P.R.: Surf. Sci.
298 (1993) L181.
93C Chakarian, V., Shuh, D.K., Yarmoff, J.A., Hakansson, M.C., Karlsson, U.O.: Surf. Sci. 296
(1993) 383.
93F Fan, W.C., Ignatiev, A.: Surf. Sci. 296 (1993) 352.
93G Godfrey, D.C., Hayden, B.E., Murray, A.J., Parsons, R., Pegg, D.J.: Surf. Sci. 294 (1993) 33.
93H Hamawi, A., Walldén, L.: Surf. Sci. 285 (1993) 93.
93J Johansson, L.S.O., Reihl, B.: Phys. Rev. B 47 (1993) 1401.
93K Kastanas, G.N., Koel, B.E.: Appl. Surf. Sci. 64 (1993) 235.
93K2 Kadodwala, M., Jones, R.G.: J. Vac. Sci. Technol. A 11 (1993) 2019.
93K3 Klingenberg, B., Grellner, F., Borgmann, D., Wedler, G.: Surf. Sci. 296 (1993) 374.
93L Leschik, G., Courths, R., Wern, H.: Surf. Sci. 294 (1993) 355.
93M Mundt, C., Benndorf, C.: Surf. Sci. 287-288 (1993) 119.
93M2 Ma, P., Slavin, A.J.: J. Vac. Sci. Technol. A 11 (1993) 2003.
93N Nienhaus, H., Mönch, W.: Appl. Surf. Sci. 66 (1993) 632.
93N2 Neumann, A., Christmann, K., Solomun, T.: Surf. Sci. 287-288 (1993) 593.
93O Ota, K., Usami, S.: Surf. Sci. 287-288 (1993) 99.
93O2 Over, H., Hertel, T., Bludau, H., Pflanz, S., Ertl, G.: Phys. Rev. B 48 (1993) 5572.
93P Pan, J.-M., Diebold, U., Zhang, L., Madey, T.E.: Surf. Sci. 295 (1993) 411.
93R Radnik, J., Gitmans, F., Pennemann, B., Oster, K., Wandelt, K.: Surf. Sci. 287-288 (1993)
330.
93R2 Rotermund, H.H., Lauterbach, J., Haas, G.: Appl. Phys. A 57 (1993) 507.
93R3 Ruckman, M.W., Xia, B., Qiu, S.L.: Phys. Rev. B 48 (1993) 15457.
93S Surnev, S.: Surf. Sci. 282 (1993) 10.
93S2 Schmidt, M., Wolter, H., Schick, M., Kalki, K., Wandelt, K.: Surf. Sci. 287-288 (1993) 983.
93S3 Sprunger, P.T., Plummer, E.W.: Phys. Rev. B 48 (1993) 14436.
93S4 Shi, X., Tang, D., Heskett, D., Tsuei, K.-D., Ishida, H., Morikawa, Y., Terakura, K.: Phys.
Rev. B 47 (1993) 4014.
93S5 Shi, X., Tang, D., Heskett, D., Tsuei, K.-D., Ishida, H., Morikawa, Y.: Surf. Sci. 290 (1993)
69.
93S6 Su, C., Shi, X., Tang, D., Heskett, D., Tsuei, K.-D.: Phys. Rev. B 48 (1993) 12146.
93S7 Stolz, H., Höfer, M., Wassmuth, H.-W.: Surf. Sci. 287/288 (1993) 564.
93S8 Solymosi, F., Révész, K.: Surf. Sci. 280 (1993) 38.
93T Troost, D., Koenders, L., Mönch, W.: Appl. Surf. Sci. 66 (1993) 619.
93T2 Tang, D., Su, C., Heskett, D.: Surf. Sci. 295 (1993) 427.
93V van Slooten, U., Koppers, W.R., Bot, A., van Pinxteren, H.M., Moutinho, A.M.C., Frenken,
J.W.M., Kleyn, A.W.: J. Phys. Condens. Matter 5 (1993) 5411.
93W Weinelt, M., Zebisch, P., Steinruck, H.-P.: Surf. Sci. 287-288 (1993) 471.
93W2 Weinelt, M., Zebisch, P., Steinrück, H.-P.: Chem. Phys. 177 (1993) 321.
93W3 Wolter, H., Schmidt, M., Wandelt, K.: Surf. Sci. 298 (1993) 173.

94A Atli, A., Abon, M., Beccat, P., Bertolini, J.C., Tardy, B.: Surf. Sci. 302 (1994) 121.
94B Blaszczyszynowa, M., Blaszczyszyn, R., Ciszewski, A.: Surf. Sci. 304 (1994) 325.
94B2 Bönicke, I., Kirstein, W., Spinzig, S., Thieme, F.: Surf. Sci. 313 (1994) 231.
94B3 Bönicke, I. A., Kirstein, W., Thieme, F.: Surf. Sci. 307-309 (1994) 177.
94B4 Bender, M., Al-Shamery, K., Freund, H.-J.: Langmuir 10 (1994) 3081.
94E Ernst, K.-H., Schwarz, E., Christmann, K.: J. Chem. Phys. 101 (1994) 5388.
94E2 Eckhardt, M., Kleine, H., Fick, D.: Surf. Sci. 319 (1994) 219.
94F Fischer, N., Schuppler, S., Fauster, Th., Steinmann, W.: Surf. Sci. 314 (1994) 89.
94F2 Fallavier, M., et al.: Surf. Sci. 311 (1994) 24.
94G Grellner, F., Klingenberg, B., Borgmann, D., Wedler, G.: Surf. Sci. 312 (1994) 143.
94G2 Gensterblum, B., Hevesi, K., Han, B.-Y., Yu, L.-M., Pireaux, J.-J., Thiry, P.A., Caudano, R.,
Lucas, A.-A., Bernaerts, D., Amelinckx, S., Van Tendeloo, G., Bendele, G., Buslaps, T.,
Johnson, R.L., Foss, M., Feidenhans’l, R., Le Lay, G.: Phys. Rev. B 50 (1994) 11981.
94G3 Gordon, J., Shechter, H., Folman, M.: Phys. Rev. B 49 (1994) 4898.
94G4 Gorodetsky, D.A., Melnik, Yu.P., Usenko, V.A., Yas’ko, A.A., Yarigin, V.I.: Surf. Sci. 315
(1994) 51.
94H Hashim, K.I., Jones, J.P.: Thin Solid Films 245 (1994) 64.
94H2 Hugenschmidt, M.B., Gamble, L., Campbell, C.T.: Surf. Sci. 302 (1994) 329.
94H3 Hertel, T., Over, H., Bludau, H., Gierer, M., Ertl, G.: Surf. Sci. 301 (1994) 1.
94J Jiang, L.Q., Koel, B.E.: Phys. Rev. Lett. 72 (1994) 140.
94J2 Jänsch, H.J., Huang, C., Ludviksson, A., Martin, R.M.: Surf. Sci. 315 (1994) 9.
94J3 Jacobi, K.: in Landolt-Börnstein Vol. III/24B "Physics of Solid Surfaces",
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94K2 Kovacs, I., Iost, N., Solymosi, F.: J. Chem. Phys. 101 (1994) 4236.
94K3 Kondoh, H., Nozoye, H.: Surf. Sci. 318 (1994) 158.
94M2 Mundt, C., Benndorf, C.: Surf. Sci. 307-309 (1994) 28.
94M3 Mizuno, S., Tochihara, H., Kawamura, T.: Phys. Rev. B 50 (1994) 17540.
94N Naparty, M.K., Skonieczny J.: Vacuum 45 (1994) 361.
94O Okuda, T., et al.: Surf. Sci. 321 (1994) 105.
94R Rohwerder, M., Benndorf, C.: Surf. Sci. 307-309 (1994) 789.
94S Szczudlo, Z., Sendecka, K., Gubernator, W., Ciszewski, A.: Vacuum 45 (1994) 263.
94S2 Schmidt, M., Wolter, H., Wandelt, K.: Surf. Sci. 307-309 (1994) 507.
94S3 Schmidt, M., Wolter, H., Nohlen, M., Wandelt, K.: J. Vac. Sci. Technol. 12 (1994) 1818.
94S4 Sato, M.: Appl. Surf. Sci. 82-83 (1994) 532.
94V Vlachos, D., Kamaratos, M., Papageorgopoulos, C.: Solid State Commun. 90 (1994) 175.
94W Wilke, S., Hennig, D., Lober, R., Methfessel, M., Scheffler, M.: Surf. Sci. 307-309 (1994) 76.
94W2 Wilke, S., Hennig, D., Lober, R.: Phys. Rev. B 50 (1994) 2548.
94W3 Weitering, H.H., Chen, J., Pérez-Sandoz, R., Di Nardo, N.J.: Surf. Sci. 307-309 (1994) 978.
94W4 Whitten, J.E., Gomer, R.: Surf. Sci. 316 (1994) 1.
94Z Zhang, C.-S., Bing Li, Norton, P.R.: Surf. Sci. 313 (1994) 308.
94Z2 Hong Zeng, Dongjin Byun, Jiandi Zhang, Vidali, G., Onellion, M., Dowben, P.A.: Surf. Sci.
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95B Basset, D.W.: Surf. Sci. 325 (1995) 121.
95D Derraa, A., Lee, M.J.G.: Surf. Sci. 329 (1995) 1.
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95H Held, G., Menzel, D.: Surf. Sci. 327 (1995) 301.
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97H Hoffmann, W., Benndorf, C.: Surf. Sci. 377-379 (1997) 681.
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H.J.: Surf. Sci. 412/413 (1998) 586.
98F Fedorus, A., Bauer, E.: Surf. Sci. 418 (1998) 420.
98G Grüne, M., Radnik, J., Wandelt, K.: Surf. Sci. 402-404 (1998) 236.
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98M3 Mundt, C., Benndorf, C.: Surf. Sci. 405 (1998) 121.
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98W Whitten, J.E., Gomer, R.: Surf. Sci. 409 (1998) 16.
98Y Young Sir Chung, Evans, K., Glaunsinger, W.: Appl. Surf. Sci. 125 (1998) 65.
98Y2 Yoshihara, J., Campbell, J.M., Campbell, C.T.: Surf. Sci. 406 (1998) 235.
99B Böttcher, A., Niehus, H.: Phys. Rev. B 60 (1999) 14396.
99F Farias, D., Schilbe, P., Patting, M., Rieder, K.H.: J. Chem. Phys. 111 (1999) 559.
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13401.

D. SANDER , H. IBACH,
4.4.1 Introduction
The surface free energy per area and the surface stress are macroscopic excess quantities, specific to
surfaces of condensed matter. In short, the free energy is defined as the work per area necessary to create a
surface. It is denoted as γ and called surface energy for simplicity in the following. The surface stress is
the work per area necessary to strain an already existing surface. Both, surface energy and surface stress
have the same dimension of an energy per area (J/m2). In order to emphasise the difference between the
two we quote surface stresses in N/m. An alternative, sometimes useful definition of the surface stress
follows directly from the definition as change in the surface energy per area with applied strain: The
surface stress is the excess force per length which has to be applied to the surface in order to keep the
surface undeformed when the material is cut perpendicular to the surface along a line, with the material on
the right hand side of the cut removed in a Gedanken experiment. This definition leads to a qualitative
useful insight into the connection between the local charge density distribution in the outermost atom
layers near the surface and the sign and magnitude of the surface stress. The distinction between surface
energy and surface stress was first pointed out by Gibbs [61Gib]. Excess free energies and stresses can
also be defined for condensed matter interfaces, e. g. the solid-liquid interface. However, this section
focuses entirely on surfaces, i. e. the solid-vacuum or the liquid-vacuum interface. The microscopic origin
for the surface energy and the surface stress is that atoms or molecules at the surface of a solid or a liquid
have a different local environment than the atoms in the bulk. This leads to a redistribution of the
electronic charge compared to the bulk which affects both surface energy and surface stress.
The strain of a surface is a second rank tensor ε ij with (i, j = 1,2) denoting the in-plane components.
The energy associated with the strain, the surface stress, is therefore likewise a second rank tensor. Its
components are denoted as τ (ijs) (i, j = 1,2). The work per area A associated with straining a surface is
given by the derivative of the excess free energy of the surface Fs with respect to the strain ε ij at constant
temperature
(s) ∂Fs ∂ ( γA) ∂A ∂γ ∂γ

τ = = =γ +A = γδ ij + (1)
ij ∂ε ij ∂ε ij ε ij ∂ε ij ∂ε ij
in which δij is the Kronecker symbol. This equation was first derived by Shuttleworth [50Shu, 53Her] and
is named after him. The second term in the Shuttleworth equation makes for an important difference
between the surface stress of liquids and solids. Isothermic stretching of the surface of a liquid results in a
completely plastic deformation: The change of surface area leads to a flow of molecules from the interior
to the surface, provided the liquid film is not too thin. The local environment of a surface molecule
therefore does not change upon straining the surface, and consequently all area specific excess quantities
such as the surface energy γ remain constant. Thus for liquids, the second term in eq. (1) is zero and the
surface stress is equal to the surface energy in that case. For solids, on the other hand, no plastic flow of
molecules or atoms to the surface occurs (unless the temperature is close to the melting point) and the
strain derivative of γ does not vanish. The surface deforms elastically when the material is strained. The
local environment of each surface atom therefore changes due to the strain in the surface layer and
consequently the stress differs from the specific surface energy. For liquids, the term surface tension is
frequently used for the specific surface energy γ. Since the word tension bears the connotation of "stress"
the term surface "tension" should be avoided for solid surfaces where stress and specific energy are
different. Calculations predict that the strain derivative of γ can be of the same magnitude as γ itself

New Series III/42A2
4.4 -2 4.4 Surface free energy and surface stress [Ref. p. 4.4 -44
[97Fei, 97Fill]. The sign of ∂γ / ∂ε can be positive or negative. A positive value indicates that the
ij
surface energy is lowered by reducing the surface strain, i.e. by increasing the density of surface atoms,
and vice versa. A different surface density compared to the underlying bulk layers is equivalent to a
surface reconstruction and the sign and magnitude of ∂γ / ∂ε has therefore been associated with the
ij
propensity of the surface to reconstruct to a new structure with a higher or lower density of atoms in the
surface layer [90Wol, 92Cam1, 92Cam2, 94Wol1, 93Cho, 93Nee, 97Bac, 97Iba1, 97Iba2]. Parameters
β = ( τ − γ ) / ( Gb) [92Cam1, 94Cam], with the shear modulus G and the Burger’s vector b, and
α = ( τ − γ ) / ( E c a 0 ) [97Iba1], with the cohesion energy Ec and the lattice constant a0, have been
introduced as an indicator for the propensity of a surface to reconstruct. Both parameters are proportional
to the magnitude of the second term of equation (1). A large value of this term has been proposed as a
driving force for reconstruction, both for the reconstruction of clean surfaces as well as for the adsorbate
induced reconstructions. An example for a reconstruction of a clean surface driven by surface stress is
presumably the reconstruction of the Au(111) surface [97Bac]; an example for a reconstruction driven by
the adsorbate induced stress is the carbon induced p4g reconstruction of Ni(100) [86Mül, 92San, 97Iba1].
For data on surface reconstruction and relaxation see LANDOLT-BÖRNSTEIN New Series III/24a.
The surface energy necessarily is a positive quantity. The material would desintegrate if it was not.
The surface stress, on the other hand, can be positive or negative. For anisotropic surfaces the components
of the stress tensor can be of opposite sign. A famous and frequently studied example is the reconstructed
Si(100) surface [88Ale, 88Men, 94Web]. If the surface free energy increases upon an expansion of the
surface area, i. e. the surface has the propensity to contract, the stress is called tensile. The sign of the
stress τ(s) is defined as positive in that case (comp. eq. (1)). If the surface elastic energy would be lowered
by an expansion, the surface stress is called compressive and the sign of the surface stress is negative. All
calculations of the surface stress of clean metals indicate a positive surface stress. The stress may,
however, become negative upon adsorption, in particular upon adsorption of electronegative atoms. On
some clean semiconductor surfaces, the stress is negative, i. e. compressive. The absolute magnitude of
the surface stress depends on the material and on the surface orientation. Large values are predicted for
the 5d elements. For Pt(111), a surface stress as large as 6.27 N / m has been calculated [97Fei]. The
surface stress of inert gas crystals, on the other hand, is slightly compressive, and amounts only to about -
10-3 N / m [50Shu].
Due to the lack of methods, reliable experimental data for surface energy and surface stress are not
available for clean solid surfaces at room temperature. Surface energy data are almost exclusively
obtained near the melting point of the solids using the method of zero creep. So far, only cleavage
experiments have shown the potential to determine absolute surface energy data at low temperatures.
Recently, Bonzel has proposed a new method to determine the absolute value of the surface energy of
singular surfaces from the temperature dependence of the size of a facet [2000Bon]. However, the new
method has not been applied to an experimental system yet. The surface stress of clean surfaces is likewise
difficult to measure directly. Several methods which have been proposed are discussed in 4.4.3. Changes
of the surface stress due to adsorption, on the other hand, can be measured with sub-monolayer sensitivity
and experimental data exist for a number of systems and are presented in section 4.4.9.
4.4.2 Experimental determination of surface free energy
Despite the fundamental importance of the surface free energy γ in sintering, diffusion, nucleation and
growth of inclusions, for the strength of materials, and for thin film growth, experimental data on γ are
mostly from experiments performed at high temperatures near the melting point or for the liquid state.
Early experimental data show a considerable scatter due to contamination and due to experimental
difficulties inherent to the experimental methods [88Ida]. Nevertheless experimental data on the surface
free energy of (bona fide) clean metals are compiled in this contribution as they serve as an important
reference when the change of the surface free energy due to adsorption is discussed. References to

New Series III/42A2
Ref. p. 4.4 -44] 4.4 Surface free energy and surface stress 4.4 -3
empirical relations between surface free energy and other physical properties like the cohesion energy, the
heat of sublimation, the work function and the compressibility are given in section 4.4.2.5.
Experimental techniques to measure the surface free energy of liquids have been thoroughly discussed
by Bakker [28Bak], Hondros [70Hon], and Adamson [90Ada]. The sessile drop method [59All], the
pendant drop method [63All], the drop weight method [63All] and Lenard’s wire frame method have been
applied [68Ger] to obtain the surface energy of liquid metals. Other experimental techniques like cleavage
and zero creep experiments have been described by Bikerman [65Bik], Hondros [70Hon] and Blakely
[73Bla].
4.4.2.1 Cleavage experiments
Cleavage experiments were introduced by Obreimoff who deduced the surface energy of mica from
splitting thin mica sheets [30Obr]. He was the first to consider the influence of gas adsorption on the
surface free energy in order to explain the vastly higher value of the surface free energy measured in
vacuum as compared to data obtained from splitting in air. Gilman [60Gil] determined the surface energy
of the ionic crystals LiF, MgO, CaF2, BaF2, CaCO3 and of Si and Zn by quantitative cleavage
experiments. The method has been applied also to KCl [63Wes1], MgO [63Wes2], to Zn [69Mai], to W
[65Hul] and to the fluorides CaF2, SrF2 and BaF2 [78Bec]. The elasto-mechanical aspects of the cleavage
experiments have been critically analysed [64Gil, 65Gil, 68Wie]. The issue of plastic flow at the tip of the
propagating crack [73Fre] and the influence of viscous fluids on crack propagation have been discussed
[87Gen]. The application of cleavage experiments seems to be well suited to determine the surface free
energy of brittle materials [73Kel, 93Law] and to investigate the fracture surface energy of bonded
interfaces [36Ray, 98Krä, 99Plö]. For most metals however, plastic flow has to be anticipated near the
front of the propagating crack, giving rise to irreversible processes which result in too high values of the
surface energy [60Gil]. In how far this fundamental limitation of the technique to brittle materials can be
circumvented to apply the technique to metals by working at low temperatures to hinder plastic flow has
apparently not been investigated any further since the early experiments on Zn, Fe and W.
w
t
L Fig. 1. Double cantilever cleavage experiment. A tensile test
machine is used to apply a force F to a presplit sample of width
w and thickness t. For a given force F the equilibrium crack
length L is measured to calculate the surface energy. For a
discussion see [60Gil, 63Wes1, 64Gil].
F
Cleavage experiments can be performed by applying a force on a partially pre-split sample as indicated in
Fig. 1. Equating the work done by advancing the crack incrementally by applying a force to the split
sample with the increase of the elastic bending energy of the sample beams and with the increase of the
surface energy due to the increased surface area, leads to the following expression for the determination of
the surface free energy
6F 2 L2
γ= . (2)
Ew 2 t 3
The force applied to the bent beams is given by F, L denotes the length of the crack, E is Young’s
modulus for the appropriate orientation, the beam width and thickness are given by w and t, respectively.

New Series III/42A2
This equation is applicable for vanishing values of t/L, otherwise corrections of order t/L have to be
considered [64Gil, 68Wie].
Surface energy data obtained by cleavage experiments are presented in section 4.4.7.1 in Table 2.
These experiments were performed at room temperature or at low temperatures and represent the only
measurements of γ which were not performed at high temperature.
4.4.2.2 Pendant drop and drop weight method
Values of the surface free energy of metals in their liquid state have been obtained from the pendant drop
method and from the drop weight method, as compiled by Allen [63All]. The end of a high purity rod is
heated under vacuum to the melting temperature. In the former method, the profile of a pendant drop
hanging from the supporting rod of the same material is analysed to extract the maximum diameter dm and
the diameter ds at a distance dm from the end of the drop, as sketched in Fig. 2. A shape factor H has to be
taken from tables for the given value of S=ds/dm to facilitate the calculation of
ρgd 2
γ= m (3)
H
with the density of the liquid given by ρ and the gravitational acceleration g. Values of the correction
factor H as a function of S = ds / dm have been tabulated [70Hon, 90Ada] with S ranging from 0.3 to 1,
yielding values of 1/H from 7.1 to 0.31. In this range of S, 1/H can be approximated by the following
relation 1/ H = 59.71 − 375.355 S + 991.543 S2 − 1331.321S3 + 899.366 S4 − 241.668 S5 .
2r
ds Fig. 2. The pendant drop method. A rod of diameter 2r is heated close to

the melting temperature until a stable drop of maximum diameter dm is
dm formed. One measures dm and in the distance dm from the bottom end of
dm the drop the diameter ds. The surface energy of the liquid vapour interface
is determined with equation (3) from the ratio of both diameters[63All,
88Ida, 90Ada].
The drop weight method relies on the measurement of the weight of a drop of material which drops off the
end of a heated rod with radius r. It has been introduced as early as 1868 by Quincke [1868Qui]. The most
basic evaluation is known as Tate’s law, stating that the weight of the drop, m g, is equilibrated by the
surface free energy of the liquid metal acting along its circumference, γ 2 π r. A correction f depending on
the ratio r / V1/3 has to be employed to account for the liquid which remains at the end of the rod after the
drop has fallen.
mg
γ= (4)
2 πrf
The correction f approaches one for small rod diameters [70Hon, 90Ada]. Therefore, measurements
performed on rods with different diameter can be extrapolated to zero diameter rods to obtain the correct
value of γ [63All]. From a measurement of the mass of a drop, the volume of the drop V is calculated with
the density of the liquid [88Ida]. Then the ratio between rod diameter r and V1/3 is calculated to determine
f from a table [70Hon, 90Ada]. The following empirical relation gives the correction factor
f = 0.89 − 0.703 a + 0.413a 2 for a = r/V in the range 0.3 < a <1.0.
1/3

New Series III/42A2
It is claimed that the pendant drop technique and the drop weight technique give very accurate values
which agree within 4 % [63All]. Surface energy data on the liquid vapour interface which were obtained
by both techniques are given in section 4.4.7.2 in Table 3.
Both techniques could be employed to determine the change of the surface free energy under partial
pressures of various adsorbates. However, such measurements have not been performed yet.
4.4.2.3 Zero creep experiments
The pendant drop and the drop weight method investigate the surface free energy of a metal in the liquid
state with respect to its vapour pressure or with respect to vacuum. In a narrow temperature range, starting
approximately at 70 % of the melting temperature Tm up to Tm, the surface free energy can be extracted
from zero creep experiments [49Udi, 51Ale, 52But1, 63Inm, 64Pri, 70Hon].
(a) (b)
10
8
6
2 cm 4
Strain X 103
2
0 -4
1 2 3 4 5 6 7 8 X 10
-2 Stress [Pa]
-4
-6
-8
-10
Fig. 3a, b. Schematic of a zero creep experiment. (a) Fine Cu wires (∅ ≈ 0.07 mm) are loaded with different weights
of the same material of up to 100 mg and heated in a vacuum oven. (b) The strain of the wires after heating for 72 h
3
to 1000° C is measured. Depending on the load, positive and negative strains of the order 10- are observed. The
load which gives zero strain ("zero creep") is inserted in equation (5) or (6) to determine the surface energy. Data
points from [49Udi].
Thin wires with diameters of order several ten µm are suspended in a vacuum oven and loaded with
different weights, as schematically indicated in Fig. 3. While the oven and the wire are heated, the heavily
loaded wires will stretch, while the lightly loaded wires will shrink due to the contractile action of the
surface energy. The mass m of the load which leads to zero strain rate of the wire with radius r at high
temperature determines the surface free energy
mg
γ= . (5)
πr
The surface free energy is calculated from the zero crossing of the strain vs. load curve [49Udi].
The Nabarro-Herring mechanism [50Her] describes this viscous flow from material from the sides of
the wire to the end at low stress and high temperature [51Ale, 52Gre, 52But1, 63Inm, 64Pri, 76Bau].
Usually the wire undergoes structural changes in the process of thermal annealing which lead to the
formation of grain boundaries, kinks, and bulges and waists [51Ale, 63Pri]. Grain boundaries are formed
with a density of n per unit length, and they lie normal to the wire axis, extending over the wire cross

New Series III/42A2
section. The data evaluation has to be modified to account for the surface energy of the grain boundaries
γb [70Hon, 73Hod, 73McL]
mg
γ= + nr γ b . (6)
πr
The energy of the grain boundary has to be determined independently. Relative values of γb / γ can be
obtained from a measurement of the dihedral angle at a surface of a grain boundary groove, e.g. by
electron microscopy [63Inm, 73Hod, 73McL]. An approximation is γb = γ/3 [52But2, 64Pri, 70Hon,
73Hod, 73McL, 76Bau].
The rather limited temperature range in which zero creep experiments are performed is typically less
than 100 K. It has been extended to 330 K by replacing the wire sample with a thin foil of the material
with a thickness of ≈10 µm. An advantage of using foils instead of wires was ascribed to the elimination
of the contribution of grain boundary energies to the measurement by careful dimensioning of the foil
[67Hon, 68Hon, 70Hon]. Surface free energies of metals measured by zero creep experiments are
compiled in section 4.4.7.2 in Table 3.
The zero creep method has been used to study the influence of gaseous adsorbates on the value of the
surface free energy γ [52But2, 67Hon, 76Bau]. Starting from the Gibbs’ adsorption isotherm, a relation
between the excess surface concentration Γ of an adsorbed species at constant temperature T and the
dependence of the surface free energy on the partial pressure p of the adsorbate in the gas phase can be
derived [73Hir] (see also H. P. Bonzel in this volume):
1 ∂γ
Γ=− . (7)
kT ∂ ln p
Measurement of the change of the surface energy due to adsorption have been performed to obtain the
adsorbate surface concentration. For the application of eq. (7) to an experimental situation it is necessary
that the surface and the bulk of the material are in thermodynamic equilibrium, a condition which is not
always fulfilled. Phase changes due to chemical reactions between substrate and adsorbate, or temperature
driven phase transitions like the α-Fe, γ-Fe , δ-Fe transition [63Pri, 64Pri] might set in, e. g., and a
straightforward interpretation of the change of the surface free energy as a function of the adsorbate partial
pressure is not possible [68Hon, 73McL, 76Bau]. A new compound might form which has a different
creep behaviour, or the new compound has a different surface free energy, and comparing to the surface
free energy of the clean substrate is not meaningful. Experimental data on the change of the surface free
energy with adsorption and adsorbate-driven compositional changes of the surface are given in
section 4.4.8.
Due to the problems noted above and also because numerous other methods to obtain the surface
concentration are available for the solid gas interface the use of eq. (7) is no longer pursued. It may be
useful to comment, however, that an equivalent relation for the dependence of the interface energy as a
function of the electrode potential is still the major source of quantitative data on adsorbate concentrations
at the solid-liquid interface (“chronocoulometry” [66Ans, 86Ric]).
4.4.2.4 Orientation dependence of the surface free energy
Experiments on the equilibrium shape of small crystallites and on the groove angle at grain boundaries
indicate an orientation dependence of the surface free energy. The value the surface free energy varies by
several percent for different surface orientations at high temperature. This anisotropy is e.g. responsible
for the faceted shape of the crystallites shown in Fig. 4.

New Series III/42A2
Fig. 4. Scanning electron microscopy image of the anisotropic

faceted morphology of a lead crystallite. This equilibrium shape
has been analysed to derive the orientation dependence of the
surface free energy at various temperatures, see chapter 4.4.7.3.1
[83Hey].
Most experiments on the surface free energy which have been discussed in the preceding sections have
been performed on polycrystalline material. One exception is the zero creep technique when applied to
foils which can be prepared as single crystal surfaces [67Hon]. Absolute values for the surface free energy
of a specific orientation have also been obtained by the cleavage technique, see data in section 4.4.7.1.
The free energy specific to a particular crystal face is denoted as γhkl with the Miller indices hkl as a
subscript. While the absolute value of the surface free energy is difficult to determine experimentally and
the results are not very accurate, the dependence of the surface free energy on the crystalline orientation of
the surface can be obtained with very high accuracy from the equilibrium shape of the crystals using an
inverse Wulff construction [01Wul, 51Her, 53Her, 67Win, 73Win, 88Wor].
Electron microscopy using a replica technique on small particles of µm size, which were prepared to
mimic equilibrium equilibrium shapes, has been analysed to determine the ratio of surface free energies
for different orientations [64Sun]. Typically, the variation of γ is plotted in a stereographic projection and
reveals a variation with orientation of less than 10 %. Scanning electron microscopy, transmission electron
microscopy and reflection electron microscopy has been used to image equilibrium shape crystallites of
Au, In, Pb, and Si directly [80Hey, 83Hey, 86Hey, 98Ber, 99Hey]. Data on the temperature dependence
of the surface free energy and its anisotropy are presented in section 4.4.7.3 and 4.4.7.3.1.
(a) (b)
Fig. 5. Pd induced faceting of W(111). (a) Large area scanning tunneling microscopy image (100 nm × 100 nm) of
Pd-W(111), after deposition of 1.2 atomic layers of Pd and annealing at 1075 K for 3 minutes. Three sided pyramids
form a faceted surface. (b) The small area image (11 nm ×11nm) identifies the atomic row and trough structure of the
bcc(211) facets, which form the three sided pyramids of (a). Images from [99Mad].
The grooves at the boundaries of grains of different orientation have been studied by electron microscopy
to derive relations between the grain boundary energy and orientation [57Myk, 58Moo, 61Myk, 64McL,

New Series III/42A2
64Rhe]. These data are analysed to derive the orientation dependence of the ratio of the surface free
energy of γhkl / γref , where γref is assigned to the (100) or the (111) orientation.
The anisotropy of γ increases with decreasing temperature and is influenced by adsorption [62Rhe,
86Hey]. Both effects are important factors in the discussion of faceting of single crystal surfaces. Gas
adsorbates [98Gra] and monolayer coverage of metallic films [97Che, 99Mad, 99Nie] have been
identified as driving force for substrate faceting. An example for adsorbate driven faceting is presented in
Fig. 5 for the Pd-W(111) system. A monolayer coverage of Pd induces a large area faceting of initially
planar W(111), exposing {211} pyramidal facets after annealing. The faceting has been ascribed to an
increased anisotropy of the surface free energy due to the Pd coverage [99Mad].
4.4.2.5 Empirical relation between surface free energy and other quantities
There are several empirical relations in the literature which favour the physically appealing conclusion
that a high bond strength leads to high values of the surface free energy [63All, 76Lan, 88Ida]. A very
small scatter of the experimental data points for γ around the linear plot of γ vs. Tm / (Vm)2/3, with the
melting temperature Tm and the molar volume at the melting point Vm , supports this view [63All, 88Ida].
A plot of the surface free energy vs. the heat of vaporisation reveals that high surface energies are
correlated with high energies of vaporisation, as originally proposed by Skapski [48Ska, 56Ska, 63All,
76Lan, 78Mie1, 88Ida]. A linear relation between the surface free energy and the bulk modulus B has
been suggested from a plot of γ vs. B [72Waw, 73Waw]. This finding has been exploited to calculate the
alleged temperature dependence of γ from ultrasonic measurements of the elastic constants as a function
of temperature [72Waw, 73Waw, 75Waw1, 75Waw2]. However, this procedure should be viewed with
caution as there seems to be no physical justification for the assumed similar temperature dependence of
both surface energy and compressibility [78Mie2]. Qualitative aggreement between an estimate of the
surface free energy from phonon frequencies has been reported [76Tys]. This approach exploits the
Orowan-Polanyi estimate [76Tys] between the ideal tensile strength and the surface energy. A
proportionality between the electron work function and the surface energy has been proposed and verified
empirically. This relation is based on the correlation between the electron work function and the heat of
sublimation [73Mis, 78Mie2].
4.4.3 Experimental determination of the absolute value of the surface stress

4.4.3.1 Lattice parameter of small particles
The stress at the surfaces of a solid body leads to a compression (or expansion) of the material. While the
deformation is small it becomes measurable for small particles. The measurement of the lattice parameter
of small particles may therefore be used to determine the surface stress. For simplicity we consider a
sphere of a radius R of an elastically isotropic solid with a compressibility K subject to an isotropic
surface stress τ(s). The incremental work against the surface stress and the bulk elasticity by expanding the
body is
1 ∆V
δW = τ (s ) δA + δV (8)
K V
In equilibrium the variation of the work δW is zero. By expressing δA and δV in terms of the radius δR
one obtains
1 ∆V 3 ∆a
τ (s ) = − =− (9)
2K V 2K a
where ∆a/a represents the relative change of the lattice constant. A positive surface stress will lead to a
compression of the lattice parameter, ∆a < 0 .

New Series III/42A2
Using electron diffraction the lattice parameters of small Au [68May], Ag [52Ber, 70Was], Pt and Cu
[72Was] particles with diameters between 30 Å and 200 Å have been determined. The lattice parameter of
the smallest particles was found to be smaller than that of a continuous film by 0.1 % (Cu) up to 0.6 %
(Ag). A plot of the relative strain of the lattice parameter against the inverse of the particle dimension,
∆a / a vs. 1 / R, displayed a linear behaviour, and the surface stress was calculated from the slope of the
curve. The method has also been recently applied to determine the interface stress of an oxide film on a
nanosized Si particle, and a compressive interface stress, leading to a larger lattice constant of the smaller
particles has been reported [99Hof]. Inherent deficiencies of the method are due to the dependence of the
positions, intensities and breadths of the electron diffraction lines on the particle size, shape and structure,
which complicates the determination of the lattice parameter from a diffraction image [52Ber, 70Was,
84Mon]. In addition, neither the anisotropy of the elastic constant nor the anisotropy of the surface stress
is considered in eq. (9). Depending on the orientation of the surfaces of the particle the actual mean
compression of the lattice constant is a result of a rather complex interplay between the stress on the
various surfaces of the particle and the anisotropic elastic behaviour of the material. So far neither the
elastic anisotropy nor the actual, irregular shape of the small crystallites has been taken into account.
Furthermore, the values of the elastic constants and equilibrium lattice spacings of the nanosized materials
are unknown. In conclusion, the quantitative determination of surface stress from an apparent lattice strain
of small crystallites remains a challenge for the future.
4.4.3.2 Surface phonons as indicator of surface stress
The dispersion relation of elastic surface waves of a solid, so-called Rayleigh waves, has been
investigated to study the elastic interactions near the surface layer [71All1, 71All2, 71All3, 84Iba, 87Leh,
92Iba]. It has been proposed that the dispersion relation of Rayleigh waves should be an indicator of the
surface stress [86Mül, 87Leh, 88Dau, 92Iba, 97Iba1]. The idea is based on the following consideration:
the excitation of surface wave involves an enlargement of the surface area. In a simple picture [97Iba1], a
positive (tensile) surface stress opposes the increase of the surface area, and is expected to provide an
additional restoring force, leading to an upward shift of the frequency of the surface wave. A negative
(compressive) surface stress should soften the vibrational mode. While this concept appears appealing and
may be qualitatively sound it falls short of producing quantitative data. Firstly, because a quantitative
evaluation of the surface stress using this concept would require the knowledge of the dispersion as it
would be without a surface stress. Secondly, the most significant changes in the dispersion occur at the
zone boundary where short range interactions between the atoms determine the frequency, rather than the
macroscopic quantity surface stress. A general correlation between surface stress and the frequency of the
Rayleigh wave can therefore rightfully be questioned [89Gas]. The situation differs from the case of
capillary waves of liquids [66Lan, 78Som], also called ripples or ripplons. In the latter case, the surface
stress (tension) is the only restoring force providing for a nonzero frequency of the ripplons, and
interfacial energies as well as other visco-elastic properties of liquid surfaces or interfaces can be obtained
from the study of ripplons [86San, 90Ada].
4.4.3.3 Absolute surface stress from the bending of thin crystal plates
The physical concept of surface stress as a force per length which acts in the surface layer of a solid leads
to the idea, that the effective elasticity of small particles should be altered by the combined action of bulk
elasticity and surface stress. A tensile surface stress would induce an apparent increase of the elastic
stiffness whereas a compressive surface stress would soften the elastic behaviour. Müller and Kern
suggested to measure the deflection of a thin circularly shaped crystalline sample in the gravitational field
[94Mül]. According to their calculation, the deflection of the thin sample depends on the magnitude of the
surface stresses acting on both crystal faces. A tensile surface stress leads to a smaller deflection as
compared to a surface stress free situation, a compressive surface stress leads to a larger deflection
[94Mül]. However, the magnitude of the effect of surface stress on the deflection depends, among other
variables, on the diameter-to-thickness-ratio of the sample, and for a 1 cm diameter Si plate it is suggested
that the thickness should be of the order 20 µm. Although such thin crystalline plates with well defined

New Series III/42A2
surfaces are available for semiconductors, other experimental difficulties are anticipated, and no
experiments along these lines have been performed yet.
4.4.4 Experimental determination of changes of surface stress due to adsorption

The most powerful technique to determine changes in the surface stress exploits the bending moment of a
surface stress acting on thin samples. The idea of this measurement is that any difference of the surface
stress between the front and the back surface will lead to a bending of the sample. The difference of
surface stress between the two crystal faces can be determined in absolute numbers from a measurement
of the bending. Continuum elasticity theory is applied to consider the elastic properties and the elastic
anisotropy of the substrate properly [96Mar1, 96Mar2, 97Iba1, 99San1, 2000Dah]. Then the relation
between the bending of the substrate, often expressed as radius of curvature R and the stress difference
between front and back side ∆τ ( s) is derived. The basic idea of the technique is sketched in Fig. 6.
Fig. 6a, b. Cantilever bending technique. (a) A rectangular

sample is clamped along its width to a sample manipulator.
The free sample length l is of the order 10 mm, the sample
width w is 2 mm. (b) Side view. Any difference of stress
between the front and back side of the sample with
thickness t induces a sample deflection ζ, which
corresponds to a change of slope of the surface ζ ′ or a
curvature ζ ′′ . The curvature κ is the inverse of the radius
of curvature R [97Iba1, 99San1].
From a measurement of the deflection ζ, the slope ζ ′ , or the curvature κ = 1 / R = (ζ′(l1) − ζ′(l2 )) /(l1 − l2 ) ,
the radius of curvature is determined. The Stoney relation is employed to calculate the stress difference
∆τ ( s) = Yt 2 / (6(1 − ν) R ) [97Iba1]. Only the elastic properties of the substrate enter via the Young
modulus Y and the Poisson ratio ν. The sample thickness is given by t. This analysis of the bending beam
or cantilever bending technique has a long tradition in film stress measurements [09Sto], where the film
stress τ(f) is calculated from a measurement of the sample curvature [66Hof, 88Doe, 89Nix, 90Abe] for a
given film thickness tf, with ∆τ ( s) replaced with τ(f)tf . In general, the possible anisotropy of both stress and
elastic properties require a refined analysis, as described below.
The first measurements of surface stress induced bending were performed on III-V semiconductor
compounds [64Cah, 64Fin, 66Dru], where the (111)- or (0001)-surface are formed by either the group III
or the group V element [60Gat]. The bending of ultrathin crystals was investigated, e.g., in an electron
microscope to determine the difference of the surface stress between crystal faces formed by the two
constituents Al and N on AlN crystals in the thickness range 380 Å to 3500 Å [66Dru]. For InSb a surface
stress difference between the two (111) faces of 1.15 ± 0.23 N / m [62Han], and for AlN a stress
difference of 3.63 ± 0.15 N / m [66Dru] was reported. The influence of H2S and NH3 atmosphere on the
radius of curvature of GaAs and InSb crystals has been investigated [64Fin]. NH3 exposure was found to
increase the radius of curvature, whereas H2S induced a decrease of the radius of curvature.
The high sensitivity of optical [90Sch, 90Mar, 95San1, 97Deg], capacitive [91San, 94Web] and tunnel
current [97Bac, 97Iba1] deflection measurements allows to measure stress effects with sub-monolayer
sensitivity [97Iba1, 99San1]. The change of surface stress on one crystal face due to adsorption [91San,
92San, 94Iba, 99San2], surface reconstruction [92San], film growth [90Sch, 90Mar, 96Gro, 97Koc,
98San, 99San2], film magnetisation [94Web, 99San1, 2001Dah] and surface reactions [95Gro] has been
measured under ultra-high vacuum and in electrochemical cells [97Bac, 97Hai, 97Iba2].

New Series III/42A2
surfaces are available for semiconductors, other experimental difficulties are anticipated, and no
experiments along these lines have been performed yet.
4.4.4 Experimental determination of changes of surface stress due to adsorption

The most powerful technique to determine changes in the surface stress exploits the bending moment of a
surface stress acting on thin samples. The idea of this measurement is that any difference of the surface
stress between the front and the back surface will lead to a bending of the sample. The difference of
surface stress between the two crystal faces can be determined in absolute numbers from a measurement
of the bending. Continuum elasticity theory is applied to consider the elastic properties and the elastic
anisotropy of the substrate properly [96Mar1, 96Mar2, 97Iba1, 99San1, 2000Dah]. Then the relation
between the bending of the substrate, often expressed as radius of curvature R and the stress difference
between front and back side ∆τ ( s) is derived. The basic idea of the technique is sketched in Fig. 6.
Fig. 6a, b. Cantilever bending technique. (a) A rectangular

sample is clamped along its width to a sample manipulator.
The free sample length l is of the order 10 mm, the sample
width w is 2 mm. (b) Side view. Any difference of stress
between the front and back side of the sample with
thickness t induces a sample deflection ζ, which
corresponds to a change of slope of the surface ζ ′ or a
curvature ζ ′′ . The curvature κ is the inverse of the radius
of curvature R [97Iba1, 99San1].
From a measurement of the deflection ζ, the slope ζ ′ , or the curvature κ = 1 / R = (ζ′(l1) − ζ′(l2 )) /(l1 − l2 ) ,
the radius of curvature is determined. The Stoney relation is employed to calculate the stress difference
∆τ ( s) = Yt 2 / (6(1 − ν) R ) [97Iba1]. Only the elastic properties of the substrate enter via the Young
modulus Y and the Poisson ratio ν. The sample thickness is given by t. This analysis of the bending beam
or cantilever bending technique has a long tradition in film stress measurements [09Sto], where the film
stress τ(f) is calculated from a measurement of the sample curvature [66Hof, 88Doe, 89Nix, 90Abe] for a
given film thickness tf, with ∆τ ( s) replaced with τ(f)tf . In general, the possible anisotropy of both stress and
elastic properties require a refined analysis, as described below.
The first measurements of surface stress induced bending were performed on III-V semiconductor
compounds [64Cah, 64Fin, 66Dru], where the (111)- or (0001)-surface are formed by either the group III
or the group V element [60Gat]. The bending of ultrathin crystals was investigated, e.g., in an electron
microscope to determine the difference of the surface stress between crystal faces formed by the two
constituents Al and N on AlN crystals in the thickness range 380 Å to 3500 Å [66Dru]. For InSb a surface
stress difference between the two (111) faces of 1.15 ± 0.23 N / m [62Han], and for AlN a stress
difference of 3.63 ± 0.15 N / m [66Dru] was reported. The influence of H2S and NH3 atmosphere on the
radius of curvature of GaAs and InSb crystals has been investigated [64Fin]. NH3 exposure was found to
increase the radius of curvature, whereas H2S induced a decrease of the radius of curvature.
The high sensitivity of optical [90Sch, 90Mar, 95San1, 97Deg], capacitive [91San, 94Web] and tunnel
current [97Bac, 97Iba1] deflection measurements allows to measure stress effects with sub-monolayer
sensitivity [97Iba1, 99San1]. The change of surface stress on one crystal face due to adsorption [91San,
92San, 94Iba, 99San2], surface reconstruction [92San], film growth [90Sch, 90Mar, 96Gro, 97Koc,
98San, 99San2], film magnetisation [94Web, 99San1, 2001Dah] and surface reactions [95Gro] has been
measured under ultra-high vacuum and in electrochemical cells [97Bac, 97Hai, 97Iba2].

New Series III/42A2
An analytical solution of the bending problem cannot be given for anisotropic surface stress acting on an
elastically anisotropic substrate of arbitrary surface orientation with the substrate being clamped to a
sample holder or otherwise hindered to deform freely [2000Dah]. However, the experiments can be
performed such that a straightforward evaluation of the curvature data is feasible and even the influence of
the clamping can be considered. The anisotropy of the elastic properties is taken into account by
performing the appropriate transformation of the elastic compliances sij′ for the surface orientation of the
substrate. The prime indicates properties in the coordinate system of the substrate. In general, two
curvatures κ1 and κ2 have to be measured along the surface directions 1 and 2 to determine the
components of the surface stress tensor [99San2, 2001He]
t 2  s ′22 s′ 
τ 1( s) =  κ 1 − 12 κ 2 
6  s s 
(10)
t2 ′
 s11 s′ 
τ (2s) =  κ 2 − 12 κ 1  , s = s11
′ s ′22 − s12
′ 2.
6  s s 
Stoney’s relation follows from this general expression for elastic isotropy in the surface plane with
Y = 1 / s11, ν = -s12 / s11 for cubic (100) surfaces. The result of the appropriate tensor transformations for
some surface orientations is given in Table 1, examples of how tensor transformations are performed for
arbitrary surface orientations are given in the literature [85Nye, 97Iba1, 99San1].
Table 1. Young’s modulus Y and Poisson’s ratio ν for selected surface orientations. Y and ν are isotropic
in the (111) plane, but anisotropic in the (100) plane. The values refer to directions along the crystal axes.
The anisotropy parameter A = 2 (s11 − s12 ) / s 44 is included, A=1 indicates elastic isotropic behaviour of
the bulk material. Elastic compliances were taken from [69Hea, 84Hea].
Material Y(100) ν[010] Y(111) ν(111) A

GPa GPa
Cu 67 0.42 131 0.50 3.23
Ni 133 0.38 224 0.41 2.45
Si 129 0.28 168 0.26 1.56
Pt 136 0.42 185 0.45 1.59
W 408 0.28 410 0.28 1.01
A necessary condition for the presented discussion of substrate bending is that the concept of small
bending of thin plates applies [59Tim, 84Sza]. Small bending means, that the resulting deflection of the
substrate due to the stress imbalance between the two surfaces should be much smaller than the substrate
thickness, which is of the order 100 µm. In most experimental situations R is of the order 100 m, and a
minute deflection of 500 nm at the end of a 10 mm long sample results, in agreement with the assumption
of small bending. If the deflection is of the order of the sample thickness or larger, the hindered Poisson
contraction in plates [84Sza] as opposed to the behaviour of beams has to be considered, and the two
dimensional bending can no longer be expressed by two radii of curvature [23Tim, 50Ash]. A substrate is
considered thin, if its lateral dimensions are much larger than its thickness. This condition is usually met
by typical substrates with a length of the order l = 10 mm, a width of w = 3 mm, and a thickness
t = 100 µm. In conclusion, the condition of small bending of thin substrates can be experimentally fulfilled
and eq. (10) describes the two dimensional bending due to anisotropic surface stress properly.
The influence of the clamping of the substrate, usually performed along the top end of a rectangular
substrate, on the bending behaviour is much more demanding to describe. Now, the lateral dimensions as
well as the anisotropy of the elastic properties of the substrate enter. Only the limiting case of pure one
dimensional bending can be solved analytically. Here, the sample curves only along one direction, usually
along the sample length, and remains flat along the width. This situation is approximately realised in

New Series III/42A2
experiments in which a sample with a length-to-width-ratio of the order of one or less is clamped along the
width at the top and at the bottom end. Then, the curvature along the width vanishes and eq. (10) can be
used with κ2 = 0 without significant errors. A finite element analysis of the bending of thin plates reveals
that for a sample clamped along its width at only one end the case of one dimensional bending is realised
for a length-to-width ratio of 0.1 [97Wat, 2000Dah].
The influence of clamping of the substrate can be described by introducing a dimensionality D of the
bending problem [97Iba1, 2000Dah]. If one considers isotropic surface stress, τ1( s) = τ (2s) = τ ( s) , and a
′ = s′22 , eq. (10) can be modified to introduce the dimensionality D
surface symmetry which warrants s11
t 2Y
τ( s ) = κ, ′ ,
Y = 1 / s11 ′ / s11
ν = −s12 ′ . (11)
6(1 − ν)(1 + (2 − D)ν)
The dimensionality is two for a free substrate, and the clamping leads to a reduction of the dimensionality
from D = 2 to D = 1, depending on the length-to-width ratio a and the Poisson ratio ν. No analytical
relation is available for the dependence of the substrate deflection ζ, the change of slope ζ′, or the
curvature ζ′′ on the various parameters. Instead, the results of numerical calculations using the finite-
element-method are presented in [2000Dah]. The results of these calculations apply to homogenous,
isotropic surface stress on substrates with s11 ′ = s ′22 [2000Dah]. This symmetry is always given on
elastically isotropic substrates with A = 1, or on (100)-, and (111)-surfaces of cubic materials, and for
(0001)-orientations of hcp materials [99San1]. Amorphous substrates can be considered elastically
isotropic, but most elements show a pronounced elastic anisotropy as indicated from the range of values of
A for various elements given in Table 1. The dimensionality D is taken from the plots of Fig. 7 for
different experimental situations, and eq. (11) should be used to take the effect of clamping into
consideration. Fig. 7(c) indicates that the direct measurement of the curvature is beneficial, as already for
a length-to-width ratio of 2 a dimensionality of D = 1.99 is calculated, whereas the measurement of the
deflection, Fig. 7(a), leads to D ≈ 1.8, with a pronounced dependence on ν.
The inclusion of an elastic anisotropy ( A ≠ 1 ) leads to a wider range of dimensionality values for a
given length-to-width ratio, which depends drastically on the Poisson ratio [2000Dah]. Again the
conclusion of these calculations is that one should measure the curvature directly to minimize the
influence of the clamping. Reference [2000Dah] should be consulted to obtain the appropriate
dimensionality for a given experimental situation.
In conclusion, the finite-element analysis supports the intuitively appealing finding that the larger the
length-to-width ratio, the smaller the effect of clamping on the bending of the substrate. A direct
measurement of the curvature near the free end of the substrate yields results which are closer to the D = 2
situation, as compared to measurements of the slope or of the deflection. The use of the latter most
indispensably requires a consideration of the clamping effect. Neglecting the effect on clamping on the
curvature and using eq. (11) with D = 2 in a situation where D is different due to the clamping leads to an
error. The magnitude of the error can be seen immediately from eq. (11) in connection with Fig. 7.
Recent molecular dynamics calculations with many-body potentials consider the curvature of a slab of
material as an additional degree of freedom to deduce the surface stress difference due to different
adsorbate coverages or reconstructions on the two surfaces of the slab from its curvature [99Pas]. These
calculations promise in principle a self-contained description of both the curvature analysis and the
physical origin of surface stress.
In section 4.4.9 experimental data changes of surface stress induced by the adsorption of gases, alkali
metals, semiconductors and metals on single crystal surfaces are compiled from cantilever bending
experiments.

New Series III/42A2
Fig. 7a-c. Finite element analysis of the effect

of clamping on the curvature of a cantilevered
substrate. (a) Deflection ζ, (b) slope ζ′, and
(c) curvature ζ′′ as a function of the length-to-
width ratio for A=1 and with the Poisson ratio
ν as a parameter. From [2000Dah].
4.4.5 Calculations of surface free energy and surface stress

The surface free energy of a solid at T = 0 K can be calculated in a two-step process from an integration
of the interaction energy of a single atom in the interior of a solid with atoms situated in the half space
above it. This energy value U′ is equal to the energy cost per atom when the atoms of the upper half space
are removed, i.e. when the atom is moved to the surface layer. However, the surrounding atoms in the
surface layer and underneath the surface layer will relax to minimise the total energy of the remaining half
space of material. By this relaxation the energy cost U′ to create the surface will be lowered by U′′, and
finally the surface free energy is given by γ = U ′ − U ′′ . The effect of relaxation on the lowering of the
surface free energy can be small, as in the case of inert gas crystals [49Shu, 64Ben, 67Ben] or substantial,
as for ionic crystals [49Shu, 50Shu, 65Ben, 67Ben, 79Tas] and metals [86Ack, 91Man, 94Sto]. Surface
stress can then be calculated from the strain dependence of γ, as described by eq. (1). Surface stress is also

New Series III/42A2
accessible in slab calculations without knowledge of the surface free energy by an evaluation of the work
which is necessary to strain a slab infinitesimally to increase its surface area. Work has to be performed
against bulk and surface stress, and calculating this work as a function of slab thickness allows to
discriminate between the constant contribution of surface stress and the contribution of bulk stress, which
grows in proportion to the thickness of the slab [97Iba1].
The calculation of surface free energy and surface stress data depends critically on the model used for
the interatomic interactions. Therefore, calculations for inert gas crystals, ionic crystals, covalent crystals
and metals are treated separately as each crystal class is described best by different models of the
interactions.
4.4.5.1 Inert gas crystals
The interatomic potential of inert gas crystals can be described by a Lennard-Jones potential [50Shu,
64Ben, 67Ben] with a repulsive interaction term which is proportional to r-12 and an attractive van der
Waals term proportional to r-6, where r is the distance between the atom and its surrounding neighbours.
Buckingham potentials, where the repulsive interaction is described by an exponential expression give
similar results [64Ben, 67Ben]. A face-centered-cubic arrangements of atoms is considered. The
calculations of the surface free energy by Shuttleworth [50Shu] with a Lennard-Jones potential and by
Benson and Yun [67Ben] with a Buckingham potential agree within a few percent and are presented in
section 4.4.7.4 in Table 4. The calculations indicate a slight outward relaxation by 2.5 % of the outermost
(100)-layer, which leads to a negligible correction of the surface free energy by less than 1 %, and
relaxation processes are not considered in the calculation. The surface free energy of inert gas crystals
with (100) faces is of order several ten mJ / m2. Surface stress was calculated by Shuttleworth [50Shu], his
results are given in Table 4. A slight compressive surface stress of the order of 10-3 N / m is calculated for
inert gas crystals.
It appears that these surface properties of inert gas crystals have not been studied experimentally, and a
critical assessment of the validity of the calculated data cannot be given.
4.4.5.2 Ionic crystals
The ionic interaction of alkali halides has been described by a Born-Mayer-Huggins potential which
considers Coulomb interactions ∼ r-1, van der Waals dipole-dipole interactions ∼ r-6 and dipole-quadrupole
interactions ∼ r-8, and exponential repulsive interactions [49Shu, 50Shu, 67Ben]. Composite potentials,
which have been spline-fitted to produce a continuous potential have been employed also [79Tas]. The
calculations indicate that the consideration of relaxation is essential. Early calculations of Shuttleworth
[50Shu] seem to have overestimated the effect of relaxation, leading to negative surface stress for all
alkali halides, except for NaF. More recent calculations by Benson and Yun [67Ben] and by Tasker
[79Tas] still support the importance of relaxation effects on both, surface free energy and surface stress,
but give positive surface stress values for the alkali halides.
The parameters of the potential function are adjusted to give the best description of bulk properties of
the ionic crystal. However, different parameters contribute differently to the surface properties as
compared to the bulk properties and the choice of one parameter set might be good for bulk, but
questionable for surface properties. Therefore, the results of the calculations of the surface free energies
and of the surface stresses in section 4.4.7.5 in Table 5 should be understood merely as estimates,
although the agreement with the scarce experimental data on surface free energy of liquid salts is within
10 %.
The tables show that the surface energy of most (100) alkali halide surfaces lies in the range 0.1 J / m2
to 0.4 J / m2, the surface stress varies from 0.1 N / m to 1 N / m.

New Series III/42A2
4.4.5.3 III-V compounds
The zinc-blende structure of III-V compounds is of special interest since this structure leads to the
peculiarity that opposite (111) surface orientations are populated solely either by group III or by group V
elements [60Gat, 62Han]. This leads to an inherent asymmetry of both surfaces due to the different
bonding situations on the two surfaces. Group III elements are bonded triply to the neighbouring group V
partners. However, group III elements are often bonded in planar sp2-hybrids to three partners, whereas
they are forced into a sp3-like tetrahedral bonding environment at the surface. It was argued [64Cah], that
a compressive stress should result on the group III surface, as the atoms would show the propensity to
retain a planar bonding geometry. On the surface terminated by group V elements, the bonding geometry
is very similar to a sp3-hybridization, which is known as a stable configuration of triply bonded group V
elements with dangling bonds, like NH3. Due to the slight bond angle deviation of the triply bonded group
V element from the tetrahedral configuration, a slight tensile stress was proposed for the group V
terminated surface [64Cah]. This simple electronic picture was put forward to explain the spontaneous
curvature of thin III-V compounds with (111) surface orientations [64Cah], see section 4.4.4.
Cahn and Hanneman introduced a non-central force model which considers bond-stretching and bond-
bending contributions to the interaction energy explicitly to calculate the surface stress difference between
group III and group V terminated surfaces [64Cah]. A compressive stress of order –1 N / m was
calculated for the group III terminated surface and a smaller tensile stress of order 0.5 N / m was derived
for the group V terminated surface, leading a surface stress difference of order 1.5 N / m. The calculations
are in rough qualitative agreement with experimental results on InSb [64Cah].
The surface energy of covalent III-V compounds was claimed to be in good approximation the energy
associated with the broken nearest neighbour bonds on the surface. The energy per bond was
approximated from the sublimation energy and lies in the range of 0.6 J / m2 to 2 J / m2. The surface stress
differences of (111) surfaces and the surface free energies for different orientations of various III-V
compounds are tabulated in section 4.4.7.6 in Table 6.
4.4.5.4 Group IV materials
Non-central force models have been applied to investigate the surface reconstruction and subsurface
relaxation of Si(100) [78App] and Si(111) [85Tro]. The interatomic potential was described by a model
due to Keating [66Kea], which takes central bond straining energy, and non-central bond bending energy
into account by two parameters which can be expressed as function of the cubic bulk elastic constants c11,
c12, and c44. The relation 2c 44 ( c11 + c 12 ) / ((c11 − c12 )(c11 + 3c12 )) = 1 has to be fulfilled in order to
express the atomic interaction with just two parameters. This condition is valid for the semiconductors of
the diamond structure diamond, Si and Ge [66Kea].
Pseudopotential methods have been employed to calculate surface free energy and surface stress of Si
and Ge slabs with (100) and (111) surface orientations [87Van, 89Mea1, 89Mea2, 89Pay]. The surface
energy Es is related to the energy per slab unit cell Eslab by E s = E slab − NE bulk , where N is the number of
atoms in the slab unit cell, and E bulk is the energy per atom of the bulk [89Mea1]. The surface stress is
1 dE s
calculated from the strain dependence of the surface energy τ (ijs) = , where A is the unit cell area
A dε ij
[89Mea1, 89Mea2]. The surface free energy follows as γ = E s / A . The effect of surface reconstruction
and of adsorption on the surface energy and the surface stress has been calculated [89Mea1, 89Mea2,
89Pay]. Adsorption is found to modify the surface free energy and the surface stress. The adsorbate
induced surface stress is mainly ascribed to the unnatural bonding topology of the adsorbate-substrate
complex [89Mea2]. The results of these calculation are presented together with the other calculated
properties in section 4.4.7.7 in Table 7 and in section 4.4.7.8 in Table 8. The calculations indicate surface
free energies of Si and Ge of order 1.7 J / m2 (1.4 eV / 1x1 cell), and report a compressive surface stress
of the clean and unreconstructed surfaces of the order – 0.7 N / m (– 0.5 eV / 1x1 cell).

New Series III/42A2
4.4.5.5 Metals
Pair potentials [90Wol, 91Wol] and many body potentials, corresponding to an effective medium theory
or embedded atom method, have been employed to calculate surface energy and surface stress for various
metals [86Ack, 87Ack1, 87Ack2, 88Dod, 91Gum, 90Wol, 91Wol, 94Wol1, 94Sto]. Many-body potentials
have been employed to study surface reconstruction in the glue model [86Erc, 87Erc], and the concept of
surface strain was introduced as a driving force for reconstruction [88Dod]. The role of surface stress for
reconstruction has been elucidated [92Cam1, 92Cam2, 94Wol1, 94Wol2, 93Nee, 93Cho]. The effect of
surface and interface stress on the elastic properties of metallic films and multilayers has been investigated
by the embedded atom method [91Gum, 94Str1, 94Str2].
Pseudopotential total energy calculations in the local density approximation have been applied to
calculate the surface energy and surface stress using a slab of material and a vacuum region which are
repeated throughout space [87Nee, 89Pay, 90Nee, 91Nee, 91Man]. Surface energy and surface stress are
calculated as the difference between surface and bulk properties. Pseudopotentials which use the linear
combination of atomic orbitals (LCAO) in the local density approximation have been employed to
calculate surface energy, surface stress and adsorbate induced changes of surface stress [95Fei1, 97Fei].
Unfortunately, an often cited paper which gives calculated values of surface stress and discusses the role
of surface stress for reconstruction remained ambiguous as to whether the stress or the difference between
the stress and the energy was tabulated [93Fio] (stress was tabulated). Furthermore, the stress was
apparently calculated for unrelaxed surfaces. Later calculations for the same system lead to lower surface
stresses [99Iba, 97Fill].
Calculated values of surface free energy and surface stress are presented in sections 4.4.7.9
and 4.4.7.10 in Table 9 and Table 10, respectively. Structural relaxations of the surface layer are
considered to influence both properties considerably, and calculations which consider these relaxations
should be regarded as providing more reliable results.
4.4.5.6 Calculated adsorbate-induced surface stress
First principles calculations of the effect of gas adsorption on the surface stress of Pt(111) have been
performed [97Fei]. The adsorption of hydrogen and oxygen was found to relief the tensile stress of the
clean Pt(111) surface partially. The results of this study are presented in section 4.4.7.11 in Table 11 and
in Fig. 11 and Fig. 12. These calculations suggest that the modification, i.e. weakening, of the surface
bonds of the substrate in the vicinity of the adsorbate is an important issue in the discussion of adsorbate-
induced stress.
Recent ab-initio cluster calculations using the local density approximation provide a qualitative
understanding of adsorbate-induced stress in terms of the charge transfer involved in the surface bond
[99Mül]. It was found that tensile (compressive) stress correlates with increase (decrease) of charge in the
metal-metal-bonds of the surface plane. Fig. 8 shows the change in the charge density induced by the
adsorption of oxygen and potassium on the surface plane of a Pt(111) surface, which was represented in
the calculation by a two-layer Pt25 cluster. The continuous (dashed) contour lines represent increase
(decrease) of charge and show the regions of the surface plane where the bonding is strenghtened
(weakened) by the adsorption. For O-adsorption the calculation shows that the induced compressive stress
is due to a charge transfer from Pt-Pt bonds to the adsorbate. Fig. 8(a) shows a depletion of charge away
from the three Pt-Pt bonds closest to the adsorbate, which is transferred to the O-atom. This charge
transfer is due the interaction of empty O–2p states with Pt–5d orbitals, which is so strong that the 5d
orbitals rotate in space to optimize the orbital overlap with the O-atom, leading to the weakening of the
nearest-neighbour Pt–Pt bonds and to the observed compressive stress. For K-adsorption on the other
hand, the calculation shows that the induced tensile stress is due to a charge transfer from the K-atom to
surface Pt–Pt bonds, which are strengthened by the adsorption. Fig. 8(b) shows that the transferred charge
goes into the region between the three Pt-atoms closest to the adsorbate. The K-surface bond is due to the
interaction of the K–4s state with Pt–6s states. In the clean surface the Pt–6s states lie above the Fermi
level, but due to the interaction with the K–4s state they move down and become locally occupied leading
to the increased Pt–Pt bonding. It is worth noticing that the Pt–5d states do not interact with the K–4s

New Series III/42A2
state. The latter state is so extended that it is essentially constant over the volume of the 5d states, such
that the positive and negative parts of the 5d function cancel out in the overlap integral.
This issue was raised by Feibelman, who pointed out that the unoccupied states at the Fermi level of Pt
are antibonding, which means that a direct K→Pt charge transfer would actually lead to weakening of the
Pt–Pt bonds, in contradiction with the experimental results for K [97Fei]. The point here is that the
transferred charge remains constrained within the range of the 4s state of the K-atom. Because of the large
extension of the 4s state this may not immediately apparent in some calculations.
Fig. 8a, b. (a) Difference charge density ∆ρ = ρ(Pt25O)-ρ(Pt25)-ρ(O) induced on the surface plane by the adsorption
of a O-atom on a Pt25 cluster representing a Pt(111) surface. The adatom is out of the plane. The continuous (∆ρ > 0)
and dashed (∆ρ < 0) contour lines represent density contours n310-5 eÅ-3, for n = −15,...,+15. (b) Id. for the adsorption
of a K-atom. For a discussion see [99Mül].

New Series III/42A2
4.4.6 Data
In the following section 4.4.7 experimental data and calculated values of surface free energy and surface
stress of clean solid surfaces are compiled. The data are organised as follows:
Table 2. Surface free energy from cleavage experiments

Table 3. Surface free energy measured at high temperature with an estimate of the temperature dependence
Fig. 9. Measured temperature dependence of the surface free energy of Cu

Fig. 10. Measured temperature dependence of the anisotropy of the surface free energy of Pb
Table 4. Calculated surface free energy and surface stress for inert gas crystals
Table 5. Calculated surface free energies and surface stress for alkali halides
Table 6. Calculated surface free energy and surface stress of III-V compounds
Table 7. Calculated surface free energy and surface stress for Si and Ge for different surface reconstruction
Table 8. Calculated adsorbate-induced changes of stress on semiconductor surfaces
Table 9. Calculated surface free energies of metals
Table 10. Calculated surface stress of metals
Table 11. Calculated adsorbate induced surface stress on Pt(111).
First principles calculations of adsorbate-induced surface stress for H and O on Pt(111) are quoted in
section 4.4.7.11 in Fig. 11 and Fig. 12.
Experimental results on adsorbate-induced changes of surface free energy are listed in section 4.4.8. The
following data are presented:
O / Ag Fig. 13 O / Fe Fig. 15
O / Fe-3% Si Fig. 14 O / Cu Fig. 16
Adsorbate-induced changes of surface stress are compiled in section 4.4.9 for the following systems.
O / Si(100) Fig. 17 K / Pt(111) Fig. 33

O / Si(111) Fig. 17 Ge / Si(100) Fig. 34
S / Ni(100) Fig. 18 As / Si(100) Fig. 35
O / Ni(100) Fig. 19 Ge / As / Si(100) Fig. 36
C / Ni(100) Fig. 20 Fe / Si(111) Fig. 37
S / Ni(111) Fig. 21 Ag / Pt(111) Fig. 38
O / Ni(111) Fig. 23 Fe / Cu(100) Fig. 39
C / Ni(111) Fig. 25 Co / Cu(100) Fig. 40
CO / Ni(100) Fig. 27 Ni / Cu(100) Fig. 41
CO / Ni(111) Fig. 28 Fe / W(100) Fig. 42
CO / Pt(111) Fig. 29 Co / W(100) Fig. 43
O / Pt(111) Fig. 29 Ni / W(100) Fig. 44
O / CO / Pt(111) Fig. 30 Pd / W(100) Fig. 45
O / W(110) Fig. 31 Fe / W(110) Fig. 46
Cs / Ni(111) Fig. 32
Ga / Si(111): Only the stress difference τ Si ,7 × 7 − τ Ga , 3× 3

= 1.28 N / m has been measured [90Mar].
Ag / Si(100): Only the Ag induced reduction of the surface stress of Si(100) has been reported for a
coverage of 0.25 ML Ag: τSi – τ0.25 ML Ag/Si = 0.45 N/m [97Deg]

New Series III/42A2
4.4.7 Clean surfaces

4.4.7.1 Surface free energy from cleavage experiments
Table 2. Surface free energy from cleavage experiments.
Material Cleavage plane T [K] Ambient atmosphere G [J/m2] Reference
LiF (100) 77 liq. N2 0.34 60Gil

MgO (100) 77 liq. N2 1.2 60Gil
CaF2 (111) 77 liq. N2 0.45 60Gil
CaCO3 (100) 77 liq. N2 0.23 60Gil
Si (111) 77 liq. N2 1.24 60Gil
Zn (0001) 77 liq. N2 0.105 60Gil
Zn (0001) 300 air 0.575 69Mai
W (001) 77 liq. N2 6.3 65Hul
Fe-Si3% (100) 20? liq. H2 1.36 60Gil
MgO (100) 298 air 1.15 +/- 0.08 63Wes2
KBr (100) 295 air 0.23 78Bec
KCl (100) 295 air 0.24 78Bec
NaCl (100) 295 air 0.34 78Bec
LiF (100) 295 air 0.64 78Bec
BaF2 (111) 295 air 0.35+/-0.12 78Bec
SrF2 (111) 295 air 0.42+/-0.08 78Bec
CaF2 (111) 295 air 0.51+/-0.14 78Bec
4.4.7.2 Surface free energy of metals near the melting point
Most experimental values of the surface free energy are obtained at temperatures near the melting point of
the material to ensure plastic flow for zero creep experiments performed on the solid state or to apply the
pendant drop or drop weight methods to the liquid state. Both experiment and theoretical considerations
suggest that the temperature dependence of the surface free energy is rather small, see section 4.4.7.3. An
upper limit is of the order of -0.0002 J / (m2 K), and this temperature dependence does not vary by more
than a factor of two for the different materials. Thus, in the following compilation, only the melting point
is given to indicate the temperature range at which the experiments have been performed. This
simplification seems tolerable in view of the rather large experimental deficiencies of the methods
employed. When comparing surface free energy data obtained for the liquid state with data of the solid
state, an approximately 13 % larger value for the solid state should be accounted for due to the energy
contribution from the heat of fusion [78Mie2]. All data have been extracted from the following review
articles [63All, 71Jon, 72All, 75Tys, 76Lan, 77Lan, 78Mie1, 78Mie2, 83Kum ].

New Series III/42A2
Table 3. Surface free energy γ from drop-weight and pendant-drop methods, measured at the respective
melting point under high vacuum. The free energy data are understood as describing the liquid-vapour
interface energy. The data of the drop weight method have been extrapolated to zero rod diameter. Only
zero creep experiments are considered for surface free energy data of the solid state. These data describe
the solid-vapour interface energy. Where available, zero creep data measured under vacuum are listed. For
measurements performed under a gas atmosphere, only data obtained for an inert gas atmosphere are
considered. If several values have been obtained, the average and its standard deviation are listed. The
calculated value of the temperature coefficient of γ for the solid state is taken from [78Mie2]. The melting
point temperatures are taken from [88Ida].
Material Melting drop weight pendant drop zero creep dγ / dT Ref.

point [K] method [J / m2] method [J / m2] method [J / m2] [J /(m2K)]
Ag 1234 1.205 ± 0.026 −0.00015 76Dig
1.005 ± 0.009 51Fun
Au 1336 1.410 ± 0.037 –0.00014 76Dig
1.350 ± 0.100 66Mul
Bi 544 0.501 ± 0.004 –0.00009 72She
Cd 594 0.675 ± 0.010 –0.00014 72Kho
β-Co 1765 2.424 ± 0.023 76Dig
Co 1765 1.9 1.855 ± 0.015 –0.00020 63All
Cr 2178 2.090 ± 0.020 –0.00017 76Dig
Cu 1356 1.520 ± 0.014 –0.00019 76Dig
1.750 ± 0.089 63Hoa
1356 1.31 1.295 ± 0.008 63All
δ-Fe 1808 1.910 ± 0.19 64Pri
γ-Fe 1808 2.170 ± 0.330 64Pri
Fe 1808 1.87 1.902 ± 0.007 –0.00019 63All
Ga 303 0.767 ± 0.006 –0.00012 72Kok
Hf 2480 1.6 1.628 ± 0.008 –0.00011 63All
In 430 0.633 ± 0.004 –0.00012 72Kho
Ir 2727 2.18 2.278 ± 0.013 –0.00016 63All
Mo 2895 2.630 ± 0.050 –0.00014 76Dig
1.920 ± 0.200 71Jon
2895 2.246 ± 0.013 2.239 ± 0.01 63All
Nb 2740 2.210 ± 0.054 –0.00014 76Dig
2.100 ± 0.100 61Rad
2740 1.924 ± 0.003 1.888 ± 0.005 63All
Ni 1728 1.940 ± 0.046 –0.00020 76Dig
1.820 ± 0.180 59Hey
1728 1.77 1.728 ± 0.01 63All
Os 2973? 2.4 2.511 ± 0.009 –0.00015 63All
Pb 601 0.560 ± 0.004 –0.00011 72Kho
Pd 1828 1.44 1.501 ± 0.007 –0.00016 63All
Pt 2047 1.950 ± 0.015 –0.00016 76Dig
2047 1.83 1.773 ± 0.005 63All
Re 3440 2.7 2.638 ± 0.017 –0.00016 63All
Rh 2239 1.9 2.013 ± 0.015 –0.00016 63All
Ru 2723? 2.23 2.223 ± 0.016 –0.00017 63All
Sn 505 0.673 ± 0.007 –0.00011 72Kho
0.685 ± N.A. 53Gre
Ta 3123 2.480 ± 0.070 –0.00014 76Dig
3123 2.15 ± 0.015 2.086 ± 0.009 63All

New Series III/42A2
Material Melting drop weight pendant drop zero creep dγ / dT Ref.

point [K] method [J / m2] method [J / m2] method [J / m2] [J /(m2K)]
Ti 1998 1.938 ± 0.042 –0.00013 69Lik
1.700 ± N.A. 68Kos
1998 1.6 1.656 ± 0.004 63All
Tl 576 0.562 ± 0.006 –0.00011 72She
V 1973? 1.9 1.948 ± 0.007 –0.00016 63All
W 3655 2.690 ± 0.022 –0.00015 76Dig
3655 2.471 ± 0.038 2.545 ± 0.012 63All
Zn 693 0.868 ± 0.014 –0.00018 72Kok
0.830 ± N.A. 65Bry
Zr 2130 1.85 –0.00011 73Kos
2130 1.48 1.469 ± 0.004 63All
4.4.7.3 Temperature dependence of the surface free energy
Fig. 9. The surface free energy of Cu vs. temperature.

The melting temperature Tm is indicated by the dashed
vertical line, data in the solid state have been obtained by
the zero creep technique [49Udi], data of the liquid by
the sessile drop technique [59All]. The jump of γ at the
melting temperature is ascribed to the heat of fusion. The
slope of the solid line in the liquid range is
-0.00031 Nm-1K-1 (data from [59All]).
The limited temperature range of experiments which exploit viscous flow for T < Tm in connection with
the scatter of the data on γ does not warrant to determine experimental data on the temperature coefficient
in the solid state. The scatter of surface free energy data for the solid state can be appreciated from Fig. 9.
The experimental determination of the temperature dependence of γ seems to be tractable only in the
liquid state. A jump of ∆γ in passing through the melting temperature is ascribed to the heat of fusion Hf ,
scaled to the area per atom A: ∆γ = H f / A , in agreement with the experimental values of Fig. 9 [59All].
According to the Gibbs-Duhem relation the temperature dependence of the surface free energy is given
by the surface entropy S(s), ∂γ / ∂T = −S ( s) [69Eri, 73Cou, 85Spa, 90Ada]. Configurational and vibrational
contributions to the surface entropy have been estimated [75Tys, 77Tys, 78Mie2] and an estimate of the
temperature coefficient dγ / dT is given for high temperature values of γ in section 4.4.7.2.

New Series III/42A2
4.4.7.3.1 Temperature dependence of the anisotropy of the surface free energy
The equilibrium shape of Pb crystallites of micrometer size on a graphite substrate has been analyzed by
scanning electron microscopy to derive the polar diagram of the surface free energy. From shape analyses
performed at different temperatures, the temperature dependence of the surface free energy anisotropy,
expressed as ratio γ {hkl} / γ {111} has been determined. The result is presented in Fig. 10. The surface free
energy anisotropy decreases non-linearly with increasing temperature.
{110}
{113}
Pb
X
1.06
{115} X
1.05 {331}
{112} X
1.04
{221}
X
1.03
#{111}
#{ hkl}
{100}
1.02
Fig. 10. Temperature dependence of the surface

1.01 free energy anisotropy of Pb. Equilibrium shapes of
Pb crystallites on graphite have been analysed at
473 K, 523 K, 548 K and 573 K. A decrease of the
1.00 anisotropy with increasing temperature is apparent
400 500 600 from the negative slopes of the curves [83Hey].
T [K]
4.4.7.4 Calculated surface free energy and surface stress for inert gas crystals
Surface free energies of fcc inert gas crystals have been calculated with a Lennard-Jones Potential for
{100}, {111}, and {110} surface orientations [49Shu, 64Ben, 67Ben]. The calculated values of the
different authors agree on average within 5 %, and the more recent calculations are quoted. Surface stress
has been calculated for the {100} surface [50Shu]. Structural relaxations have been considered in all
calculations.
Table 4. Calculated surface free energy γ of inert gas crystals for {111}, {100} and {110} orientations
and of the surface stress τ of the {100} surface in a [100] direction. Calculations were performed for
T = 0 K.
Material γ{111} [J / m2] γ{100} [J / m2] γ{110} [J / m2] τ[100] [N / m]

[64Ben] [64Ben] [64Ben] [50Shu]
Ne, fcc 0.0197 0.0203 0.0213 -0.0019
Ar, fcc 0.0432 0.0446 0.0468 -0.0046
Kr, fcc 0.0528 0.0545 0.0572 -0.0059
Xe, fcc 0.0621 0.0641 0.0673 -0.0067

New Series III/42A2
4.4.7.5 Calculated surface free energies and surface stress for alkali halides
The calculated values of surface free energy and surface stress depend strongly on the details of the
potential which is used in the calculation. Although bulk properties are well reproduced by different
potentials, the calculation of surface properties seems to be much more demanding. As experimental
values for both properties are scarce and exhibit wide scatter, a comparison to experimental data does not
help and no preference for one calculation can be given. Therefore calculations by Benson and Yun
[67Ben] and by Tasker [79Tas] are presented in the following table.
Table 5. Calculated surface free energy γ of alkali halide crystals for {100} and {110} surface orientation.
Surface stress τ is calculated for the {100} surface in a [100] direction. Values by two groups [67Ben,
79Tas] are given for comparison. Calculations were performed for T = 0 K.
Material γ{100} [J / m2] γ{100} [J / m2] γ{110} [J / m2] γ{110} [J / m2] τ[100] [N / m] τ[100] [N / m]
[67Ben] [79Tas] [67Ben] [79Tas] [67Ben] [79Tas]
LiF 0.142 0.480 0.568 1.047 0.494 0.407
LiCl 0.107 0.294 0.340 0.542 0.624 0.252
LiBr 0.086 0.252 0.280 0.444 0.591 0.213
LiI 0.073 0.216 0.226 0.356 0.546 0.224
NaF 0.216 0.338 0.555 0.741 0.741 0.442
NaCl 0.158 0.212 0.354 0.425 0.438 0.256
NaBr 0.138 0.187 0.304 0.362 0.386 0.221
NaI 0.118 0.165 0.252 0.294 0.341 0.182
KF 0.184 0.239 0.423 0.516 0.495 0.655
KCl 0.141 0.170 0.298 0.350 0.264 0.401
KBr 0.123 0.154 0.262 0.311 0.229 0.320
KI 0.113 0.139 0.222 0.268 0.191 0.237
RbF 0.171 0.228 0.380 0.439 0.427 0.474
RbCl 0.138 0.150 0.277 0.295 0.222 0.309
RbBr 0.122 0.136 0.246 0.264 0.192 0.264
RbI 0.104 0.118 0.210 0.222 0.176 0.222
CsF 0.148 0.341 0.371
CsCl 0.219
CsBr 0.200
CsI 0.175
4.4.7.6 Calculated surface free energy and surface stress of III-V compounds
A simple bond-straining bond-bending potential has been used to calculate surface stress on group III and
group V surfaces due to the non-ideal bonding geometry of the surface atoms [64Cah]. The surface energy
has been calculated from the number of broken bonds per surface area and using the sublimation energy as
an estimate for the bond energy [64Cah].

New Series III/42A2
Table 6. Calculated mean surface free energy γ for various orientations, and surface stress on the
group III (A) and on the group V (B) terminated surface of (111) oriented III-V compounds
γ 111 = 1 / 2( γ 111
A
+ γ 111
B
) . Calculations were performed for T = 0 K.
Material γ{100} γ{110} γ{111} τA, {111} τB, {111} Reference

2 2 2
[J / m ] [J / m ] [J / m ] [N / m] [N / m]
InSb 1.1 0.75 0.6 -0.6 0..3 64Cah
GaAs 2.2 1.5 1.3 -1.0 0.5 64Cah
InAs 1.4 1.0 0.84 -0.7 0.3 64Cah
GaSb 1.6 1.1 0.91 -0.8 0.4 64Cah
InP 1.9 1.3 1.1 64Cah
AlSb 1.9 1.3 1.1 -0.8 0.4 64Cah
AlAs 2.6 1.8 1.5 64Cah
GaP 2.9 2.0 1.7 64Cah
AlP 3.4 2.4 2.0 64Cah
4.4.7.7 Calculated surface free energy and surface stress for Si and Ge
Structural relaxations have been considered in the calculations of the following data.
Table 7. Calculated surface free energy γ and surface stress τ on various surface structures of Si and Ge.
τx represents the surface stress along a dimer bond on the (100) surface, τy represents the stress
perpendicular to the dimer bond. *Data for the Ge(100) dimer reconstruction represent the energy in eV
per dimer. Calculations were performed for T = 0 K.
Material γ [J / m2] Reference τx [N / m] τy [N / m] Reference

Si(100), 1 × 1 2.75 0.93 89Pay
2 × 1 , symmetric dimer 0.75 -2.11 89Pay
reconstruction
2 × 1 , asymmetric dimer 0.56 -0.56 88Ale
Si(111), 1 × 1 1.82 89Mea1 -0.68 -0.68 89Mea1

1 × 1 , faulted 1.89 89Mea1 0.14 0.14 89Mea1
3× 3 1.59 89Mea1 2.13 2.13 89Mea1
2 × 2 , adatom on top 1.55 89Mea1 2.08 2.08 89Mea1
2 × 2 , adatom on top, faulted 1.59 89Mea1 2.37 2.37 89Mea1
2 × 2 , adatom on hollow site 1.64 89Mea1 1.48 1.48 89Mea1
Ge(100), dimers 0* 89Pay

buckled, 2 × 1
buckled, 4 × 1 0.036* 89Pay
buckled, c 4 × 2 -0.066* 89Pay
buckled, 2 × 2 -0.070* 89Pay
Ge(111), 1 × 1 1.61 89Mea1 -0.84 89Mea1

1 × 1 , faulted 1.67 89Mea1 -0.3 89Mea1
2 × 2 , adatom on top 1.38 89Mea1 1.65 89Mea1
2 × 2 , adatom on top, faulted 1.41 89Mea1 1.93 89Mea1

New Series III/42A2
Material γ [J / m2] Reference τx [N / m] τy [N / m] Reference

Ge(111), 1 × 1 , unrelaxed 1.41 89Pay
1 × 1 , relaxed 1.15 89Pay
2 × 2 , adatom on top 1.20 89Pay
2 × 2 , adatom on hollow site 1.30 89Pay
3 × 3 , without adatoms 1.29 89Pay
3 × 3 , with adatoms 1.01 89Pay
4.4.7.8 Calculated adsorbate-induced changes of stress on semiconductor surfaces
Structural relaxations have been considered in the calculation of the following data.
Table 8. Calculated surface stress on substitutional and

adsorbate covered Si and Ge surfaces. Calculations were
performed for T = 0 K.
Material τ [N / m] Reference
Si(111), 1 × 1 -0.68 89Mea2
Al:Si(111), substitutional -8.08 89Mea2
As:Si(111), substitutional 2.84 89Mea2
B:Si(111), substitutional 6.1 89Mea2
Ga:Si(111), substitutional -5.58 89Mea2
Ge:Si(111), substitutional -1.4 89Mea2
3 × 3 Si / Si(111) 2.13 89Mea2

2 × 2 Si / Si(111) 2.08 89Mea2
3 × 3 As / Si(111) 2.93 89Mea2
3 × 3 Ga / Si(111) 1.69 89Mea2
Ge(111), 1 × 1 -0.84 89Mea2

As:Ge(111), subsitutional 3.04 89Mea2

New Series III/42A2
4.4.7.9 Calculated surface free energies of metals
No structural relaxation has been considered in [98Vit], and consequently these values are expected to be
significantly changed if relaxations are included. All other sources considered structural relaxations.
Table 9. Calculated surface free energy γ of metals for various orientations. The subscripts A and B refer
to the two possible surface terminations of (10 1 0) surfaces of hcp crystals [91Ove], where the
termination with the smaller lattice spacing is denoted A [98Vit]. Calculations were performed for
T = 0 K. The method of calculation is indicated: FS: empirical n-body Finnis-Sinclair potential, PSP: total
energy pseudopotential, EAM: embedded atom method, DFT: density functional theory, FPLAPW: full
potential linear combination of augmented waves, FPLMTO: full potential linear combination of muffin
tin orbitals.
Material γ [eV / atom] γ [J / m2] method Reference

Ac(100), fcc 0.764 0.732 DFT 98Vit
Ac(110), fcc 1.006 0.681 DFT 98Vit
Ac(111), fcc 0.786 0.868 DFT 98Vit
Ag(100) 0.59 DFT 93Fio
1.3 FPLAPW 89Wei
0.70 EAM 91Gum
1.27 FPLAPW 91Ers
1.21 FPLMTO 92Met
0.653 1.2 DFT 98Vit
0.759 FS 87Ack2
Ag(110), fcc 0.953 1.238 DFT 98Vit
1.4 FPLAPW 89Wei
1.26 FPLMTO 92Met
0.808 FS 87Ack2
Ag(111) 0.62 EAM 91Gum
1.21 FPLMTO 92Met
0.553 1.172 DFT 98Vit
0.576 FPLMTO 99Rub
0.620 FS 87Ack2
Al(100), fcc 0.689 1.347 DFT 98Vit
1.081 PSP 95Sch
Al(110), fcc 0.912 DFT 87Nee
1.090 PSP 95Sch
0.919 1.271 DFT 98Vit
Al(110), bcc 1.03 PSP 70Lan
Al(111) 0.96 DFT 89Pay,90Nee,
91Nee
0.704 DFT 87Nee
0.73 PSP 70Lan
0.939 PSP 95Sch
0.531 1.199 DFT 98Vit
Au(100) 0.75 DFT 93Fio
0.92 EAM 91Gum
0.895 1.627 DFT 98Vit
0.770 FS 87Ack2
Au(110), fcc 1.321 1.700 DFT 98Vit
0.816 FS 87Ack2

New Series III/42A2

Au(111) 1.248 DFT 89Pay, 91Nee
0.79 EAM 91Gum
1.04 PSP 91Tak
0.611 1.283 DFT 98Vit
0.624 FS 87Ack2
Ba(100), bcc 0.616 0.353 DFT 98Vit
Ba(110), bcc 0.464 0.376 DFT 98Vit
Ba(111), bcc 1.199 0.397 DFT 98Vit
Be(0001), hcp 0.495 1.834 DFT 98Vit
1.924 FPLAPW 92Fei
2.1 PSP 89Yu
Be (10 1 0) A, hcp 1.083 2.126 DFT 98Vit
Be (10 1 0) B, hcp 1.626 3.192 DFT 98Vit
Bi(100), sc 0.356 0.537 DFT 98Vit
Bi(110), sc 0.507 0.541 DFT 98Vit
Ca(100), fcc 0.535 0.542 DFT 98Vit
Ca(110), fcc 0.811 0.582 DFT 98Vit
Ca(111), fcc 0.484 0.567 DFT 98Vit
Cd(0001), hcp 0.300 0.593 DFT 98Vit
Co(0001), hcp 0.961 2.775 DFT 98Vit
Co (10 1 0) A, hcp 1.982 3.035 DFT 98Vit
Co (10 1 0) B, hcp 2.476 3.791 DFT 98Vit
Cr(100), bcc 2.020 3.979 DFT 98Vit
Cr(110), bcc 1.258 3.505 DFT 98Vit
Cr(111), bcc 3.626 4.123 DFT 98Vit
Cr(211), bcc 2.420 3.892 DFT 98Vit
Cr(310), bcc 3.030 3.775 DFT 98Vit
Cs(100), bcc 0.228 0.093 DFT 98Vit
Cs(110), bcc 0.10 PSP 70Lan
0.142 0.082 DFT 98Vit
Cs(111), bcc 0.390 0.092 DFT 98Vit
Cs(111), fcc 0.10 PSP 70Lan
Cu(100) 1.29 EAM 91Gum
1.802 FPLAPW 95Bro
0.906 2.166 DFT 98Vit
1.144 FS 87Ack2
Cu(110), fcc 1.323 2.237 DFT 98Vit
1.233 FS 87Ack2
Cu(111) 1.18 EAM 91Gum
1.94 FPLMTO 94Pol
0.707 1.952 DFT 98Vit
0.947 FS 87Ack2
Eu(100), bcc 0.653 0.463 DFT 98Vit
Eu(110), bcc 0.484 0.485 DFT 98Vit
Eu(111), bcc 1.282 0.524 DFT 98Vit
Fe(100), bcc 1.265 2.222 DFT 98Vit
Fe(110), bcc 0.978 2.430 DFT 98Vit
Fe(111), bcc 2.694 2.733 DFT 98Vit
Fe(211), bcc 1.804 2.589 DFT 98Vit
Fe(310), bcc 2.153 2.393 DFT 98Vit

New Series III/42A2

Fr(100), bcc 0.2021 0.081 DFT 98Vit
Fr(110), bcc 0.122 0.069 DFT 98Vit
Fr(111), bcc 0.346 0.080 DFT 98Vit
Ga(001), bct 0.376 0.661 DFT 98Vit
Ga(110), bct 0.507 0.797 DFT 98Vit
Ga(100), bct 0.695 0.773 DFT 98Vit
Hf(0001), hcp 1.400 2.472 DFT 98Vit
Hf (10 1 0) A, hcp 2.471 2.314 DFT 98Vit
Hf (10 1 0) B, hcp 2.892 2.709 DFT 98Vit
Hg(0001), hcp 0.111 0.165 DFT 98Vit
In(001), bct 0.342 0.488 DFT 98Vit
In(110), bct 0.422 0.560 DFT 98Vit
In(100), bct 0.632 0.592 DFT 98Vit
Ir(100) 1.85 DFT 97Fill
1.73 DFT 93Fio
1.772 3.722 DFT 98Vit
Ir(110) 2.59 DFT 97Fill
2.428 3.606 DFT 98Vit
Ir(111) 1.31 DFT 97Fill
3.264 DFT 89Pay, 91Nee
1.225 2.971 DFT 98Vit
K(100), bcc 0.249 0.142 DFT 98Vit
K(110), bcc 0.140 PSP 70Lan
0.167 0.135 DFT 98Vit
K(111), bcc 0.462 0.152 DFT 98Vit
K(111), fcc 0.140 PSP 70Lan
La(0001), hcp 0.909 1.121 DFT 98Vit
La (10 1 0) A, hcp 1.398 0.915 DFT 98Vit
La (10 1 0) B, hcp 1.690 1.106 DFT 98Vit
Li(100), bcc 0.383 0.522 DFT 98Vit
0.506 PSP 96Kok
Li(110), bcc 0.230 PSP 70Lan
0.289 0.556 DFT 98Vit
0.545 PSP 96Kok
Li(111), bcc 0.750 0.590 DFT 98Vit
0.623 PSP 96Kok
Li(111), fcc 0.360 PSP 70Lan
Lu(0001), hcp 1.102 1.604 DFT 98Vit
Lu (10 1 0) A, hcp 1.845 1.424 DFT 98Vit
Lu (10 1 0) B, hcp 2.093 1.616 DFT 98Vit
Mg(0001), hcp 0.437 0.792 DFT 98Vit
0.641 PS 94Wri
0.694 FPLAPW 92Fei
Mg (10 1 0) A, hcp 0.814 0.782 DFT 98Vit
Mg (10 1 0) B, hcp 1.072 1.030 DFT 98Vit
Mg(110), bcc 0.640 PSP 70Lan
Mg(111), fcc 0.540 PSP 70Lan
Mn(111), fcc 1.043 3.100 DFT 98Vit

New Series III/42A2

Mo(100), bcc 2.410 3.837 DFT 98Vit
3.52 FPLMTO 92Met
3.97 FPLMTO 99Rub
2.09 3.32 DFT 99Mar
2.1 FS 86Ack
Mo(110), bcc 1.534 3.454 DFT 98Vit
3.14 FPLMTO 92Met
1.6 3.6 FPLMTO 99Rub
1.829 FS 86Ack
Mo(111), bcc 4.068 3.740 DFT 98Vit
Mo(211), bcc 2.738 3.600 DFT 98Vit
Mo(310), bcc 3.601 3.626 DFT 98Vit
2.07 FS 86Ack
Na(100), bcc 0.290 0.264 DFT 98Vit
Na(110), bcc 0.230 PSP 70Lan
0.197 0.253 DFT 98Vit
Na(111), bcc 0.546 0.287 DFT 98Vit
Na(111), fcc 0.210 PSP 70Lan
Nb(100), bcc 1.987 2.858 DFT 98Vit
3.1 FPLAPW 89Wei
2.86 FPLMTO 92Met
2.88 FPLMTO 99Rub
Nb(100), fcc 1.956 FS 86Ack
Nb(110), bcc 1.320 2.685 DFT 98Vit
2.9 FPLAPW 89Wei
2.36 FPLMTO 92Met
1.2 2.53 FPLMTO 99Rub
1.669 FS 86Ack
Nb(111), bcc 3.668 3.045 DFT 98Vit
Nb(211), bcc 2.410 2.829 DFT 98Vit
Nb(310), bcc 3.145 2.861 DFT 98Vit
2.014 FS 86Ack
Ni(100) 1.57 EAM 91Gum
0.969 2.426 DFT 98Vit
1.444 FS 87Ack2
Ni(110), fcc 1.337 2.368 DFT 98Vit
1.548 FS 87Ack2
Ni(111) 1.44 EAM 91Gum
0.695 2.011 DFT 98Vit
1.153 FS 87Ack2
Np(111), fcc 1.252 2.208 DFT 98Vit
Os(0001), hcp 1.869 4.566 DFT 98Vit
Os (10 1 0) A, hcp 3.874 5.021 DFT 98Vit
Os (10 1 0) B, hcp 4.595 5.955 DFT 98Vit
Pa(100), bct 2.075 2.548 DFT 98Vit
Pa(110), bct 1.648 2.902 DFT 98Vit
Pa(001), bct 2.638 2.661 DFT 98Vit
Pa(111), fcc 1.424 2.302 DFT 98Vit
Pb(100), fcc 0.307 0.377 DFT 98Vit
Pb(110) 0.56 PS 91Man
0.513 0.445 DFT 98Vit
Pb(111) 0.496 PS 91Man
0.226 0.321 DFT 98Vit

New Series III/42A2

Pd(100) 0.91 DFT 93Fio
1.86 FPLMTO 92Met
2.3 FPLAPW 89Wei
1.152 2.326 DFT 98Vit
2.130 PS 96Wac
Pd(110) 2.5 FPLAPW 89Wei
1.97 FPLMTO 92Met
1.559 2.225 DFT 98Vit
Pd(111) 1.64 FPLMTO 92Met
1.559 2.225 DFT 98Vit
0.848 FPLMTO 99Rub
Po(100), sc 0.306 0.437 DFT 98Vit
Po(110), sc 0.370 0.373 DFT 98Vit
Pt(100) 1.21 DFT 93Fio
1.64 EAM 91Gum
1.378 2.734 DFT 98Vit
Pt(110) 2.009 2.819 DFT 98Vit
Pt(111) 2.067 PS 95Fei2
2.192 DFT 89Pay, 91Nee
1.44 EAM 91Gum
1.004 2.299 DFT 98Vit
Pu(111), fcc 1.104 2.007 DFT 98Vit
Ra(100), bcc 0.515 0.286 DFT 98Vit
Ra(110), bcc 0.377 0.296 DFT 98Vit
Ra(111), bcc 1.010 0.324 DFT 98Vit
Rb(100), bcc 0.229 0.112 DFT 98Vit
Rb(110), bcc 0.120 PSP 70Lan
0.150 0.104 DFT 98Vit
Rb(111), bcc 0.417 0.118 DFT 98Vit
Rb(111), fcc 0.110 PSP 70Lan
Re(0001), hcp 1.781 4.214 DFT 98Vit
Re (10 1 0) A, hcp 3.689 4.628 DFT 98Vit
Re (10 1 0) B, hcp 4.770 5.985 DFT 98Vit
Rh(100) 1.26 DFT 93Fio
2.81 FPLMTO 92Met
2.65 PS 93Mor
2.592 FPLAPW 90Fei
1.310 2.799 DFT 98Vit
Rh(110), fcc 1.919 2.899 DFT 98Vit
2.88 FPLMTO 92Met
Rh(111), fcc 1.002 2.472 DFT 98Vit
2.53 FPLMTO 92Met
1.136 FPLMTO 99Rub
Ru(0001), hcp 1.574 3.928 DFT 98Vit
1.472 FPLMTO 99Rub
3.0 PS 87Cho
4.3 PS 87Cho
Ru (10 1 0) A, hcp 3.201 4.236 DFT 98Vit
Ru (10 1 0) B, hcp 3.669 4.856 DFT 98Vit
Sb(100), sc 0.365 0.608 DFT 98Vit

New Series III/42A2

Sb(110), sc 0.560 0.659 DFT 98Vit
Sc(0001), hcp 1.080 1.834 DFT 98Vit
Sc (10 1 0) A, hcp 1.694 1.526 DFT 98Vit
Sc (10 1 0) B, hcp 2.011 1.812 DFT 98Vit
Sn(001), bct 0.387 0.611 DFT 98Vit
Sn(110), bct 0.509 0.620 DFT 98Vit
Sn(100), bct 0.716 0.616 DFT 98Vit
Sr(100), fcc 0.484 0.408 DFT 98Vit
Sr(110), fcc 0.725 0.432 DFT 98Vit
Sr(111), fcc 0.440 0.428 DFT 98Vit
Ta(100), bcc 2.174 3.097 DFT 98Vit
2.328 FS 86Ack
Ta(110), bcc 1.531 3.084 DFT 98Vit
1.980 FS 86Ack
Ta(111), bcc 4.201 3.455 DFT 98Vit
Ta(211), bcc 2.799 3.256 DFT 98Vit
Ta(310), bcc 3.485 3.139 DFT 98Vit
2.512 FS 86Ack
Tc(0001), hcp 1.527 3.691 DFT 98Vit
1.472 FPLMTO 99Rub
Tc (10 1 0) A, hcp 3.040 3.897 DFT 98Vit
Tc (10 1 0) B, hcp 3.893 4.989 DFT 98Vit
Tc(100), fcc 3.83 FPLMTO 99Rub
Th(100), fcc 1.233 1.468 DFT 98Vit
Th(110), fcc 1.722 1.450 DFT 98Vit
Th(111), fcc 1.073 1.476 DFT 98Vit
Ti(0001), hcp 1.234 2.632 DFT 98Vit
2.194 FPLAPW 96Fei
Ti (10 1 0) A, hcp 2.224 2.516 DFT 98Vit
Ti (10 1 0) B, hcp 2.435 2.754 DFT 98Vit
Tl(0001), hcp 0.221 0.297 DFT 98Vit
Tl (10 1 0) A, hcp 0.494 0.352 DFT 98Vit
Tl (10 1 0) B, hcp 0.529 0.377 DFT 98Vit
U(111), fcc 1.367 2.356 DFT 98Vit
V(100), bcc 1.725 3.028 DFT 98Vit
3.18 FPLAPW 98Vit
1.733 FS 86Ack
V(110), bcc 1.312 3.258 DFT 98Vit
1.473 FS 86Ack
V(111), bcc 3.494 3.541 DFT 98Vit
V(211), bcc 2.402 3.443 DFT 98Vit
V(310), bcc 2.921 3.244 DFT 98Vit
1.745 FS 86Ack
W(100), bcc 2.955 4.635 DFT 98Vit
4.78 FPLAPW 98Vit
2.924 FS 86Ack

New Series III/42A2

W(110), bcc 1.806 4.005 DFT 98Vit
2.575 FS 86Ack
W(111), bcc 4.916 4.452 DFT 98Vit
W(211), bcc 3.261 4.177 DFT 98Vit
W(310), bcc 4.338 4.303 DFT 98Vit
3.036 FS 86Ack
Y(0001), hcp 1.077 1.506 DFT 98Vit
Y (10 1 0) A, hcp 1.676 1.243 DFT 98Vit
Y (10 1 0) B, hcp 2.059 1.527 DFT 98Vit
Yb(100), fcc 0.484 0.478 DFT 98Vit
Yb(110), fcc 0.721 0.503 DFT 98Vit
Yb(111), fcc 0.423 0.482 DFT 98Vit
Zn(0001), hcp 0.385 0.989 DFT 98Vit
Zn(110), bcc 0.580 PSP 70Lan
Zn(111), fcc 0.440 PSP 70Lan
Zr(0001), hcp 1.288 2.260 DFT 98Vit
2.044 PS 94Yam
1.729 FPLAPW 96Fei
1.216 FPLMTO 99Rub
Zr (10 1 0) A, hcp 2.269 2.111 DFT 98Vit
Zr (10 1 0) B, hcp 2.592 2.411 DFT 98Vit
4.4.7.10 Calculated surface stress
Table 10. Calculated surface stress τ for metals for various orientations. The surface stress τaver is the
average value τ = 0.5( τ x + τ y ) for the (110) and (310) surfaces, where x: [ 1 10] and y: [001] for the
(110) plane and x: [ 1 30] and y: [001] for the (310) plane. Calculations were performed for T = 0 K. Ref.
[97Fill] did not clearly identify the two in-plane directions for Ir(110).
Material τ [001] τ [ 1 10] τaver τ [001] τ [ 1 10] or τ [ 1 30] Reference

[eV / atom] [eV / atom] [ N / m] [N / m] [N / m]
Ag(100) 0.88 93Fio
0.82 91Gum
1.172 87Ack2
Ag(110), fcc 0.738 87Ack2
Ag(111) 0.64 91Gum
0.620 87Ack2
Al(110), fcc 1.84 1.984 87Nee
Al(111) 1.248 89Pay, 90Nee, 91Nee
2.32 87Nee
Au(100) 1.62 93Fio
1.79 91Gum
1.822 87Ack2
Au(110), fcc 1.107 87Ack2
Au(111) 2.768 89Pay, 91Nee
1.51 91Gum
1.056 87Ack2

New Series III/42A2
Material τ [001] τ [ 1 10] τaver τ [001] τ [ 1 10] or τ [ 1 30] Reference

[eV / atom] [eV / atom] [ N / m] [N / m] [N / m]
Cu(100) 1.38 91Gum
1.696 87Ack2
Cu(110), fcc 0.957 87Ack2
Cu(111) 0.86 91Gum
0.626 87Ack2
Ir(100) 1.86 97Fill
2.94 93Fio
Ir(110) 1.70 ? 3.21 ? 97Fill
Ir(111) 1.96 97Fill
5.296 89Pay, 91Nee
2.241 86Ack
Mo(100), bcc 2.4 2000Mar
Mo(110), bcc 0.775 2.019 86Ack
Mo(310), bcc 1.184 2.247 86Ack
Nb(100), bcc 2.532 86Ack
Nb(110), bcc 0.301 2.168 86Ack
Nb(310), bcc 1.267 2.405 86Ack
Ni(100) 1.27 91Gum
0.977 87Ack2
Ni(110), fcc 0.707 87Ack2
Ni(111) 0.882 87Ack2
Pb(110) 1.28 1.17 91Man
Pb(111) 0.816 91Man
Pd(100) 1.05 93Fio
Pd(110) 1.22 1.79 1.86 2.74 95Fei1
Pd(111) 1.48 3.68 95Fei1
Pt(100) 2.69 93Fio
2.69 91Gum
Pt(110) 1.21 3.40 1.81 5.07 95Fei1
Pt(111) 2.77 6.75 95Fei1
5.60 89Pay, 91Nee
2.86 91Gum
Rh(100) 1.94 93Fio
Ta(100), bcc 3.249 86Ack
Ta(110), bcc 0.392 2.535 86Ack
Ta(310), bcc 1.647 3.085 86Ack
V(100), bcc 2.424 86Ack
V(110), bcc 0.263 1.939 86Ack
V(310), bcc 1.255 2.335 86Ack
W(100), bcc 3.032 86Ack
W(110), bcc 0.271 2.385 86Ack
W(310), bcc 1.450 2.833 86Ack

New Series III/42A2
4.4.7.11 Calculated adsorbate induced surface stress on Pt(111)
Structural relaxations are considered in the following calculations.
Table 11. Calculated surface stress of clean and adsorbate covered Pt(111). Coverage 1.0 equals one
adsorbate atom per Pt surface atom. Calculations were performed for T = 0 K.
Material Coverage τ [N / m] Reference

Pt(111) clean 6.27 97Fei
2 × 2 H / Pt(111) 0.25 5.18 97Fei
2 × 2 H / Pt(111) 0.75 2.78 97Fei
1 × 1 H / Pt(111) 1 1.7 97Fei
2 × 2 O / Pt(111) 0.25 3.07 97Fei
8.0
N/m Surface stress of Pt(111)
calculated for T = 0 K
6.4
4.8
surface stress
3.2
1.6
0
0 0.2 0.4 0.6 0.8 1.0
H coverage
Fig. 11. Calculated energy per surface Pt(111) atom vs. Fig. 12. Calculated surface stress vs. H coverage on
15 2
surface strain. The curves for the (1x1)-H and p(2x2)-O Pt(111) (coverage 1.0: 1.50×10 atoms / cm ). Data
covered surface are vertically displaced for clarity. The from [97Fei].
slope of the energy curves at strain 0 give the surface
stress . Note, that this slope is largest for the clean
surface, bottom curve, and smallest for the H coverage,
middle curve (data from [97Fei]).
4.4.8 Adsorbate-induced changes of surface free energy
The zero creep technique described in section 4.4.2.3 has been employed to measure the influence of gas
adsorbates on the surface free energy for oxygen on silver [52But2], oxygen on Fe-3 % Si [67Hon],
oxygen on Fe [68Hon] and for oxygen on copper [73McL, 76Bau].

New Series III/42A2
Fig. 14. The variation of the surface free energy of the

(100) plane of silicon iron for different partial pressures
of oxygen. An oxygen surface concentration of
Fig. 13. Surface free energy of Ag as measured by the
5.6 × 10 −14 cm is deduced from the slope of the curve
-2
zero creep technique in dependence of the oxygen
partial pressure. The slope of the solid curve indicates at 1330 °C, at 1410 °C the slope indicates 4.9 × 10 −14
-2
. × 1015 cm
-2
an oxygen surface concentration of 198 cm . Data from [67Hon].
[52But2].
Fig. 16. Variation of the surface free energy of copper

with oxygen pressure. Filled circles represent data
Fig. 15. The surface free energy of iron as a function of measured by the zero creep technique at 927 °C
the oxygen partial pressure. An oxygen surface concen- [73McL], open squares are from measurements at
14 -2
tration of 4.08x10 cm is calculated from the slope of 1027 °C [76Bau]. In the intermediate pressure range an
the linear section. At higher partial pressures oxidation 14 -2
oxygen surface concentration of 4.27x10 cm is
sets in and the zero creep technique measures the calculated from the slope of the curve. At higher
surface energy of two interfaces, iron-iron oxide and oxygen pressure, oxidation sets in that leads to an
iron oxide-oxygen gas. Data from [68Hon]. increase of the surface energy [76Bau].

New Series III/42A2
4.4.9 Adsorbate-induced changes of surface stress

The data of section 4.4.9 are all from cantilever bending experiments. The influence of sample clamping
on the reduced dimensionality of the sample curvature, see section 4.4.4, has been considered where
required.
4.4.9.1 Gas adsorption
Fig. 18. S-induced surface stress on Ni(100) vs. S

coverage. Data from [92San], rescaled to account for
the one dimensional bending.
15 2
(coverage 1.0: 1.61×10 atoms / cm ).
Fig. 17. O-induced surface stress on Si(111) vs. O

coverage. The slope of the solid line indicates an
oxygen induced compressive surface stress of
-5.7 N / m per monolayer O. The inset shows the result
for adsorption on Si(100). A slight tensile stress of
order 0.2 N / m is induced per monolayer O. Data from
[91San], rescaled to account for one dimensional
bending [97Iba1]
(Si(100): coverage 1.0: 6.78×1014 atoms / cm2,
Si(111): coverage 1.0: 7.83×1014 atoms / cm2 ).
Fig. 19. O-induced surface stress on Ni(100). Data from

[92San], rescaled to account for the one dimensional
bending. (coverage 1.0: 1.61×1015 atoms / cm2).
Fig. 20. C-induced surface stress on Ni(100). The plateau in

the stress curve starting at a coverage of 0.3 indicates the
formation of the p4g reconstruction. Data from [92San],
rescaled to account for the one dimensional bending.
(coverage 1.0: 1.61×1015 atoms / cm2).

New Series III/42A2
Fig. 22. Schematic of the S-induced recon-

struction of Ni(111). The black S atoms reside in
four-fold coordinated sites on the reconstructed
Fig. 21. S-induced surface stress on Ni(111). Data from surfaces, which exhibits a structure similar to the
[97Iba1]. The leveling off of the stress curve at a coverage of p4g reconstruction of Ni(100). From [97Iba1].
0.3 indicates a restructuring of the Ni(111) surface, which is
schematically shown in Fig. 22. Deposition at higher T leads
to a complete restructuring of the surface with a small
residual stress [97Iba1].
Fig. 23. O-induced surface stress on Ni(111). The

kink in the curve at a coverage of 0.3 is ascribed
to a repulsive interaction of O in hcp and p(2x2)
sites, schematically shown in Fig. 24. Data from
[97Iba1]. (coverage 1.0: 1.86×1015 atoms / cm2).

New Series III/42A2
Fig. 24. Schematic of the O adsorption sites, shown in lighter grey, at a coverage of 0.3. From [97Iba1].
Fig. 26. Model of the C-induced reconstruction

of Ni(111). C, shown in black, resides in four-
Fig. 25. C-induced surface stress on Ni(111). The leveling off fold coordinated sites on a (100)-like surface.
of the stress curve at a coverage of 0.4 is ascribed to a From [97Iba1].
restructuring of the Ni(111) surface to a (100)-like structure,
shown in Fig. 26. Data from [97Iba1].
Fig. 27. CO-induced surface stress on Ni(100).

The solid line is calculated in a model, which
uses a tensile stress for CO molecules without
nearest and next-nearest neighbours and a
compressive stress due to such neighbours. Data
from [97Iba1].

New Series III/42A2
Fig. 28. CO-induced surface stress on Ni(111). The Fig. 29. CO- and O-induced surface stress on Pt(111).
adsorption in bridge and three-fold coordinated hollow Both adsorbates induce compressive stress. Data from
sites induces compressive stress for all coverages. Data [97Iba1]. Considerably larger surface stress is induced
from [94Gro]. (coverage 1.0: 1.86×1015 atoms / cm2). as compared to adsorption on Ni(111), see Fig. 28 and
Fig. 23. This is ascribed to the much higher tensile
surface stress of Pt(111) as compared to Ni(111), see
Table 10. (coverage 1.0: 1.50×1015 atoms / cm2).
Fig. 30. Change of the surface stress of CO precovered Fig. 31. O-induced anisotropic surface stress on
Pt(111) at a coverage of 0.45 after exposure to O2. The W(110). At 800 s the sample has been exposed to O2
solid line is a simulation of the CO2 production which with a doser which has been closed at 1000 s. A 2x1-O
leaves a O covered surface behind. Data from [97Iba1]. structure with a coverage of 0.5 is formed which
(coverage 1.0: 1.50×1015 atoms / cm2). induces a compressive stress of -1.1 N / m along
[ 1 10], upper curve, and no measurable stress along
[001], lower curve.
After an initial O-uptake of the frontside the further
oxidation slows down and the slower oxidation of the
backside brings the stress difference between front and
backside close to zero. The begin of the arrow indicates
the formation of the (2x1)-O structure. The stress
asymmetry is ascribed to the anisotropic tensile surface
stress of W(110), see Table 10. Data from [99San2].

New Series III/42A2
4.4.9.2 Alkali metal deposition
Fig. 32. Cs-induced surface stress on Ni(111). The Fig. 33. K-induced surface stress on Pt(111).
solid curve is a guide to the eye. The first monolayer of Deposition at lower T, upper curve, induces tensile
Cs is completed at a coverage of 0.26 (coverage 1.0: stress which is ascribed to adsorbed K. Deposition at
1.86×1015 atoms / cm2). The tensile stress is ascribed to higher T, lower curve, favours incorporation of K,
a charge transfer from Cs to Ni (data from [97Iba1]). which induces compressive stress. Data from [97Iba1]
Semiconductor and metal deposition
4.4.9.3 Semiconductor and metal deposition
Fig. 34. Ge-induced surface stress on Si(100) during

deposition at 500 °C. Ge induces compressive surface Fig. 35. As-induced surface stress on Si(100) during
stress which levels off after a deposition of 6 ML, a deposition at 500 °C. The stress curve levels off after
total of 7 ML has been deposited. Data from [94Sch] 160 s when an As coverage of 1 is reached. A
(1 ML: 6.78×1014 atoms / cm2). monolayer As induces a tensile stress of 1.4 N / m.
Data from [94Sch] (1 ML: 6.78×1014 atoms / cm2).

New Series III/42A2
0
N/m Ag / Pt(111)
-5 T = 300 K
-10
-15
)
-20
0 2 4 6 8 ML 10
Ag coverage
Fig. 37. Ag-induced surface stress on Pt(111). The Ag-

induced compressive stress is larger than the calculated
Fig. 36. Surface stress on As-precovered Si(100)
misfit stress. Data from [97Iba1] (coverage 1.0:
during the co-deposition of Ge and As at 500 °C. At
9 ML Ge coverage a slight kink in the stress curve 1.50×1015 atoms / cm2).
indicates the end of pseudomorphic layer-by-layer
growth and defects are formed for higher coverages.
Data from [94Sch].
Fig. 38. Fe-induced surface stress on Si(111) during deposition at 600 K

and 300 K (inset). At higher temperature a silicide formation sets in which
leads to high tensile stress. The stress continues to increase even after
termination at the deposition of 1.2 nm Fe. Deposition of 1.5 nm at 300 K
leads only to a minute stress which is ascribed to the growth of Fe islands
on the intermixed Fe-Si interface. Data from [95San2].

New Series III/42A2
Fig. 39. Fe-induced surface stress on Cu(100) at 300 K. Fig. 40. Co-induced surface stress on Cu(100).
Deposition proceeds beyond 15 ML. The kinks of the Deposition proceeds beyond 15 ML. The slope
stress curve at 3 ML and at 11 ML indicate structural corresponds to a tensile film stress of 2.5 GPa. The
transitions in the Fe film from fct to fcc and from fcc to lattice mismatch of 2 % is expected to induce a tensile
bcc, respectively. Data from [99Gut] (1 ML: film stress of 2.9 GPa as calculated from 3rd order
1.53×1015 atoms / cm2). continuum elasticity. Data from [99Gut] (1 ML:
1.53×1015 atoms / cm2).
Fig. 41. Ni-induced surface stress on Cu(100). Fig. 42. Fe-induced surface stress on W(100). The kink
Deposition proceeds beyond 15 ML. The slope in the stress curve around 3 ML indicates the end of
corresponds to a tensile film stress of 4.3 GPa. The pseudomorphic growth. The initial compressive stress
lattice mismatch of 2.5 % is expected to induce a is of opposite sign than the calculated misfit stress. The
tensile stress of 4.2 GPa as calculated from 3rd order slope of the data points from 1 to 3 ML corresponds to
continuum elasticity. Data from [99Gut] (1 ML: a tensile film stress of 9.7 GPa. Data from [99Gut]
1.53×1015 atoms / cm2). (1 ML: 1.00×1015 atoms / cm2).

New Series III/42A2
3 4
N/m
N/m Co / W(100) 3 Ni / W(100)
2 T = 300 K T = 300 K
2 closed
1 1 open
open
0 0
-1
)
)
-1
-2
-2
0 2 4 6 8 ML 10 0 2 4 6 8 10 12 14 16 18 ML
Co coverage Ni coverage
Fig. 43. Co-induced surface stress on W(100). Fig. 44. Ni-induced surface stress on W(100). The kink
Deposition proceeds beyond 10 ML. The kink in the in the stress curve at 2 ML indicates the end of
data points at 2.5 ML indicates a structural transition in pseudomorphic growth. The initial compressive stress
the film from pseudomorphic to hcp growth. The initial is of opposite sign than the calculated misfit stress.
compressive stress is of opposite sign than the Data from [99Gut] (1 ML: 1.00×1015 atoms / cm2).
calculated misfit stress. Data from [99Gut] (1 ML:
1.00×1015 atoms / cm2).
Fig. 45. Pd-induced surface stress on W(100). The kink

Fig. 46. Anisotropic Fe-induced surface stress on
in the stress curve at 2 ML indicates the end of
pseudomorphic growth and the onset of hcp growth. W(110). Stress components along [ 1 10], upper curve,
Data from [99Gut] (1 ML: 1.00×1015 atoms / cm2). and along [001], lower curve have been measured. The
kink at 1.2 ML is ascribed to the formation of misfit
distortions and indicates the end of pseudomorphic
growth. The inset shows a blow-up of the small
coverage range. Data from [99San2] (1 ML:
1.42×1015 atoms / cm2).

New Series III/42A2
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New Series III/42A2
4.5 Surface phonon dispersion
M.A. ROCCA
Acronyms and symbols

ARP - Angle Resolved Photoemission
DFT - Density Functional Theory
FT - Frustrated Translation
HATOF - He Atoms Time of Flight
HREELS - High Resolution Electron Energy Loss Spectroscopy
IRAS - Infrared Reflection Absorption Spectroscopy
L - Longitudinally polarised mode
LDA - Local Density Approximation
LDM - Lattice Dynamical Model
LEED - Low Energy Electron Diffraction
ML - Monolayer
NEXAFS - Near Edge X-rays Absorption Fine Structure
q|| - Phonon wavevector
RBS - Rutherford Back Scattering
RW (R) - Rayleigh Wave
SCP - Self Consistent Pseudopotential
SBZ - Surface Brillouin Zone
SEXAFS - Surface Extended X-rays Absorption Fine Structure
SH - Shear Horizontally polarised mode
SV - Shear Vertically or sagittally polarised mode
T - Crystal temperature
ϑi - Angle of incidence of probe particles
ϑf - Angle of scattering of probe particles
θ - Adsorbate coverage
ω - Phonon frequency
4.5.1 Introduction
4.5.1.1 Background and general layout
The surface phonon spectrum consists of the continuum of the projection of the bulk modes onto the two
dimensional surface Brillouin zone (SBZ) and of surface modes, localised in the gaps of the bulk bands.
The amplitude of such modes is large near to the surface and decreases rapidly towards the bulk. The
presence of the surface may moreover modify the amplitude of the bulk modes leading to the formation of
so-called surface resonances. In presence of adsorbates, new modes will be present because of the extra
degrees of freedom connected with the motion of the adatoms or of the admolecules. If the latter interact
with each other, either directly or via the substrate, their vibrations will behave collectively and disperse
with parallel wavevector, q||. Depending on the relevant interatomic forces, the adsorbate modes may lie
in the frequency domain of the substrate atoms and hybridise with modes of the same symmetry. Energy
gaps will then open up in the dispersion curves. If hybridisation takes place with volume modes, the
adsorbate vibration becomes a surface resonance and its energy will leak into the substrate and give rise
to a finite linewidth. Substrate and adsorbate phonon frequency and dispersion are determined by the
interatomic forces, which are intimately linked to the surface structure. The knowledge about the
spectrum of surface phonons can therefore provide important clues to understand the structure as well as
the nature of forces driving the surface into one particular structure [89Yan, 90Voi2, 97Nag].

4.5-2 4.5 Surface phonon dispersion [Ref. p 4.5-68
Pure surface modes are usually denoted by Sn, where the index n numbers the branches starting from the
one at the lowest frequency. Similarly, the surface resonances are denoted by MSn or Rn and numbered
with the same criterion. The acoustic mode with slowest velocity is usually, but not always, mainly shear
vertically polarised and coincides with the Rayleigh wave (RW) in the elastic continuum limit [1887R].
The adsorbate induced modes are denoted by the chemical symbol of the adsorbate and by a suffix
indicating the relevant motion, e.g. || (⊥) for modes polarised primarily parallel (perpendicular) to the
surface plane. The surface phonon spectrum is influenced by physisorbed as well as by chemisorbed
species, either because of the hybridisation of the adsorbate induced modes with those of the substrate, or
because of the modification of the interaction between the substrate atoms induced by adsorption. The
latter effect can change the frequency of the substrate modes or induce the spill out of new modes off the
bulk bands. Moreover, at a given wavevector, new surface bands will be generated because of the
symmetry reduction associated to the backfolding of the surface Brillouin zone. Finally, adsorption can
induce the reconstruction of the surface.
Dipole active adsorbate and substrate modes had been investigated already in the seventies by infrared
absorption spectroscopy (IRAS) and by high resolution electron energy loss spectroscopy (HREELS).
The first surface phonon dispersion curves were measured, however, only at the beginning of the '80-ties
by inelastic He atom scattering (HATOF, He atom time of flight spectroscopy) and by HREELS in impact
scattering. The former technique exploits the supersonic expansion of He from a nozzle source, by which
a thermal energy beam (Ei=20-60 meV) is generated with resolutions which can go down to 200 µeV.
Phonon measurements with HATOF are therefore limited in the frequency domain by the low energy of
the impinging projectiles. He atoms interact with the low density tail of the surface electron density and
have therefore an absolute surface sensitivity. On the other hand, HREELS relies on inelastic low energy
(20 <Ei<200 eV) electron scattering in the so-called impact scattering regime, in which the energy loss
occurs during the short range interaction with the ion cores. Since electrons in this energy range penetrate
some 10 to 20 Å below the surface, the inelastic information is mediated over the outermost two or three
layers. Modes with maximum amplitude in deeper layers (and especially in the second layer) can thus be
excited. The main limitation of HREELS with respect to HATOF is the resolution, which, in spite of the
recent improvements, is limited to 2 meV for out-of-specular measurements. The latter problem can be
however overcome by exploiting multiple scattering which causes a strong, and mode specific, energy
dependence of the inelastic cross section, allowing to tune the spectrometer on each particular phonon
branch and thus to distinguish between features whose difference in frequency is smaller than the energy
resolution [85Xu, 89Wu]. The comparison of experimental cross sections with the theoretical forecast
proved in some cases to be essential for a correct assignment of the loss peaks to the different vibrational
modes. The modification of the force constant between surface atoms may indeed shift the different
phonon branches to such an extent that the knowledge of the spectrum expected from the bulk force
constants can be insufficient to interpret the data. On the theoretical side lattice dynamical models (LDM)
based on force constants were developed in the early years [71All, 74Arm] and allowed reliable
predictions of the surface phonon spectrum. More recently, thanks to the remarkable advances achieved
in the development of computational schemes based on density functional theory (DFT) and to the
availability of supercomputers, it became possible to perform ab-initio calculations of the surface phonon
spectrum also for adsorbate covered surfaces [96Bun, 99Fri1].
Over the past decades progress in the field of surface phonon dispersion of clean and adsorbate
covered surfaces has been surveyed in a number of review articles, including those of Rocca et al.
[86Roc1], Ibach [90Iba, 91Iba, 92Iba1, 94Iba], Wöll [91Wöl], Toennies [92Toe], Benedek and Toennies
[94Ben], and Fritsch and Schröder [99Fri1]. Worth mentioning is also the book dealing principally with
surface phonons of clean surfaces, edited by Kresse and de Wette [91Kre]. A collection of the data
available on surface phonons of bare surfaces (research status of 1994) can be found in Landolt Börnstein,
New series Vol. III/24 B, Chapt. 4.

Ref. p. 4.5-68] 4.5 Surface phonon dispersion 4.5-3
4.5.1.2 Symmetry considerations, energy and momentum conservation and relevant selection rules
in inelastic scattering
The surface phonon spectrum is usually measured and computed along the border of the irreducible part
of the two dimensional surface Brillouin zone, whose principal points and directions are defined in Fig. 1
for the principal fcc and bcc surfaces. Along mirror planes the normal modes will split into two
subgroups, whose atomic displacement pattern is, respectively, even (sagittal modes) or odd (shear
horizzontal modes) with respect to reflection. For scattering experiments performed with in-plane
scattering geometry and for which the scattering plane coincides with a mirror plane of the crystal, only
the excitation of sagittally polarised phonons is allowed. Since most experiments take advantage of this
selection rule no measurements of the dispersion of SH modes exist for adsorbate covered surfaces,
contrary to the case of bare surfaces [92Bal]. Similarly, in presence of glide planes (as e.g. for C, N and
CO on Ni(100)) the inelastic scattering selection rules along the glide plane require that the excitable
modes are symmetric with respect to glide reflection in the first SBZ and antisymmetric in the second
SBZ [88Rah]. Totally symmetric modes are moreover dipole active. Accurate measurements of the
frequency of such phonons at vanishing wavevector can therefore be performed with HREELS or with
IRAS with sub meV resolution.
In inelastic scattering experiments energy and momentum conservation read:
!2 2
!ȦT || ) = (k f − k i2 ) (1)
2m
& & &  cosĳ f   cosĳ i 

ǻk || = g || + q || = k f sinș f   − k i sinș i  . (2)
 sinĳ f   sinĳ i 
where ω and q|| are the energy and the wavevector of the phonon, respectively. The polar angles ϑi and ϑf
are measured from the surface normal and ϕi and ϕf are the azimuth angles in the surface plane usually
& &
chosen to be zero. k i and k f are the wavevectors of the impinging and of the outgoing particles. A
positive value of ∆k(q||) corresponds to the creation of a phonon, a negative value to its destruction.
Similarly we will refer to a positive q|| as an event in which a forward directed phonon is created. In an
& &
usual experiment k i and k f are chosen in the sagittal plane and, in order to take advantage of the selection
rules and to compare the experimental results with theoretical predictions, the latter is aligned with a high
symmetry crystallographic direction. For this special case the conservation equations can be conveniently
visualized with the aid of the Ewald construction, shown in Fig. 2. The vertical bars are the surface
reciprocal lattice rods; the circle shows the final momentum states accessible in elastic scattering; and the
arrow indicate the wavevectors of incident and reflected particles. For HREELS the impact energy (of
the order of several tens of eV) is much larger than the energy loss so that the spectrum recorded for a
given scattering angle, ϑf, corresponds effectively to a constant momentum transfer. For HATOF, on the
other hand, the measurements correspond to parabolic scan curves in the ω - q|| space. Scattering events
corresponding to different values of q|| are therefore present in the same spectrum. For construction
reasons HATOF apparatuses usually have the constraint that ϑi + ϑf is constant and the measurements are
recorded by rotating the crystal.
4.5.1.3 Folding of the surface Brillouin zone by symmetry reduction, mode mixing,
phonon crossing and opening of energy gaps
If the adsorbate builds a superstructure or induces a reconstruction with a larger unit cell than the one of
the bare substrate, the size of the new Brillouin zone will be reduced. Previously independent reciprocal
space regions may therefore coincide after adsorption, a phenomenon that is usually referred to as folding
of the zone. The folding process is shown in Fig. 3 for the case of a (100) face covered with c(2x2) and
p(2x2) overlayers. As one can see, for the former case the size of the zone is halved so that the Γ and the
M points of the clean substrate coincide, and so do the previously independent ∆ and Υ directions. For

the latter case the zone is reduced to one fourth, so that also Χ is folded back to Γ . Frequency gaps will
open up at the new zone boundaries or at crossing points of phonon branches of the same symmetry. The
new normal modes can then be obtained by linear combinations of the old substrate and/or adsorbate
modes.
As an example let us discuss the displacement pattern for phonons of the c(2x2) fcc(100) geometry at
ī and Χ , which are shown in Fig. 4. The relevant surface point symmetry group is C4v so that the modes
belong either to the symmetric representation, A1, or to the antisymmetric representations, B1 and B2 or to
the non symmetric degenerate representation, E. For the latter modes linear combinations can be drawn
whose displacement pattern is either even or odd with respect to the (1 1 0) mirror plane. The E symmetry
modes d and e at Γ originate, respectively, from the longitudinal and from the shear horizontal modes of
the clean surface at Γ and M ; the B2 mode comes from the displacement pattern of the Rayleigh wave at
the former M point; the A1 mode f exists also for the clean surface, while the E modes g and h are
combinations of the previously longitudinal and SH modes. The modes a, b and c correspond principally
to the motion of the adsorbate and are in a different frequency range (usually higher for light
chemisorbates) than the corresponding substrate modes d, e and f.
At X the modes with A and B symmetry arise from the combination of the displacement patterns of
the longitudinal and SH phonons previously located at the two Χ points of the clean surface, while the E
modes are generated from the Rayleigh wave. In particular the A1 mode is a true surface phonon as it
comes from the longitudinal surface mode S6, present in a gap near X , which is preserved upon
backfolding. The displacement pattern of the A2 and B2 modes corresponds to established reconstruction
patterns. They occur, respectively, for the p4g(2x2) structures of C on Ni(100) [79Onu] and of O on
Rh(100) [98Alf, 99Alf], and suggest that the reconstruction takes place via the softening and freezing of
such modes.
4.5.1.4 Phonon anomalies
4.5.1.4.1 Effect of mass loading, modification of force constants and surface stress
Mode softening and, in general, anomalies of the substrate phonon frequencies can be induced by the
adsorbate by modifying the force fields acting between the substrate atoms. This phenomenon was first
observed for O/Ni(100) [83Sze]. The phonon dispersion curve for the c(2x2) structure along Γ – Χ is
reported in Fig. 5. The frequency of the RW at X , which is equal to 130 cm–1 for the bare surface,
decreases to 80 cm–1. The effect cannot be accounted for by the loading of the surface atoms, which reads
[67Ben]
ma
Ȧ 2 = Ȧ 02 (1 − θ ), (3)
ms
where ma and ms are the adsorbate and substrate mass, respectively, ω0 is the frequency of the mode for
the bare surface, and ș is the coverage. A dramatic change in the interaction between the substrate atoms
must therefore occur and indeed the frequency shift can be reproduced by LDM either (left panel in
Fig. 5) by reducing by 70 % the force constant between the Ni atoms in the first and in the second crystal
layer (second derivative of the interaction potential) or (right panel) by introducing a compressive surface
stress (first derivative of the pairwise interaction potential) at the surface. The two causes cannot be easily
distinguished just by measuring the phonon dispersion curves since both LDM can give best fits of
equivalent quality.
The adsorbate induced compressive surface stress was however demonstrated to be relevant for the
O/Ni(100) system because it explains also other findings: i) the observed frequency shift depends on the
order state of the adsorbate and is smaller when the oxygen is adsorbed disorderly [85Roc], an effect that
would not be expected if the adsorbate affects only the surface force constants between the substrate
atoms; ii) Ni(100) reconstructs with clockwise and anti-clockwise rotations of the substrate atoms around
the adsorbate when the latter is C or N instead of O or S. The displacement pattern of such p4g

reconstruction coincides with the one of the A2 modes at the X point of the c(2x2) structure (see right
panel of Fig. 4, mode g), suggesting that the latter gets frozen into the surface by a soft phonon
mechanism [85Rah]. Without adsorbate induced stress, however, the freezing of the A2 mode would
imply the unphysical result that the force constant between first and second Ni layer, k12, vanishes.
Moreover the B2 mode should freeze in first when k12 is reduced [88Sze]. On the contrary in the presence
of a compressive stress, the freezing in of the A2 mode occurs first and for a non vanishing value of k12
[86Rah, 90Yan]. The proposed mechanism is hence that the adsorbate pushes against the substrate atoms
at the border of the fourfold hollow and that the atoms can adjust to such forces by relaxing for the loose
p(2x2) structure and for the disordered phase, but not for the c(2x2) phase, for which therefore a
compressive stress builds up. For C or N chemisorption the adsorption distance is much smaller than for
O and the stress is correspondingly larger. When a certain threshold is overcome, the stress is released by
the lateral shift of the substrate atoms. The stress induced by adsorption on Ni(100) was measured directly
in a later experiment [91San, 92San1, 97Iba]. In accord with the above explanation the build up of surface
stress has been found indeed to be much larger for the c(2x2)-O than for the p(2x2)-O structure and even
larger for C adsorption. It stops as soon as the p4g surface reconstruction sets in at the coverage of 0.3
ML of carbon. Cluster calculations confirm the picture showing that the strong C–Ni bond removes
charge from the Ni–Ni bonds that are no longer able to balance the repulsive interaction between the
incompletely screened Ni nuclei [86Mül]. The same mechanism was proposed to account also for the
stiffening of the Rayleigh wave for the bare Ni(100) surface, which had been previously ascribed to a
20% increase of the force constant between the Ni atoms of first and second crystal plane. Accordingly
tensile surface stress is present on the bare surface. This mechanism has the advantage that it does not
imply a reduction of the first interlayer spacing which is present for Ni(100) [83Fre1, 83Fre2] but not for
Cu(100) [86Wut] that has a comparable stiffening of the Rayleigh wave at X . Surface stress was
proposed to play a role also for other phonon anomalies as e.g. for the softening of the RW at Υ on
Ni(110) upon H adsorption [87Leh1]. For Rh(100) p4g c(2x2) O, on the other hand, a different
mechanism must be active as the stress caused by adsorption is small, the adsorption distance being much
larger than for C or N on Ni(100). Indeed the reconstruction pattern corresponds then to the displacements
of the B2 mode at X of the c(2x2) overlayer (see Fig. 5), which gets soft because of the adsorbate induced
reduction of the force constants between the substrate atoms [98Alf, 99Alf, 99Bar].
Another effect observed quite systematically is the strong reduction of the cross section of the
longitudinal surface resonance, which dominates the HATOF spectra for fcc (111) surfaces and which
originates from a strong reduction of the in-plane force constant between surface atoms. Especially H is
often seen to have the effect of eliminating the anomaly, restoring the surface force constants to the bulk
value [87Ber]. This adsorbate was intensively studied also for elemental semiconductors, being important
because of technological applications as well as because it enables to study the dynamics of the
unreconstructed bare surface [96Grä2].
4.5.1.4.2 Kohn anomaly
Phonon anomalies are induced also by the coupling of phonons with the electronic excitation spectrum.
This mechanism, called Kohn anomaly, corresponds to the breakdown of the adiabatic separation of ionic
and electronic degrees of freedom and takes place for wavevectors corresponding to significant Fermi
surface nesting. This is the case for H/W(110) [92Hul1, 93Hul1, 93Hul2, 94Bal2, 96Bal] and H/Mo(110)
[93Hul1, 93Hul2, 97Krö] that show indeed a phonon anomaly. The HATOF data for H/W(110) along the
[001] direction is reported in Fig. 6, together with a scan curve crossing the critical region in reciprocal
space. For q|| ≤ 0.6 Å–1 two modes are present and correspond to the Rayleigh wave (lower frequency
mode) and to the longitudinal resonance (higher frequency points). Around q||c =0.93 Å–1, however, a
strong softening of the lower phonon branch occurs, which is accompanied by the appearance of a third
branch whose frequency nearly vanishes at q||c. The peaks labeled with 4 and 1 in the bottom panel
correspond to the upper and lower branch of the splitted lower frequency mode. Peak 1 is distinctly
broader than peak 4. The anomaly is present for all wavevectors whose x-component ([001] direction or
Γ – H ) is close to 0.9 Å , indicating that the anomaly has a one-dimensional character. Along Γ – S ,
–1
e.g. q||c is at 1.225 Å , corresponding to (q||x =1.00, q||y = 0.707) Å–1.

–1

HREELS investigation demonstrated that also the longitudinal surface phonon has a shallow dip at the
same wavevector [94Bal2, 96Bal]. The lowest branch was however not observed. First principle
calculations of the phonon spectrum [96Bun] reproduced the shallow dip and confirmed that branch 1 is
the RW. The current understanding of branch 4 is that it corresponds to the excitation of electron hole-
pairs [95Koh], for which He atom scattering is more sensitive than electron scattering. The effect arises
because He atoms interact with the low density tail of the electron distribution outside of the surface,
while electrons are scattered by the high electron density close to as the nuclei of the substrate.
Alternatively it was proposed that the excitation is connected with a plasmon like motion of the H atoms
[96Bun]. The latter explanation holds however only for H/W(110) as the H adatoms on Mo(110) are
fairly localised [97Krö]. The critical wavevector at which the anomaly occurs for Mo(110) is linked to
nesting of the Fermi-surface contours associated to the (d3z2–r2,dxy) band, which has nearly one
dimensional character. It runs parallel to Γ – N , and perpendicular to Γ – S , in significant parts of the
surface Brillouin zone, and is shifted to lower energies by hydrogen adsorption, thus becoming localised
at the surface [95Koh, 96Koh1, 96Koh2, 97Koh]. For H/W(110), on the other hand, the situation is more
complicated. Recent angle resolved photoemission (ARP) data [98Rot] demonstrated that two different
surface states, arising from the splitting of a surface band due to spin orbit coupling, are present upon H
saturation and suggesting that the relevant Fermi nesting is between them.
4.5.1.5 Dispersion of adsorbate induced modes
The dispersion of the adsorbate induced modes allows to infer information about the interaction between
the adatoms and it is therefore frequently reported also in studies in which the substrate phonons were not
investigated. While such studies are omitted from this data collection, they may show some quite general
effects. Let us therefore discuss briefly the HREELS investigation of CO adsorption on Ir(100) [91Kis]. A
c(2x2) structure is formed when adsorption occurs on the unreconstructed substrate, while the LEED
pattern reverts to (1x1) for adsorption on the (5x1) reconstructed substrate indicating that long range order
is inhibited. The phonon dispersion is reported in Fig. 7. Four modes are visible. The internal stretching
vibration is at 2070 cm–1. Such frequency is indicative of adsorption in on-top sites. The other modes are
the dipole active Ir–CO stretch at 500 cm–1, the CO rotational mode at 430 cm–1 and the frustrated
translational motion at 55 cm–1. No substrate related modes were detected. The rotational mode, the
frustrated translation and the Ir–CO stretch show little or no dispersion, while the internal CO stretch
frequency decreases strongly when moving out of Γ . The latter effect is due to the long range dipole-
dipole interaction and is always present. It is given by [78Mah]:
 Į ȣ Ȉ 0 (q || ) 
Ȧ 2 (q || ) = Ȧ 02 1 +  (4)
 1 + Į e Ȉ 0 (q || ) 
 
where ω0 is the frequency of the isolated adsorbate species, αν and αe are the vibrational and the
electronic polarisabilities, respectively, and Σ0(q||) is the so-called dipole sum
& &
iq || ⋅ ri
Ȉ 0 (q || ) = ∑ e U(ri ) (5)
i
For larger q|| and for adsorbates with smaller dipolar interaction, the dispersion can have either sign and it
is determined either by direct interactions between the adsorbates or by interactions via the substrate. In
general the dispersion curve of the adsorbate induced modes contains therefore valuable information on
the interaction between the adsorbates.
The adsorbate induced modes can couple with those of the substrate having the same symmetry, thus
leading to avoided crossing and to the opening of energy gaps also for weakly interacting systems. An
example is given in Fig. 8 for the HATOF investigation of an incommensurate Xe monolayer adsorbed on
Cu(110) [94Zep]. The avoided crossing is between the vertical stretch motion of the adsorbate against the
substrate and the Rayleigh wave. The gap at q||=0.3 Å–1 is about 0.5 meV in accord with the small
interaction of a physisorbed gas with the substrate. Another example of energy gap, which occurs at the

zone centre for the longitudinal mode, was observed for the commensurate ( 3 × 3 )R30o structure of Xe
on Cu(111) [98Bra]. From the magnitude of the gap information on the corrugation of the Xe-atom
potential and on the friction forces was derived.
Much effort was dedicated recently to HATOF studies of physisorbed hydrocarbons because of the
applied relevance of such topic, e.g. CH4 [97Gra], C2H4 [96Gra1], C2H6 [97Gra], n-hexane, n-octane, n-
decane, benzene and cyclohexane [95Wit2] on Cu(100) and d-octane, nonane and decane on Cu(111)
were investigated [96Fuh]. The substrate phonon dispersion is then affected because of the presence of
the frustrated translation perpendicular to the surface, which hybridises with the RW, opening small
energy gaps. Such effect is generally small. This data has not been included in the present collection,
unless mass loading leads to significant phonon anomalies.
4.5.1.6 Theoretical models
The variety of crystal surfaces for which the surface phonon dispersion was measured entailed the use of
a corresponding large variety of theoretical models, as the theoretical approach varies significantly from
one class of materials to another. Usually the results for the adsorbate covered surfaces are compared with
those obtained for the bare substrate. The major difficulty is thereby the larger unit cell. Otherwise the
same models developed for the bare surfaces were applied.
In the case of metals the screening of the bare ion-ion interaction by the conduction electrons is
difficult to model theoretically. Empirical lattice dynamical models (LDM) were therefore introduced in
which the force constants in the interior of the crystal are obtained by fitting the experimental dispersion
curves of bulk phonons, while the force constants coupling atoms at and near the surface are modified.
Unfortunately, as there is in many cases no consensus on a satisfactory model for the bulk crystal, it is
difficult to give a reliable forecast for the changes of the surface force constants. The difficulty can be
overcome for sp-bonded materials by carrying out self consistent pseudopotential (SCP) calculations. The
method was later extended to noble metal and transition metal surfaces. Such calculations are also
addressed as ab-initio or first principles. For semiconductor surfaces calculations were performed either
by computing from first principles the electronic structure and using then these results to set up
appropriate bond charge models from which the force constants were derived, or by calculating the
electronic and atomic structural properties within DFT-LDA and using a total energy Ansatz to determine
phonon frequencies and dispersion.
4.5.2 Data collection

The data for surface phonon dispersion determined either experimentally or theoretically for adsorbed
covered systems is reported and compared with the surface phonon dispersion of the corresponding bare
system. The data is organised according to the electrical properties of the material: firstly metals,
secondly elemental semiconductors and insulators, and finally compound semiconductors, oxides and
salts. The reported systems are collected in Table I.
TABLE I
Investigated surface phonon dispersion curves of adsorbate covered systems.
System Symmetry Coverage Exp. technique Fig. Ref.

Ag(100) bare (1x1) HREELS, HATOF 9 90Mor, 91Che, 94Bun
Ag(100) Cl c(2x2) 0.5 ML HATOF 10 83Lam, 84Lam
Ag(110) bare (1x1) HATOF 11 87Bra1, 87Bra2, 89Tat
Ag(110) O p(2x1) 0.5 ML HATOF 12 89Yan
Ag(110) O p(3x1) 0.25 ML HATOF 13 90Bra1, 90Bra2, 91Bra,
93Bra
Al(111) bare (1x1) HREELS 14a 88Loc, 93Fra, 97Nag
Al(111) Na 3× 3 0.33 ML HREELS 14b 97Nag


Al(111) Na (2x2) 0.5 ML HREELS 15 97Nag
Cu(100) bare (1x1) HREELS, HATOF 16 86Wut, 93Ben, 94Hof
Cu(100) CO c(2x2) 0.5 ML HATOF 17 95Ell
Cu(100) N c(2x2) 0.5 ML HREELS 18 86Fra
Cu(100) O c( 2 × 2 2 ) 0.5 ML HREELS 20 89Wut1, 89Wut2
Cu(100) PF3 c(4x2) 0.25 ML HATOF 21 99 Bra
Cu(100) S p(2x2) 0.25 ML HREELS 22 87Fra
Mo(110) bare (1x1) HREELS, HATOF 23 97Krö, 98Krö1, 98Krö2,
92Hul2
Mo(110) H (2x1) 0.5 ML HREELS, HATOF 24, 25 93Hul2, 97Krö
Mo(110) O p(2x2) 0.25 ML HREELS 26 98Krö1, 98Krö2
Ni(100) bare (1x1) HREELS 27 83Leh, 86Roc2
Ni(100) C p4g(2x2) 0.5ML HREELS 28, 29 87Roc
Ni(100) H (1x1) HATOF 87Ber
Ni(100) N p4g(2x2) 0.5 ML HREELS 30 86Dau, 88Rah
Ni(100) O p(2x2) 0.25 ML HREELS, HATOF 31 84Sze, 91Ber
Ni(100) O c(2x2) 0.5 ML HREELS, HATOF 32 83Leh, 84Rah, 91Ber
Ni(100) S c(2x2) 0.5 ML HREELS 34 85Leh, 86Leh, 90Yan
Ni(110) bare (1x1) HREELS 35 87Leh2
Ni(110) CO p2mg(2x1) 1.0 ML HREELS 37 90Voi2
Ni(110) H p2mg(2x1) 1.0 ML HREELS 40 89Voi
Ni(110) H (1x2) 1.5 ML HREELS 41 89Voi, 87Leh1
Ni(110) O p(2x1) 0.5 ML HREELS 42 90Voi2, 91Yan
Ni(111) bare (1x1) HREELS 43 90Men1, 90Men2
Ni(111) O p(2x2) 0.25 ML HREELS 45 90Voi2, 91Yan
Pb(111) bare (1x1) HATOF 96Fuh
Pb(111) d-octane 1.0 ML HATOF 46 96Fuh
Pt(111) bare (1x1) HATOF 85Har, 86Ker2, 87Neu
Pt(111) H (1x1) 1.0 ML HATOF 47 89Bor
Pt(111) O p(2x2) 0.25 ML HATOF 48 86Ker1, 86Ker2, 87Ker
Pt(111) O (1x1) 1.0 ML HATOF 49 87Neu
Rh(110) bare (1x2) HATOF 50 93Bel
Rh(110) O (2x2) 0.5 ML HATOF 50 93Bel
Rh(111) bare (1x1) HATOF 51 95Wit1
Rh(111) H (1x1) 1.0 ML HATOF 51 95Wit1
Rh(110) C6H6 (2 3 × 3) 1.0 ML HATOF 52 93Wit1,93Wit2
Ru(0001) bare (1x1) HATOF 53 97Bra
Ru(0001) H (1x1) 1.0 ML HATOF 53 97Bra
W(100) bare (1x1) HATOF 54 87Ern, 89Ern
W(100) H (1x1) 2.0 ML HATOF 55 92Ern
W(110) bare (1x1) HREELS, HATOF 56, 61 92Hul1, 92Hul2, 94Bal1
W(110) H p(2x1) 0.5 ML HREELS, HATOF 57, 61 92Hul1, 92Hul2, 94Bal1,
94Bal2, 96Bal
W(110) H p(2x2) 0.75 ML HREELS, HATOF 57, 61 92Hul1, 92Hul2, 94Bal1,
94Bal2, 96 Bal
W(110) H (1x1) 1.0 ML HREELS, HATOF 57, 59 92Hul1, 92Hul2, 94Bal1,
94Bal2, 96 Bal
C(100) H (2x1) 1.0 ML theory 63 96San
C(100) H (1x1) 2.0 ML theory 64 96San
C(111) H (1x1) 2.0 ML HATOF 65 96Lan, 98Gle


Ge(100) S (1x1) 1.0 ML theory 66 92Pol
Si(100) bare (2x1) theory 67 97Tüt
Si(100) As (2x1) 0.5 ML theory 69 98Grä, 99Tüt
Si(100) Ge (2x1) 0.5 ML theory 70 98Tüt2
Si(100) Sb (2x1) 0.5 ML theory 71 98Tüt1, 98Tüt2
Si(100) H (2x1) 0.5 ML theory 72 96Grä1
Si(100) H (1x1) 1.0 ML theory 73 97Grä
Si(111) As (1x1) 1.0 ML HREELS, HATOF 74 90Doa1, 90Doa2, 92San2,
94Sch
Si(111) Ga ( 3 × 3) 0.3 ML HREELS, HATOF 75 95Sch, 89Doa
Si(111) H (1x1) 1.0 ML HREELS, HATOF 76 92Stu, 92Dum, 90Doa3
GaAs(110) bare (1x1) theory 77 99Fri1
GaAs(110) H (1x1) 1.0 ML theory 78 99Fri1
GaP(110) H (1x1) 1.0 ML theory 79 99Fri1
GaP(110) Sb (1x1) 1.0 ML theory 80 99Fri1
InAs(110) H (1x1) 1.0 ML theory 81 99Fri1
InP(110) H (1x1) 1.0 ML theory 82 95Fri1
MgO(100) CO HATOF 95Ger
NaCl(100) CO2 HATOF 93Lan, 93Hei, 95Lan
NaCl(100) H2O HATOF 95Bru
NaCl(100) C2H2 HATOF 98Pic
NaCl(100) OCS HATOF 96Gle, 96Doh
4.5.2.1 Correspondence of units
Several units are used for the surface phonon energies. No attempt has been made to convert the data to a
single unit, rather the units of the original data are employed. In Table II the conversion factors between
the different units, which may be useful for comparing different sets of data, are reported.
Table II
Energy conversion factors.
THz cm–1 1013 rad/sec meV

1 THz 1 33.36 0.6283 4.136
1 cm–1 0.02998 1 0.01884 0.1240
1013 rad/sec 1.5915 53.09 1 6.583
1 meV 0.2418 8.066 0.1519 1
4.5.2.2 Metal surfaces
Ag(100)
The surface phonon spectrum of the bare surface as measured by HREELS [90Mor, 91Che] and HATOF
[94Bun] is reported in Fig. 9. The data shows evidence for a weak stiffening of the RW and for the
presence of two longitudinal acoustic surface resonances. The difference between HREELS and HATOF,
although systematic, is within experimental error.

Ag(100) Cl
Chlorine forms a c(2x2) overlayer on Ag(100). The surface phonon dispersion was investigated by
HATOF [83Lam, 84Lam] at a beam energy of 20 meV and of 64 meV showing evidence for the
excitation of the RW. Its dispersion, reported in Fig. 10, is not appreciably affected by Cl adsorption. This
result is in accord with the absence of interlayer relaxation [76Zan]. No Cl induced high frequency modes
were observed. The dispersion of the RW could be recorded only over part of the surface Brillouin zone
because of the dramatic dependence of the inelastic cross section on q||. The q|| effect is discussed
quantitatively with reference to the theoretical model of ref. [83Bor]. The data along Γ – M are
measured near to the ( 1 , 1 ) diffraction peak. The backfolded branch can be seen near M' .
Ag(110)
The surface phonon spectrum of the bare surface was measured by HATOF [87Bra1, 87Bra2, 89Tat] and
it is reported in Fig. 11. Along Γ – X apart from the RW (S1), two surface resonances (MSo and MS+ ) are
present. Along Γ – M the lowest frequency mode S1 is L polarised, while S3 is the Rayleigh wave.
Ag(110) O
The surface reconstructs upon oxygen adsorption forming regularly spaced added Ag–O rows along the
<001> direction with p(nx1) symmetry and 2<n<7 (see model in the inset of Fig. 13b). The surface
phonon dispersion curves were measured by HATOF for the p(2x1) and the p(3x1) overlayers and are
reported in Figs. 12 and 13, respectively. For the p(2x1) structure [89Yan] the lowest frequency mode
along Γ – Υ is SV polarised and originates from the RW of the clean surface. The highest branch comes
from the backfolding of a mode originally located around S . Along Γ – X the acoustic mode with
nearly linear dispersion is mainly longitudinally polarised and arises from the MS0 mode of the clean
surface. The drastic frequency reduction of this mode (from 10 meV to 4 meV) at X' is due to the added
row reconstruction of the substrate. The Rayleigh wave (S1) is the second lowest branch. The phonon
spectrum, appropriate for a saw tooth reconstructed surface, is demonstrated to be incompatible with
experimental data. The spectra are much more complicated for the p(3x1) overlayer [90Bra1, 90Bra2].
The LDM calculations show that along Γ – Υ two modes (A and B, see Fig. 13b) are present. The spectral
density of mode A in the vertical direction vanishes towards the zone boundary, but it is comparable with
the one of mode B around q|| = 0.35Å, thus explaining the spread of the experimental data points. The
other modes originate either from the backfolding of the RW or from the MS0 surface resonances of the
bare surface and from their hybridisation, except for the mode at 8 meV along Γ – Υ (dashed line). The
latter arises from a SH polarised mode of the clean surface, which becomes longitudinally polarised
because of the folding of the SBZ. The surface phonon spectrum was calculated also for an
unreconstructed and saw-tooth reconstructed substrate and turned out to be in strong disagreement with
the experimental data [90Bra1, 90Bra2, 91Bra, 93Bra].
Al(111)
The surface phonon dispersion for the bare Al(111) surface was measured by HREELS [97Nag] and
HATOF [88Loc, 93Fra]. Two modes are found, corresponding to the RW and the L mode. The HREELS
data are reported in Fig. 14a by open circles and compared to a LDM.
Al(111) Na
Sodium adsorbed on Al(111) forms two ordered structures, characterised by 3 × 3 and (2x2)
superlattices, corresponding to coverage of 1/3 and 1/2 ML, respectively. The surface phonon dispersion
was investigated by HREELS and is reported in Figs 14 and 15. For the 3 × 3 overlayer (see Fig. 14)

the RW (S1) and two surface resonances (R1 and R2) are observed, which were absent for the bare surface
[97Nag]. S1 is strongly softened by adsorption and merges with the resonance R2 at small wavevectors.
The resonance R1 is present only near Γ and is dipole active. The result of a LDM calculation assuming a
substitutional adsorption site for the Na adatoms is shown in Fig. 14b. LDM calculations were performed
also for other adsorption geometries and shown to generate surface phonon spectra incompatible with
experiment. The modes R1 and R2 are shown to be associated to the same SV motion of the Na atoms,
whereby R1 is the backfolded branch of R2. The frequency of the dipole active phonon R1 was reproduced
by ab-initio calculations. The surface phonon dispersion of the (2x2) phase was measured by HREELS
[97Nag] and is reported in Fig. 15 together with the data measured for the bare Al surface. For this phase
the surface phonon dispersion is modified less than for the 3 × 3 phase although also in this case
adsorption is suggested to be substitutional. The surface mode S1 and the resonance R1 are assigned to the
RW, R1 being the backfolded branch.
Cu(100)
The surface phonon dispersion of the clean surface, as measured by HREELS [86Wut] and confirmed by
HATOF [93Ben, 94Hof], is reported in Fig. 16. The RW is stiffer than predicted by LDM using the bulk
force constant. The phenomenon was ascribed to the presence of tensile surface stress.
Cu(100) CO
CO forms an ordered c(2x2) overlayer on Cu(100) at a coverage of 0.5 ML. The surface phonon spectrum
was measured by HATOF along both high symmetry directions and is shown in Fig. 17. The RW
frequency at the zone boundary is found to be shifted from the bare surface value because of mass loading
and for a slight modification of the force constants between the underlying Cu atoms. The opening of
hybridisation gaps is clearly visible in the data. The analysis is supported by a slab calculation [95Ell].
Cu(100) N
Nitrogen forms a c(2x2) overlayer at a coverage of 0.5 ML whose phonon dispersion was measured by
HREELS along Γ – X and is shown in Fig. 18. The frequency of the RW (S4-phonon) at X is only
slightly changed with respect to the clean surface value. The data are compared to a LDM calculation
which shows that an optimum fit to the perpendicular (N⊥) and to the parallel (N||) nitrogen modes is
obtained when the nitrogen adatom is placed 0.6 Å above the first copper layer [86Fra].
Cu(100) O
Oxygen forms a c(2x2) mesh at a coverage of 0.5 ML and induces a missing row 2 × 2 2
reconstruction of the substrate [89Zen] (see Fig. 19). The oxygen occupies the former fourfold hollows
and sits almost coplanar with the Cu atoms of the outermost crystal plane, while rows of Cu atoms are
missing along [001]. The critical nucleation coverage for the reconstructed phase is 0.34±0.02 ML. The
surface phonon dispersion was investigated by HREELS and is reported in Fig. 20. The modes at 34 meV
and 56 meV are dipole active in accord with the local Cs symmetry and correspond to the perpendicular
vibration of the adsorbate and to the frustrated translation across the missing rows. The mode at 85 meV,
visible for off-specular scattering conditions, corresponds to the frustrated translation along the missing
rows. Two branches associated to the Rayleigh wave are observed, the backfolded branch being nearly
dispersionless. This behaviour is indicative of a strong reduction of the force constants at the surface, in
accord with the missing row reconstruction. The loss at 69 meV is very weak and is assigned to the
overtone of the 34 meV mode [89Wut1, 89Wut2].

Cu(100) PF3
PF3 forms a c(4x2) structure on Cu(100) at a coverage of 0.25 ML. The surface phonon dispersion was
investigated by HATOF and is reported in Fig. 21 for isolated molecules as well as for the ordered
structure. The dispersion shows evidence of a low frequency mode, assigned to the frustrated translation
of the adsorbate (FTx), and of the RW. For the ordered structure (see panel b) the modes RW1 at 8.2 meV
and RW2 at 10.3 meV, are assigned to the RW and to its backfolded branch. The result of a LDM
calculation, for which the surface corner atoms (see inset) were replaced by heavier particles of mass
m=mCu+mPF3 is shown in panel c). It demonstrates that the principal effect of phosphor trifluoride
adsorption is mass loading [99Bra].
Cu(100) S
Sulphur on Cu(100) forms an ordered p(2x2) overlayer, corresponding to a coverage of 0.25 ML. S sits in
the fourfold hollow at a perpendicular distance of 1.39 Å from the outermost Cu plane. The surface
phonon spectrum of this system was investigated by HREELS along Γ – X and is reported in Fig. 22.
The dispersion was recorded also along Γ – M but not published. LDM calculations were performed and
compared to the experiment. The data shows evidence for: the RW at 12.5 meV at X and 16.5 meV at
M , a surface resonance around 20 meV along both directions and the S–Cu stretching vibration at 42
meV. The LDM calculations show that the force constant between the Cu atoms at the surface retains its
bulk value and that the frustrated translation, S|| is expected at about the same frequency as the vertical
mode, S⊥ [87Fra]. Further reference [87Wu].
Mo(110)
The surface phonon spectrum of bare Mo(110) consists of the RW, of the L mode and of a further
resonance at 240 cm–1 (see Fig. 23). The dispersion curves were measured by HREELS (open symbols)
[97Krö, 98Krö1, 98Krö2] as well as by HATOF (filled circles) [92Hul2].
Mo(110) H
Hydrogen forms three superstructures on Mo(110) characterised by (2x1), (2x2) and (1x1) superstructures
corresponding respectively to a coverage of 0.5 ML, 0.75 ML and 1 ML. The adsorbate resides always in
the hollow sites. The surface phonon dispersion data are shown in Fig. 24 for HATOF and HREELS
measurements. For lower coverage no anomalies are present, while at saturation a dip is observed both
for the RW and for the L mode which is ascribed to a Kohn anomaly (see also the case of W(110) (1x1) H
and the discussion in the introductory part). A further mode, whose frequency nearly vanishes at the
critical wavevector, is observed only with HATOF. It corresponds either to the excitation of electron hole
pairs [95Koh] or to a plasmon like motion of the H atoms [96Bun]. The dispersion of the H induced
modes is reported in Fig. 25. The Kohn anomaly is due to the nesting of the Fermi surface contours
associated to the (d3z2–r2,dxz)-like band, which run parallel to Γ – S and perpendicular to Γ – S over
significant parts of the SBZ [95Koh]. The effect of H is to change the potential at the surface and to shift
the Mo surface state into a region of reciprocal space where it becomes localised at the surface. The band
becomes thus two-dimensional and the nesting one-dimensional. The theoretical calculation for the Fermi
contours differs however significantly from the ARP result [89Jeo1, 89Jeo2], which shows nesting at
larger wavevectors. The presence of a Kohn anomaly was invoked also for an anomaly observed for
Mo(110) Li at 1 ML coverage [00Krö]. A subsequent paper of one of the authors questioned however this
interpretation, suggesting that the phonon anomaly can be explained by surface stress [02Dah]. Main
References: [93Hul2] and [97 Krö]. Further references: [93Hul1, 93Hul2, 98Krö1].

Mo(110) p(2x2) O
Oxygen forms a p(2x2) structure at saturation, corresponding to 0.25 ML. The surface phonon dispersion
is reported in Fig. 26. In spite of the indication by ARP [94Kev, 94Dha] that Fermi surface nesting should
occur, no surface phonon anomalies are observed, except for the stiffening of the RW at N (shift from 17
to 19 meV). The solid triangles and the dots in the p(2x2) data along Γ – Η were recorded with the crystal
at room temperature, where the additional LEED spots present at low temperature along [1 1 0] have
disappeared. The phonon spectrum is however little affected. The oxygen-surface stretch mode was
visible only in-specular despite varying the electron impact energy from 2 to 25 eV. Its energy reads 65
meV. The oxygen mode parallel to the surface was not detected. The adsorption site is identified with the
long bridge in accord with a previous investigation [92Col]. Residual occupation of the threefold hollows,
probably at the boundaries of p(2x2) islands is witnessed by a shoulder at 70 meV in the HREELS spectra
[98Krö1,98Krö2].
Ni(100)
The surface phonon dispersion on the clean surface was thoroughly investigated by HREELS [83Leh],
[86Roc2] as well as HATOF [87Ber]. HREELS data are reported in Fig. 27. HATOF data (not shown)
coincide with the HREELS result. The clean surface shows evidence for the RW and for several
resonances. The frequency of the RW (S1 along Γ M , S4 along Γ X) at the zone boundary is higher than
predicted by LDM’s assuming the bulk value of the force constant also between surface atoms. The effect
was attributed to tensile surface stress. An increase of the RW frequency is also in accord with the 3.2%
inwards relaxation of the first interplanar distance observed by RBS [83Fre1, 83Fre2].
Ni(100) C
Carbon forms above 0.25 ML a weak c(2x2) phase with splitted LEED spots indicative of the presence of
antiphase domains with the adsorbate occupying the fourfold hollow. Above of 0.3 ML glide planes form
along [1 1 0] and the symmetry becomes p4g. LEED [79Onu] and SEXAFS [87Bad] show that the
adsorbate still occupies the fourfold hollows and is 0.1 Å above the Ni atoms in the outermost crystal
plane. The geometry of the reconstructed phase implies an ordered clockwise and anticlockwise rotation
pattern of the substrate surface atoms around the adsorbates, which coincides with the displacement
pattern of the A2 mode of the c(2x2) overlayer at X (see right panel of Fig. 4, mode g). A soft phonon
mechanism was therefore proposed for the reconstruction [85Rah]. Subsequent LDM calculations [87Mil,
88Sze, 89Mil, 89Sze] showed however that the B2 mode rather then the A2 mode should freeze in first
when the force constant between Ni atoms in first and second crystal plane decreases. Inclusion of a
compressive surface stress in the LDM allows to overcome this difficulty and to obtain the correct
reconstruction [86Mül]. This model also explains the surprising absence of appreciable softening of the
RW with C adsorption [87Roc] (see Fig. 28). The surface phonon dispersion as measured by HREELS is
reported in Fig. 29 for a coverage of 0.5 ML. The data are reported for an extended zone scheme, the zone
boundary being halfway between Γ and X . By symmetry no energy gaps can form at the zone boundary
along the glide planes. The C⊥ modes at 42 meV and 51 meV at Γ and X correspond, respectively, to the
in-phase and out of phase vertical stretch motions at Γ of the two C atoms of the unit cell. Four parallel
modes are found at around 93 meV. They are doubly degenerate at Γ and X . The avoided crossing of the
dispersion of such modes along Γ – X leads to the opening of an energy gap and to the asymmetric form
of the dispersion [89Sze]. Such effect is not taken into account in the LDM calculations reported by solid
lines. The high frequency of the parallel adsorbate modes is due to the vanishing adsorption distance of
the C adatoms. Another consequence of the reconstruction is the splitting of the RW into two modes, the
upper branch being R1 (at 18 meV at X ). The dependence on carbon coverage of the RW at X and of the
frequency of the adsorbate modes at Γ are reported in Fig. 28. A sharp decrease of the Ni–C stretch at the
onset of the weak c(2x2) superstructure and no evident change at the onset of the p4g reconstruction are

observed. The strong temperature dependence of the RW frequency is indicative of strong anharmonicity.
The same effect was observed for Ni(100) p4g N. See also the introduction for further discussion on this
system. Main reference [87Roc]. Further references [89Sze, 89Mil, 88Sze, 87Mil, 85Rah, 87Rah].
Ni(100) H
Hydrogen adsorption restores the surface phonon frequencies to the values predicted by LDM
calculations using the bulk force constants. In particular, compared to the clean surface case, the RW is
softened by 0.7 meV at X and by 1.5 meV at M . The longitudinal resonance disappears almost
completely from the spectra. The data are discussed in ref. [87Ber], but no dispersion curves were
reported.
Ni(100) N
Nitrogen adsorption induces a p4g reconstruction at a coverage of 0.5 ML. In close analogy to the case of
C/Ni(100) the N atoms sit in a c(2x2) unit mesh in the fourfold hollows, while the substrate
reconstruction reduces the symmetry to (2x2). SEXAFS investigation [87Wen] shows that the adsorption
site is the fourfold hollow with an adsorption distance of 0.1 Å above the outermost Ni atom plane. The
rotational displacement around the adsorbate is 0.68 Å, slightly larger than for C/Ni(100) (0.5 Å
[87Bad]). The dispersion of surface phonons as measured by HREELS is reported in Fig. 30. The
experimental points are reported for an extended zone scheme, the zone boundary being at X . By
symmetry no energy gap can form at the zone boundary along this direction. The N⊥ mode extending
from 34 meV at Γ to 51 meV at X corresponds to the in-phase vertical stretch motions of the two N
atoms of the unit cell in the first zone and to the out-of-phase stretch motion in the second zone. The in-
phase mode at Γ falls within the bulk band and is therefore a surface resonance. Four parallel modes are
expected, but only two are observed (direct and backfolded branches in the first and second SBZ,
respectively) at around 91 meV. The high frequency of the parallel modes is due to the vanishing
adsorption distance of the N adatoms. The RW and two surface resonances are observed, too, of which
R1, originates from the backfolded branch of the RW and is a true surface mode at X . The lines are the
result of a LDM calculation for the reconstructed surface geometry [88Rah]. The RW frequency shows a
marked crystal temperature dependence at X , where it reads 13.6±0.4 meV at T=130 K and 12.0±0.6
meV at T=300 K. Main references [86Dau] and [88Rah].
Ni(100) O
Oxygen forms two ordered superstructures, p(2x2) and c(2x2), on Ni(100), corresponding to a coverage
of 0.25 ML and 0.5 ML, respectively. The adsorbate sits in both cases in the fourfold hollow at a vertical
distance of 0.86 Å from the outermost Ni plane (SEXAFS [82Stö, 87Wen], NEXAFS [83Nor], LEED
[89Oed, 90Oed]). Using nuclear methods the maximum coverage of the c(2x2) phase was determined to
be 0.42±0.04 ML [86Alk]. RBS experiments [83Fre1, 83Fre2] demonstrated that the first interplanar
distance increases by 2% for the p(2x2) and 5.2% for the c(2x2) structure. The surface phonon dispersion
for the p(2x2) O overlayer is reported in Fig. 31a for HREELS data [84Sze] and in Fig. 31b for HATOF
data [91Ber]. The branch at 420 cm–1 is the perpendicular stretch vibration of oxygen, while the frustrated
translation is observed at 640 cm–1. The Rayleigh wave is only slightly softened with respect to the clean
surface. Two resonances are present near Γ . One of them is dipole active and corresponds to the
breathing motion with A1 symmetry which originates from the backfolding of the S6 mode originally at
X . The solid lines are the result of a LDM calculation [86He]. The surface phonon dispersion for the
c(2x2) O overlayer is reported in Figs 32 a) and b) for HREELS [83Leh, 84Rah] and HATOF [91Ber],
respectively. The RW shows a strong softening at X (from 132 cm–1 to 80 cm–1) which is due to the
adsorbate induced compressive stress at the surface. A reduction of the force constant between the
substrate atoms in first and second crystal layer is also possible in view of the large outwards relaxation
of the first interplanar distance. The stress model can however explain several other findings and in

particular the dependence of the softening of the RW on the order status of the adsorbate (see Fig. 33).
See also the introductory part for further discussion on this system.
Ni(100) S
Sulfur forms at saturation (0.5 ML) a c(2x2) structure on Ni(100). The adsorbate occupies the fourfold
hollow sitting at 1.35 Å above the outermost Ni atom plane (LEED [73Dem], SEXAFS [81Bre] and
photoelectron spectroscopy [81Ros, 83Bar, 84Ord]). The surface phonon dispersion is reported in Fig. 34.
The observed branches correspond to the RW (S4), to S6 and to a surface resonance associated to the
backfolding of the RW from the M X direction. The vertical and the parallel mode of the adsorbate are
visible above the projection of the bulk phonon bands (hatched area). The LDM calculation was
performed with the bulk value of the force constants. In order to obtain a good fit with a LDM an
adsorption distance of 1.45 Å had to be assumed. This shortcoming is most probably due to neglecting of
the adsorbate induced stress [92San1]. Main reference [85Leh] and [86Leh].
Ni(110)
The surface phonon dispersion for the clean surface was measured by HREELS [87Leh2] and is reported
in Fig. 35. The RW corresponds to the S1 mode along Γ – X and to S3 along Γ – Υ . Along the latter
direction the lowest frequency mode is mainly longitudinally polarised.
Ni(110) p2mg (2x1) CO
CO forms at saturation a p2mg (2x1) structure at 1 ML coverage on Ni(110). Adsorbate geometry and
SBZ are shown in Fig. 36. The CO molecules are adsorbed in atop sites with the axis tilted away from the
surface normal. The dispersion curve, measured by HREELS, is reported in Fig. 37 over an extended
zone scheme. Two stretch motions are possible corresponding to in-phase and out-of-phase vibration of
the two CO molecules of the unit cell. The two modes are degenerate at X and Υ . The latter observation
implies that ∆Y, i.e. the lateral displacement of the chemisorption sites with respect to the substrate
atoms, is exactly one quarter of the substrate unit cell. The dispersion as well as the low symmetry
adsorption sites are caused by the repulsive dipole-dipole interaction between the close packed CO
molecules. The dipolar interaction determines the negative dispersion of the in-phase motion with q||. The
mode at 400 cm–1 corresponds to the stretch of the CO molecule against the substrate. The two substrate
modes are due to the RW and to its backfolded branch [90Voi2].
Ni(110) H
Hydrogen forms on Ni(110) a sequence of ordered structures with increasing coverage which were
attributed to the increasing density of zig-zag chains along the rows of the first layer Ni atoms (see Fig.
38). At one ML coverage the (2x1) superstructure forms which consists of an unreconstructed surface
with H atoms in the three fold sites between two first layer and a second layer atom with equal Ni–H
distances (LEED [87Rei]). Saturation coverage is at 1.5 ML. The surface is then (1x2) reconstructed with
pairing substrate rows (LEED [87Kle]). Two adsorption sites are occupied corresponding to the previous
threefold site and to a Cs site above the paired rows. A strong softening of the S1 mode was found with H
adsorption and ascribed to the build up of surface stress. The frequency shift of the phonons at Υ (Figs.
39a and b) indicates a propensity of the surface towards reconstruction. At X on the contrary (see Fig.
39c) the frequency of the RW remains unchanged up to one ML coverage indicating that H adsorption
induces a charge rearrangement that influences the substrate interaction only along [001]. The surface
phonon dispersion curve for the p2mg (2x1) H overlayer is reported in Fig. 40. The two H atoms, present
in the unit cell, are linked by the glide operation. Two modes are dipole active in accord with the reduced
symmetry of the adsorption site. A further mode is visible only off specular and along Γ – X . The mode
at 630 cm–1 has the strongest dipole character but corresponds to motion mostly parallel to the surface

plane. The perpendicular stretch mode is at 1100 cm–1. The substrate modes S1 and S3 at Υ are softened
by 10% with respect to the clean surface [89Voi]. The surface phonon dispersion curve for the (1x2) H
overlayer is reported in Fig. 41. The data are reported on an extended zone scheme, the first Brillouin
zone ending at Υ ' , halfway between Γ and Υ . At Υ a splitting of the RW and the opening of a gap is
observed. The three H atoms per unit cell give rise to four dipole active modes in accord with the reduced
symmetry of the adsorption sites. The mode at 450 cm–1 corresponds to the vibration perpendicular to the
Ni rows in the [001] direction. Symmetry considerations imply that the modes at 930 cm–1 and 1240 cm–1
are polarised within the Cs plane parallel to the Ni rows. Ab-initio calculations however assign the 1240
cm–1 loss to a vibration predominantly perpendicular and the 930 cm–1 loss to a vibration predominantly
parallel to the surface along [1 1 0] [87Fei]. References [89Voi, 87Leh1]. Further reference [87Iba].
Ni(110) O
Oxygen adsorption on Ni(110) induces a series of ordered structures leading finally to nickel oxide
formation. The (2x1) phase, observed at half a ML coverage, involves a missing row reconstruction of the
substrate. The oxygen adatoms sit in the long bridge sites at an estimated height of 0.6 Å above the
outermost Ni atoms (EXAFS [86Bab]).The surface phonon dispersion is reported in Fig. 42 for the p(2x1)
phase. Three dipole active modes are present. Two of them are associated to adsorbate vibrations, while
the one at 118 cm–1 is due to a Ni surface phonon folded back to the Γ point because of the (2x1)
reconstruction. The presence of two dipole active adsorbate modes shows that the local adsorption
symmetry is Cs, i.e. only one mirror plane is present and the adsorbate is shifted out of the long bridge in
the [1 1 0] direction. The adsorbate induced modes are polarised within the mirror plane predominantly
parallel (at 239 cm–1) and perpendicular (at 385 cm–1) to the surface in the [1 1 0] direction. The third
mode, at 790 cm–1, is polarised parallel to the surface in the [001] direction and shows a particularly
strong temperature dependence. The other modes did not change appreciably with T. The assignment is
less clear for the substrate modes. The lowest lying phonon at Υ is at 84 cm–1, i.e. close to the frequency
of the RW of the clean surface. Similarly the mode at 135 cm–1 is close to the frequency of the S3 mode of
the clean surface. Such modes are however unlikely to have survived unchanged the missing row
reconstruction. LDM calculations assign the mode at 84 cm–1 to an odd vibration which becomes visible
because the symmetry is reduced to Cs and the Γ – Υ direction is no longer a mirror plane. The mode at
118 cm–1 at Γ is dipole active and originates from a mode along X – S which is folded back on Γ – Υ for
the reconstructed surface. Along Γ – Χ the two dipole active adsorbate modes show practically no
dispersion throughout the SBZ. The lowest frequency substrate mode is assigned to the RW [90Voi2,
91Yan].
Ni(111)
The surface phonon dispersion of clean Ni(111) was measured by HREELS and is reported in Fig. 43
[90Men1, 90Men2]. Two surface modes, S1 and S6 and a surface resonance are visible. Modified surface
force constants are necessary to reproduce the dispersion with a LDM, as it is the case also for the other
Ni surfaces.
Ni(111) O
The p(2x2) O/ Ni(111) system is reconstructed with a twist deformation of three of the top layer nickel
atoms and a vertical displacement of all of the atoms in the top layer of the unit cell (LEED [90Gri]). The
oxygen coverage is 0.25 ML. A schematic view of the structure of the p(2x2) overlayer is reported in Fig.
44. The oxygen lifts three of the nickel atoms away from their original bulk positions, while the fourth
relaxes towards the second layer Ni atoms. The surface phonon dispersion measured by HREELS is
reported in Fig. 45. Five optical modes are observed. The modes at 67 and 71 meV are assigned to
oxygen adsorbate vibrations, while the lower modes lie within the bulk bands. The open (filled) circles

indicate data points recorded at an electron impact energy of 7 (160) eV. LDM calculations are presented,
too (thick solid lines). The theoretical dispersion curves for the two lower lying modes is not extended
over the whole SBZ as such modes are surface resonances which do not produce sharp spectral density
features at large wavevectors. The thin solid lines are best fit curves to the experimental data [94Tis].
Pb(111)
The surface phonon dispersion for the clean Pb surface was investigated by HATOF and is indicative of
no change in the force constants compared to the bulk value [96Fuh]. The result of the LDM is reported
in Fig. 46.
Pb(111) d-octane
d-octane adsorbs flat on the surface. The surface phonon spectrum was investigated by HATOF and
shows evidence for the frustrated translation (FTz) normal to the surface and for the RW (see Fig. 46).
The latter is strongly softened because of mass loading. The AOP1 mode corresponds to an internal
vibration of the alkane molecule [96Fuh].
Pt(111)
The surface phonon dispersion of the bare Pt surface was determined by HATOF and is reported in Fig.
49 (open symbols). The RW (dots) and the L resonance (triangle) are observed. The RW presents
anomalies along Γ – K , which were ascribed to the Kohn mechanism [85Har, 86Ker2, 87Neu].
Pt(111) (1x1) H
Hydrogen forms a (1x1) overlayer at saturation corresponding to 1 ML coverage. It adsorbs in the three-
fold fcc hollows causing an expansion of about 1.3±0.4 % of the first interlayer spacing (RBS [80Dav],
LEED [76Chr]). Theory [87Fei] predicts that the H atoms lie about 0.95 Å above the surface in agreement
with RBS results [86Koe]. The inelastic He scattering data are collected in Fig. 47. They show a
significant softening of the RW frequency at the zone boundary (from 11.1 meV to 9.5 meV at K and
from 10.8 meV to 9.3 meV at M ). Moreover the longitudinal resonance, present on the clean surface and
particularly intense along <110>, has disappeared. These changes imply a strong modification of
tangential, radial and three-body force constants especially in the surface plane, connected to a
redistribution of the electronic charge at the surface and a reduction of the sp-d hybridisation, responsible
for the directed bonding charge between atoms in the bulk [89Bor].
Pt(111) O
Oxygen forms at saturation (coverage 0.25 ML) a p(2x2) structure when adsorption occurs at T=300 K,
corresponding to a coverage of 0.25 ML. The adatoms are sitting in the three-fold hollows 1.4 Å above
the outermost Pt atoms plane as inferred from the oxygen substrate stretch at 59 meV [82Ste]. A (1x1)
coverage can be reached when the Pt crystal is annealed at a crystal temperature of 540 K in 5 10–7 mbar
of oxygen. The latter phase corresponds to the formation of a subsurface oxide [87Neu]. According to ref.
[81Nie, 81Bon] it can only be obtained in presence of silicon impurities. The phonon dispersion of the
p(2x2) overlayer was measured by HATOF along ī − M and is reported in Fig. 48. The data (panel a)
show evidence for two branches associated to the RW and of a hybridisation gap at the zone boundary of
0.85±0.2 meV. The two dispersionless modes at 9 and 10 meV originate from the backfolding of the RW
from the M - K - M' direction. In a comment it was suggested that they might be due to a single mode
[87Sze]. Theory is reported in panel b. Inclusion of threebody forces is necessary to reproduce the size of
the phonon gap. Reference [86Ker1, 86Ker2, 87Ker]. The phonon dispersion for the (1x1) phase

(coverage 1 ML) was measured by HATOF and is reported in Fig. 49. A strong softening of the RW and
of the L mode is observed along ī − M in the last third of the surface Brillouin zone [87Neu].
Rh(110)
The surface phonon dispersion of bare Rh(110) was measured by HATOF for the metastable (1x2)
missing row reconstructed surface obtained after chemical removal of the oxygen adatoms by
hydrogenation at T=360 K. No LDM exists for comparison. The data are reported in Fig. 50a [93Bel].
Rh(110) O
Oxygen forms a (2x2) overlayer on Rh(110) at 0.5 ML coverage. The substrate is reconstructed in the
same way as for the metastable (1x2) surface whose surface phonon dispersion is reported in Fig. 50a.
The surface phonon dispersion was measured by HATOF and is reported in Figs. 50c, d and e [93Bel].
Rh(111)
The surface phonon spectrum of bare Rh(111) was measured by HATOF and is reported in Fig. 51a. The
RW and a L resonance are observed along both high symmetry directions [95Wit1].
Rh(111) H
Hydrogen forms a well ordered (1x1) overlayer at the saturation coverage of 1 ML. The adsorption site is
likely to be the three-fold hollow. The dispersion curve was investigated by HATOF and is reported in
Fig. 51b [95Wit1]. The intensity of the L-modes is weaker for the hydrogenated phase, while the RW is
observed over all the SBZ. Its frequency at K and M reads 16.4 meV and 15.6 meV, respectively, and is
thus slightly decreased compared to the clean surface values. Some weak and broad peaks, observed
above the RW (open circles marked by B’), are associated to surface resonances. Moreover an additional
mode, S2, is split off from the longitudinal bulk bands along both high symmetry directions at energies of
28.5 meV and 29.7 meV at K and M , respectively. Such mode is not hydrogen induced as it does not
shift in frequency when deuterium is adsorbed. Three H vibrations were reported by HREELS at 92
meV, 136 meV and 175 meV [86 Mat].
Rh(111) ( 2 3 × 3 ) C6H6
The phonon dispersion curve for the ( 2 3 × 3 ) phase, obtained at saturation (0.16 ML), was investigated
by HATOF. The data, reported in Fig. 52, show evidence for the RW and for the frustrated translation of
benzene parallel to the surface. The two modes hybridise strongly opening an energy gap [93Wit1,
93Wit2].
Ru(0001)
The surface phonon dispersion was measured by HATOF. The data are reported in Fig. 53a. The SBZ is
reported in the inset. The two modes correspond to the RW and to the L resonance [97Bra]. No change of
surface force constants is necessary to reproduce the data with a LDM.
Ru(0001) (1x1) H
Hydrogen forms several ordered phases on Ru(0001). Only the more stable (1x1) phase, corresponding to
saturation coverage (1ML), was investigated by HATOF to determine the surface phonon dispersion. The
dispersion curve for the H saturated surface is reported in Fig. 53b. Apart from the RW and the L mode
two further features, denoted by S2, are present [97Bra].

W(100)
Clean W(100) undergoes reconstruction via a soft phonon mechanism, which was confirmed by HATOF
experiments [87Ern, 89Ern]. The surface phonon dispersion curve, reported in Fig. 54, shows a strong
Kohn anomaly at M .
W(100) H
Hydrogen forms a (1x1) phase at saturation (2 ML coverage) whose surface phonon dispersion was
investigated by HATOF. The measurements show that H removes the Kohn anomaly and the force
constants between surface atoms are restored to their bulk value [92Ern]. The data are shown in Fig. 55
and compared with the result of a LDM. Nearly dispersionless H induced modes were observed by
HREELS at: 160 meV - asymmetric stretch, 130 meV - symmetric stretch, 118 meV - optical mode, 80
meV - wagging mode. [87Ers,87Woo].
W(110)
The surface phonon dispersion was investigated by HREELS and HATOF and is reported in Fig. 56
[94Bal1, 92Hul1, 92Hul2]. The data show evidence for the RW, for the longitudinal resonance and for a
further resonance at 200 cm–1. Contrary to the case of the (100) surface, no phonon anomaly is present.
W(110) H
Three adsorbed H phases form on W(110): p(2x1) at 0.5 ML coverage, (2x2) at 0.75 ML and (1x1) at
saturation (1 ML). The phonon dispersion was investigated for all the phases by HATOF [92Hul1,
92Hul2] as well as by HREELS [96Bal, 94Bal1, 94Bal2]. The H adsorption site is in all cases the
threefold hollow, but the saturated phase corresponds to a liquid phase with propensity for one-
dimensional disorder. Moreover in the latter conditions the surface is reconstructed whereby the topmost
layer is shifted with respect to the second layer [86Chu]. The phonon dispersion curves were measured
along ī − S , ī − Ǿ and ī − N and are reported in Fig. 57. HREELS data for the RW, for the first layer L
mode and for a second layer mode are depicted as triangles, diamonds, circles and squares, respectively.
The circles close to the N point for the clean surface could also be due to a vertically polarised phonon in
the second crystal layer. Data points due to the backfolded RW, observed only close to Γ are depicted as
inverse triangles. The HATOF data are reported as small dots. The difference for the p(2x1) phase at S
between HATOF and HREELS is most probably due to a slight difference in coverage. The dispersion
of the RW of the p(2x1) phase differs around N and S from the one of the clean surface: a frequency
increase from 14.5 meV to 16.5 meV takes place at N , while a decrease from 17 to 14 meV occurs at S .
Upon further dosing the RW frequency at N stays constant, while the frequency at S drops further. The
RW dispersion shows therefore a maximum at about ζ=0.75 ( ī − S ). As soon as the (1x1) phase forms, a
strong anomaly is observed along ī − Ǿ at the incommensurate wavevector q||=0.93 Å–1 both for the RW
and for the L-mode. The Rayleigh wave is apparently splitted into two branches, out of which the lower
one is not detected by HREELS and is therefore assigned to the excitation of electron hole pairs [97Koh]
or of a plasmon-like collective excitation of the hydrogen atoms [96Bun]. As shown in Fig. 58 the
anomaly is present for all wavevectors whose component along ī − Ǿ is equal to ∼1 Å–1. The theoretical
dispersion determined ab-initio is shown in Fig. 59 [96Bun]. In accord with the electronic origin of the
loss, the lowest HATOF branch is not present in the LDM result. The HREEL spectra for the (1x1) phase
are show in Fig. 60, while the dispersion data for the H induced modes along ī − Ǿ are collected in Fig.
61 for the three phases. For p(2x1) H three modes are observed, corresponding to the three degrees of
freedom of the adsorbate. The modes at 96 meV and at 156 meV are dipole active, implying adsorption in
the hollow site. The loss at 156 meV is mainly due to the perpendicular motion [96Bal]. For the (2x2) H

phase, five H related modes are observed in-specular, while a sixth branch is only excited for off-specular
conditions. All modes display only a small dispersion, except for the modes at 94 and 106 meV. As three
H atoms are present per unit cell, a total of 9 adsorbate induced phonon branches would be expected, but
the in-phase and anti-phase modes of two of the H atoms are nearly degenerate. The mode at ∼155 meV is
due to the perpendicular stretch motion. For the (1x1) H phase, the stretch vibration is at 163 meV and
displays a stronger dispersion than for the other H phases [96Bal]. Its lineshape is anomalous, consisting
of a continuum plus a single sharp peak [94Bal2, 96Bal] (see Fig. 60). Surface disorder is not sufficient to
explain this finding as no sharp loss for the vertical vibration at 155 meV would then be expected. The
effect is ascribed to delocalisation of the adsorbates in the parallel directions. The H atoms were
suggested therefore to be in a quasi liquid like phase. [94Bal2]. See also the introduction for further
discussion. Main references [92Hul1, 92Hul2, 96Bal, 94Bal1, 94Bal2].
4.5.2.3 Elemental Semiconductors and Insulators
C(100) H
Hydrogen on diamond (100) forms a (1x1) 2H phase at saturation (2 ML coverage) and (2x1) H phase
(1ML coverage). In both cases two H atoms are present in each unit cell. The optimised surface structures
are reported in Fig 62 together with the SBZ. The surface phonon dispersion curves, as predicted by first
principle theory [96San], are reported in Figs. 63 and 64 for the two phases. The H atoms are coupled to
an essentially ideal bulk truncated diamond substrate lattice for both phases, but the surface phonon
dispersion is quite different. The projected bulk phonon bands (hatched area in Figs. 63 and 64) exhibit
only small gaps and pockets, which host no surface modes, while several surface resonances are found
within the bulk bands. Modes denoted with S and B indicate stretch and bending motions of the
adsorbate. Frustrated rotations are marked by the subscript r. Subscripts s and a indicate the symmetric
and the antisymmetric motions of the two H atoms in the unit cell. SH modes are denoted by a bar over
the symbol. The mode STOX at Χ in Fig. 63 exhibits pronounced contributions of the C atoms in the third
layer. Comparison with experiment is possible only at Γ where HREELS data exist. For the (2x1) system
[93Aiz, 94Tho] loss peaks were reported at 363 meV and 152 meV [93Aiz] and 363 meV, 155 meV and
137 meV [94Tho], which coincide with the modes Sa (363 meV), BS+ (155 meV) and STOX (133 meV).
For the (1x1) system [93Lee] losses were found at 361 and 350 meV, corresponding to the symmetric
and antisymmetric H stretch modes, respectively and at 181, 162 and 153 meV. The latter modes fall in
the region of the H bending motion. Main reference [96San].
C(111) H
Hydrogen forms a (1x1) phase at saturation (2ML coverage) and a (1x2) phase at 1 ML coverage, which
is obtained by heating the saturated surface to 1300 K. The structure was investigated by LEED [93Lee]
and He atom scattering [97Sch]. The surface phonon dispersion of the (1x1) phase was measured by
HATOF [96Lan, 98Gle] and calculated from first principles [95San1, 95San2, 97Maz, 98Gle] and is
reported in Fig. 65a. Interestingly substituting H with D (see Fig. 65b) causes quite a large isotopic effect
on the surface phonon spectrum and especially on the RW dispersion (at Χ the frequency shifts from 17
meV in presence of H to 15 meV in presence of deuterium). The phenomenon is ascribed to the different
contribution of the adatoms to the oscillation amplitude. For the description of the symbols in Fig. 65 see
discussion of C(100) H. Main reference [98Gle].
Ge(100) (1x1) S
Sulfur is used to passivate the Ge surface and was suggested as a prototype for the development of an
intuitive picture of the chemical bond at the semiconductor surface. The structural and electronic
properties were calculated within DFT-LDA for the (1x1) phase obtained at saturation (1ML coverage).
The adsorption site is identified with the bridge, while the substrate reverts to a nearly ideal bulk
termination. The surface phonon spectrum was calculated by a total energy ansatz and is shown in

Fig. 66. There are localised adsorbate induced modes both above and below the projected bulk phonon
band. A prominent resonance, due to the vibration of the S adatoms, is present at Γ and is indicated by
the dashed line [92Pol].
Si(100)
The surface phonon dispersion for the clean (2x1) reconstructed surface was calculated [97Tüt] and it is
reported in Fig. 67.
Si(100) As, Ge and Sb
The surface undergoes a (2x1) reconstruction when covered with 0.5 ML of As, Ge or Si, forming
symmetric dimers with As and Sb and tilted dimers with Ge (see Fig. 68) [90Jed, 93Krü, 94Fra]. The
surface phonon dispersion was calculated ab initio. In the case of As two methods were applied and
slightly different results were obtained. In the first method, applied also to the Ge and Sb cases, the
adiabatic bond charge model was used for which the electronic and structural properties are determined
by an ab-initio pseudopotential method [99Tüt]. The second method employs an extension of the
semiempirical total energy Ansatz, which includes the electronic properties via a band-structure energy
term treated within the empirical tight binding method [98Grä]. All information necessary to determine
the parameters of the band structure and of the elastic energy is obtained from first principles total energy
and electronic structure calculations. The surface phonon spectrum according to the method of ref.
[98Grä]. is shown in Fig. 69a. SH modes are indicated with a bar above the symbol. Three kind of modes
are discussed: A-modes, located below the projection of the bulk phonons on the SBZ and mostly
dominated by the heavy As adatoms; D-modes, surface resonances within the bulk bands with energies up
to 40 meV which involve characteristic movements of the dimer adatoms together with the first substrate-
layer Si atoms; and S-modes, optical substrate-surface modes above 40 meV to which the As atoms do
not take part. The phonon dispersion curve obtained with the method of ref. [99Tüt] is reported in Fig.
69b. The main features agree with the result of the model of ref. [98Grä], but the single features appear at
slightly different frequencies. The corresponding spectra for Ge and Sb overlayers are reported in Figs. 70
and 71, respectively [98Tüt1, 98Tüt2]. Experimental results for these systems are still lacking.
Si(100)(2x1) H
H forms a (2x1) phase at 0.5 ML coverage. This system is characterised by a large misfit between the
mass of adsorbate and of substrate atoms, consequently the motion of the adsorbate is nearly decoupled
from that of the dimer atoms. The surface phonon dispersion was computed following a semiempirical
total energy ansatz [96Grä1] and is reported in Fig. 72. Experimental data for the phonon dispersion are
lacking. The symmetric and asymmetric H stretch modes are only marginally split in frequency (62.57
Thz and 62.91 Thz) [84Cha]. The H bending modes couple to the dimer atom motion so that their
splitting is larger (ν(Bs)=18.46 Thz, ν(Ba)=18.86 Thz). Such frequencies compare well with the HREELS
value of 18.98 Thz [83Stu]. Ds at 10.54 THz and Dt at 5.95 Thz correspond to dimer stretch and tilt
motions. The D1 mode at 10.3 Thz and the D2 mode at 13.54 Thz involve mainly a bending of the dimer
bond in the xz-plane. SH modes are denoted with a bar over the symbol.
Si(110) (1x1) H
The hydrogenated Si(110) surface was studied by infrared spectroscopy [96Wat]. Hydrogen adsorption
restores the ideal bulk terminated geometry of the Si substrate at 1 ML coverage. The adsorbates sit in
atop sites. The surface phonon spectrum was calculated with a semiempirical total energy method. The
result is shown in Fig. 73 [97Grä]. Hydrogen stretch modes are denoted by S, hydrogen bending modes
by B. C-modes are chain modes of the substrate.

Si(111) (1x1) As
In contrast to the inherent instability of the clean Si(111) surface, the As capped surface (1ML coverage)
is inert. Each As atom is covalently bonded in an almost bulk-like configuration to the three underlying Si
atoms. The surface crystallography was investigated by LEED [86Olm] and medium energy ion
scattering [88Cop], which indicate only a slight outwards relaxation of the As atoms (~0.2 Å). The
surface phonon spectrum was investigated by HATOF [90Doa1, 90Doa2, 92San2] and by HREELS
[94Sch] and is reported in Fig. 74 together with a theoretical prediction. The different surface modes are
denoted by different symbols. The As overlayer affects the surface dynamics principally because of the
mass defect in the outermost layer. The two acoustic branches were found also for the (1x1) H phase and
are therefore intrinsic of the substrate. The surface phonon spectrum was calculated from first principles
following total energy schemes and ab-initio calculations based on the local density approximation of
density functional theory employing non local, norm conserving, pseudopotential [98Grä]. A similar very
good agreement with experiment was obtained independently by Honke et al., who calculated the surface
phonon dispersion using density functional perturbation theory [96Hon].
Si(111) ( 3 × 3 ) Ga
The ( 3 × 3 ) reconstruction is induced on the Si(111) surface by a number of different metals at a

coverage of 0.3 ML and consists of metal atoms occupying half of the T4 sites. Each adatom is located
directly above a Si atom in the second layer and is bonded to three Si surface atoms, such that all dangling
bonds are saturated. The phonon dispersion for the Ga overlayer was investigated by HREELS [95Sch] as
well as by HATOF [89Doa]. The HREELS results and HATOF data are compared with the result of first
principle calculations [99Fri2] in Fig. 75.
Si(111) (1x1) H
The Si(111) (1x1) H surface can be grown at 1 ML coverage with a high degree of perfection and became
therefore a prototype system for well defined experimental studies of surface phonon dispersion. HATOF
data can be found in refs. [88Har, 90Doa3], HREELS data in refs. [92Stu, 92Dum]. Theoretical
calculations were performed in refs. [88Gold, 88Mig, 95San1, 96Grä2, 96Hon]. The HATOF data
[90Doa3] are reported in Fig. 76a and compared with the theoretical prediction of ref. [88Mig]. HREELS
data [92Stu, 92Dum] are reported in Fig. 76b, together with the theory of ref. [95San1]. The theoretical
prediction for the deuterated system is reported in Fig. 76c [96Grä2]. The lowest frequency mode is the
RW. Several surface modes are found in the gaps of the projection of the bulk phonons. Due to the large
mass mismatch the H vibrational modes are decoupled from those of the substrate. The system behaves
therefore as a perfect realisation of the ideal bulk terminated Si(111).
4.5.1.2.4 Compound Semiconductors
GaAs(110)
Experimentally the surface was investigated by HATOF [87Har, 87Doa]. The result of a theoretical
model calculated by ab-initio linear response formalism is shown in Fig. 77 [95Fri1].
GaAs(110) (1x1) H
The surface phonon dispersion was determined by means of ab-initio linear response formalism [95Fri1].
No experimental data are yet available for the phonon dispersion curves. HREELS was recorded at Γ for
the hydrogen modes [96Gra2]. The hydrogenation is saturated at 1 ML coverage. The 1 ML coverage
phase has the (1x1) periodicity of the substrate and causes the removal of the relaxation present for the
clean surface and the onset of a slight counter-rotation of the atoms in the first plane of the substrate.
Direct information about the structure has been obtained by photoelectron diffraction [95Ruo] and

grazing incidence X-ray diffraction [94Ruo]. The theoretical prediction for the surface phonon dispersion
of GaAs (1x1) H [95Fri1] is shown in Fig. 78. The main differences with respect to the clean surface are:
i) the third acoustic phonon mode along Γ – Χ' predicted for the clean surface [93Fri] and confirmed by
HATOF [87Doa] is absent in the hydrogenated phase; ii) the surface optic phonon branch, characterised
by an opposing motion of the surface cations and of the second layer anions, located above the bulk band
for the clean surface (as confirmed by HREELS [94Nie]) is shifted downwards into the optic bulk bands,
becoming a surface resonance. The surface localised modes of GaAs(110) covered by 0.5 ML of
hydrogen are similar to those of the (1x1) H phase except for a vibration at 35.1 meV appearing at Γ
when hydrogen is chemisorbed on the Ga atoms. Further theoretical papers [93Ber, 95Fri1].
GaP(110) H and Sb
Similar to the case of GaAs, H and Sb form (1x1) phases at saturation on GaP (1 ML coverage). Contrary
to the GaAs case however, the acoustic and optical bulk bands are now well separated. The phonon
modes above the bulk continuum (dashed lines) are shifted into the optical bulk bands upon H adsorption.
The phonon dispersion curves are reported in Figs. 79 and 80 [99Fri1].
InAs(110) (1x1) H
The surface phonon dispersion is reported in Fig. 81 for the (1x1) phase corresponding to 1 ML coverage,
as calculated from first principles in ref. [99Fri1]. The modes are similar to those of GaP(110)(1x1) H, to
which system we refer for further discussion [99Fri1].
InP(110) (1x1) H
The interaction of H with InP(110) leads to complicated surface reactions. At saturation however this
system is very similar to GaAs(110). The surface phonon dispersion was determined by means of an ab-
initio linear response formalism [95Fri1]. No experimental data are yet available for the phonon
dispersion curves, while HREELS data [96Nie] were recorded for the Γ point. The main feature in the
HREEL spectra (not shown) is the Fuchs-Kliever mode at 54.3 meV. Hydrogen atoms bind
simultaneously to In and P atoms in each stage of the adsorption process. The hydrogenation is saturated
at 1 ML coverage with two H atoms per surface unit cell. The 1 ML coverage has the (1x1) periodicity of
the substrate. Adsorption leads to the removal of the relaxation in the first layer of the substrate and to the
onset of a slight counter-rotation of the atoms in the first plane of the substrate. The theoretical prediction
for the surface phonon dispersion of InP(110)(1x1)H [95Fri1] is shown in Fig. 82 [95Fri1].
4.5.2.5 Oxides and Salts
Quite a bit of work was performed for physisorbed species on MgO and NaCl. In all cases little or no
modification of the surface phonon spectrum occurred. These results are therefore not shown.
MgO
For the MgO(100) CO system the dispersion of the low energy adsorbate modes was measured by
HATOF [95Ger]. No evidence was found for the RW.
NaCl
Adsorption of several gases was studied on the (100) surface by HATOF: CO2 [93Lan, 93Hei, 95Lan],
H2O [95Bru], acetylene [98Pic], and OCS [96Gle,96Doh]. The RW is always a prominent structure in the
spectra. The RW dispersion curve is crossed by several modes corresponding only to the frustrated
translation parallel to the surface in the case of water admolecules and to several adsorbate induced
modes for the other gases.

Acknowledgments
The author likes to thank Mariachiara Lupi for critical reading of the manuscript and for helping in its
preparation.

Figures for 4.5
X C S
Y K
∆ T
Y ∆ D T’ (0,0)
M
Γ Σ Γ Σ X Γ Σ M
(110)
ϑi ϑs
(001) Face centered cubic (fcc) (111) e −or He e−
He
M N
Σ S
Y q II
X Γ H
Γ ∆ N’
Fig. 2. Ewald sphere construction for the inelastic
(001) (110) scattering events. For He atoms the energy loss is
Body centered cubic (bcc) comparable to the impact energy of the particles, while
for electrons it is negligible on the scale of the figure.
Fig. 1. Surface Brillouin Zone (SBZ) for the low Miller The HREELS spectra are therefore effectively constant
index surfaces of face centred cubic (fcc) and body q|| scans, while HATOF spectra run along the so-called
centred cubic (bcc) lattices discussed in the present scan curves and include losses with different q|| values.
review.
Surface phonons of (100) c (2×2) surfaces at Γ Surface phonons of (100) c (2×2) surfaces at X
Adsorbate Modes Adsorbate modes
a) b) c) a) b) c)
E,odd E,even A1,even E,odd E,even A1,even
First layer substrate modes First layer substrate modes

d) e) f) d) e) f)
E,odd E,even A1,even

E,odd E,even A1,even
g) h) i)
g) h) i)
b E,odd B2,even B1,even

a E,odd E,even B1,even
Fig. 4a, b. Displacement pattern of the surface phonons of a c(2x2) overlayer on a (100) substrate at: (a) Γ ; (b) X .

Adsorbate
p (2×2) Substrate c (2×2)
Top View
A A’ A A’
Side View
A A’ A A’
X2 X
Γ M Γ M Fig. 3. Direct and reciprocal lattice for p(2x2) and
c(2x2) superstructures on a fcc(100) surface: SBZ size
X1 reduction and folding.
Ni(100) c(2×2)O
without internal stress with internal stress
500 15 500 15
400 12 400 12
Wavenumber ν [cm−1]
Frequency ω [THz]
Frequency ω [THz]
300 9 300 9
200 6 200 6
100 3 100 3
0 0 0 0
0 0.5 1.0 0 0.5 1.0
Γ Red.wavevector coord. ξ X Γ Red.wavevector coord. ξ X
Fig. 5. Surface phonon dispersion along Γ – X for Ni(100) c(2x2) O. Two LDM are shown: in the left panel a 70%
reduction of the force constant between the Ni atoms in the first and second crystal layer is necessary to reproduce the
anomaly; in the right panel the same effect is reached by introducing a compressive stress at the surface [86Rah]. The
shaded area indicates the continuum due to the projection of the bulk phonon band. (ξ = Qx/1.26 Å–1)

20 25
1
W(110) clean clean
L T 20
15
Intensity I [kHz meV −1 ]

Phonon energy hω [meV]
15
10
2 10
2
5
5
1
0 0
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 − 20 −10 0 10 20
a Red.wavevector coord. ξ a Energy loss E loss [meV]
20 9
H-saturated 2
H-saturated 4
8
7
15
Intensity I [kHz meV −1 ]
5
6
4
5
10 1 4
3 3
3
5
5 2
2
1
1
0 0
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 − 20 −10 0 10 20
b Red.wavevector coord. ξ b Energy loss E loss [meV]
Fig. 6a, b. Surface phonon dispersion for clean and H covered W(110) (left panels) and HATOF scan curves
recorded for an impact energy Ei = 37.74 meV and ϑ i = 49 °, crossing the critical spectral region (right panel). The
solid lines in the left panel represent the lower edges of the surface projected transverse (T) and longitudinal (L) bulk
phonons. For the bare surface the data points are assigned to the RW (lowest branch) and to the L resonance (upper
branch). For the (1x1) H phase the same two branches are present below q|| ≅ 0.6 Å–1, while at larger wavevectors the
lower branch softens and splits. The numbers in the dispersion curves indicate the peaks in the HATOF spectrum
[93Hul2].

2100 Γ K M’ K’
I r(100)-(5×1)+16 L CO 6
I r(100)-(1×1)+16 L CO Cu(110):Xe
2050 5 T
2

RW
2000 4
L
H1
500 3 T
H2
2
450
1
400
0
0 0.5 1.0 1.5 2.0 2.5
60
Wavevector qII [Å−1]
20
Fig. 8. Surface phonon dispersion along [ 1 1 0 ] for an
0 0.2 0.4 0.6 0.8 1.0 incommensurate Xe monolayer deposited on Cu(110)
Γ Red.wavevector coord. ξ M measured with HATOF. The modes H1 and H2 are
generated by hybridisation of the vertical vibration of
Fig. 7. HREELS data for the dispersion curves of the the adsorbate with the RW. The mode L corresponds to
CO induced modes on Ir(100). The data are nearly the longitudinal motion of the Xe adatoms. The upper
identical for adsorption on the (1x1) surface (crosses) dispersionless feature (⊥2) corresponds to the double
and on the (5x1) reconstructed phase (squares). The excitation of the vertical vibration. The short dashed
main origin of the wavevector dependence of the lines are the calculated dispersion curves for vertical
internal CO stretch frequency is the long range dipole- (⊥) and longitudinal (L) motion assuming a perfectly
dipole interaction [91Kis]. (ξ = Q||/1.64 Å–1) hexagonal Xe lattice. The solid lines are the dispersion
curves with the actual lattice distortion taken into
account. The long dashed line indicates the substrate
RW [94Zep].
X 〈110〉 Γ 〈100〉 M
Ag(100)
20
L
L
R
10 R
SH
HAS
EELS Fig. 9. Ag(100). Surface phonon dispersion
of the bare Ag surface. [91Che, 90Mor,
0 94Bun].
1.0 0.5 0 0.5 1.0 1.5

X Γ X M‘ Γ M‘
10 15
Ag(100) c (2×2)Cl 〈110〉 〈001〉
10
5
Phonon energy ∆E [meV]
Phonon energy ∆ E [meV]

5
0 0
−5
−5
−10
−10 −15
−1.0 − 0.5 0 0.5 1.0
( 23 32 ) (1 1) ( 12 12 )
Wavevector qII [Å−1] Wavevector qII [Å−1]
Fig. 10. Ag(100)-c(2x2) Cl. Extended zone plot of the phonon energies measured by HATOF [83Lam,84Lam].
Negative frequencies correspond to phonon annihilation. The dashed lines indicate the bulk band edge, while the
solid lines are the surface modes S1 and S4 as calculated by Castiel et al. [76Cas] for bare Ag(001) surface. Along
Γ Μ the data were recorded around the ( 1 1 ) diffraction peak.
Γ [ ξ 0] X Γ [ 0ξ ] Y
18 15
Ag(110) Ag(110) MS 7
15
12
MS 7
12
9
9
MS 0
6
6 S3 S1
S1
3
3
0 0
0 0.2 0.4 0.6 0.8 1.0 0 0.2 0.4 0.6 0.8 1.0
a [0 0] Red.wavevector coord. ξ [1 0] b [0 0] Red.wavevector coord. ξ [0 1]
Fig.11a, b. Ag(110). Surface phonon dispersion of the clean Ag(110) surface measured by HATOF along (a)
Γ − Χ and (b) Γ − Υ [87Bra1, 87Bra2, 89Tat]. The solid line in (a) is the result of a LDM [89Tat].

10
Ag(110)p(2×1)O
8
MS 7
6
S3
S1 Fig. 12. Ag(110)-p(2x1)O Surface phonon

2 dispersion curves measured by HATOF
MS 0 (open circles: experimental data, solid
lines: LDM fit for the missing row
0 reconstructed surface) [89Yan,87Bra].
0.4 0.2 0.2 0.4 0.6
X‘ Γ Y
−1
Wavevector qII[Å ]
Γ X‘
10
Γ Y
12
8
Ag(110)p(3×1)O
9
6
B
6
4 A
3 3 3
22
1 1 1
3 2 2
2 3 3 3
2 2
3 3 3
2 2
1 1 1
0 0
0 0.1 0.2 0.3 0.4 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7
−1 −1
a Wavevector qII[Å ] b Wavevector qII[Å ]
Fig. 13a, b. Ag(110)-p(3x1)O. Surface phonon dispersion curves measured by HATOF along (a) Γ − X (folded
direction) and (b) Γ − Y (experimental data: open circles - intense structures; triangles - weak features). The lines
represent the result of a LDM assuming a missing row reconstructed surface and the bulk value of the force constant
between the substrate atoms. Inset in (b): added row model of the reconstructed surface. The Ag atoms are numbered
starting from the surface layer and the O atoms are represented by filled circles. Main reference: [93Bra]. Further
references: [90Bra1, 90Bra2, 91Bra].

400 50 400
Al(111)
Al(111) (√3×√3) R 30° Na
40
40
300 300
30

30
Phonon energy hω [cm−1]


200 200
20
100 R1 100
10
S1
10
R2 S1
0 0 0 0
0.5 1.0 0.5 1.0
Γ K’ M Γ K’ M
−1 −1
a Wavevector qII[Å ] b Wavevector qII[Å ]
Fig. 14a, b. Al(111) (√3 x √3) Na. Surface phonon dispersion determined by HREELS along Γ M . (a) clean
surface: HREELS data: open circles and LDM results; (b) adsorbate covered surface (HREELS: open circles) and
LDM calculation assuming a substitutional adsorption site for the Na adatoms. Shear vertically polarised surface
modes are represented by thick solid lines, shear horizontally polarized surface modes by full squares [97Nag].

400 X [ξ ξ ] Γ [ξ 0 ] M
Al(111) (2×2)Na 140
40 4.0
Cu(100)
120 3.5
Phonon wavenumber ν [cm−1]

100 3.0
Phonon frequency ν [THz]

300 2.5
80
30 2.0
60
1.5

40
1.0
20 0.5
200
20
0 0
0.5 0 0 1.0
[ 12 12 ] [0 0] [1 0]
Red.wavevector coord. ξ
R1 Fig. 16. Cu(100). Surface phonon spectrum for the bare

100 surface [86Wut]. The circles are the experimental
10
HREELS data points, dashed and solid lines are the
result of the LDM fit with bulk force constants and
with modified surface force constants, respectively.
S1
←
Fig. 15. Al(111) (2x2) Na. HREELS data for the high
0
coverage phase as measured by HREELS (filled
0
0.5 1.0 circles) along Γ M . The open circles and solid lines
Γ M’ M
−1 represent data and LDM calculations for bare Al(111)
Wavevector qII[Å ]
along the same direction [97Nag].
10 10
Ag(100) c (2×2)CO 〈110〉
〈100〉
5 5
0 0
−5 −5
−10 −10
−15 RW −15
− 2.0 −1.0 0 1.0 2.0 3.0 4.0 −1.0 0 1.0 2.0

Γ M Γ X
a Wavevector qII [Å−1]
b Wavevector qII [Å−1]
Fig. 17. Cu(100) c(2x2) CO. Surface phonon spectrum as measured by HATOF. The solid and the dashed curves are
the dispersion of the RW for the clean surface and its backfolded branch. Losses corresponding to the excitation of
the RW are plotted as open circles. Filled and open squares denote the frustrated translation mode of the CO
molecules in the c(2x2) overlayer and at defects [95Ell].

800 Cu(100) c(2×2)N 24

Cu(100) √2×√2 O
NII
700 21

400 12
N T
O
300 9
200 6 1st Cu
a 〈110〉
100 3
RW 2nd Cu
0 0
Γ 0.2 0.4 0.6 0.8 X
Fig. 18. Cu(100) c(2x2) N. Surface phonon dispersion b 〈100〉
as measured by HREELS. The shaded area indicates
the continuum of bulk modes [86Fra]. The lines Fig. 19. Cu(100) (√2 x 2√2) O. Schematic model of the
indicate surface substrate phonons and adsorbate missing row reconstructed Cu(100) c(2x2) O phase.
modes. (ξ = q||/1.23 Å–1)
800 Γ X
Cu(100)(√2×2√2 ) O Cu 400 12
O Cu(100) p(2×2)S
700
ω (S ) T
600 9
300
ω (S ) II

500
400 200 6
300
200 100 3
ω (S4 )
S1
100
0 0 0
0 0.25 0.50 0.75 1.00 0 0.5 1.0
Γ M‘ M
Red.wavevector coord. ξ Fig. 22. Cu(100) p(2x2) S. Surface phonon spectrum as
Fig. 20. Cu(100) (√2 x 2√2) O. Surface phonon measured by HREELS. Lines are surface modes
dispersion as measured by HREELS, reported on an according to a LDM model. The shaded area represents
extended zone scheme. The insets indicate schemati- the projection of the bulk phonons on the SBZ [87Fra].
cally the motion of the adatoms for each mode. TheRW (ξ = q||/1.23 Å–1)
and two resonances are observed. The RW branch
shows no dispersion in the second Brillouin zone
[89Wut1, 89Wut2]. (ξ = q||/1.74 Å–1) For Fig. 21, see next page

Γ X Γ
12
isolated PF3
Cu(100) PF3 M
9 Γ X
RW [100]
6 [110]
FTx
3
a
0
RW2 c(4×2) PF3
RW1
6
FTx
3
b
0
RW2
9
RW 1
6 Fig. 21a-c. Cu(100) c(4x2) PF3. Surface phonon

[110] dispersion measured with HATOF: (a) isolated PF3
[110] molecules (exposure 0.4 langmuirs PF3), (b) c(4x2)
3
PF3 overlayer, (c) results of a LDM assuming the bulk
radial force constant between nearest neighbour
0 c
substrate atoms [99Bra].
0 1.23 2.46
−1
Wavevector qII[Å ]
250 Mo(110)
200
150
Fig. 23. Mo(110). Surface phonon

100 dispersion of the clean surface [97Krö,
98Krö1, 98Krö2, 92Hul2].
( S Γ :ξ = q||/1.22 Å–1),
50
( Γ H :ξ = q||/1.50 Å–1)
0 ( N Γ :ξ = q||/1.41 Å–1)
1 0.5 0 0 0.5 1 1 0.5 0
S Γ Γ H N’ N Γ

240
200 Mo(110) H “(2×1)”H
160
120
80
40
240
200 (2×2)H
160
120
80
40
240
(1×1)H
200
160
120
80
40
0
1 0.5 0 0 0.5 1 1 0.5 0
S Γ Γ H N’ N Γ
Fig. 24. Mo(110) H. Surface phonon dispersion for the different H superstructures on Mo(110) along three directions
of the SBZ. Triangles indicate HREELS data for the RW, circles and diamonds indicate surface resonances. The dots
denote HATOF data. A shallow dip is observed for the H saturated phase along N Γ at a critical wavevector of
0.93 Å–1 both for the RW wave and for the L resonance [93Hul2, 97Krö]. ( S Γ :ξ = q||/1.22 Å–1), ( Γ H :ξ = q||/1.50
Å–1) and ( N Γ :ξ = q||/1.41 Å–1)

1300
Mo(110) H
1200
(1×1)H (2×2)H “(2×1)”H
1100
1000
900
Fig. 25. Mo(110) H. Dispersion of the H

800
induced modes for the different H phases
as measured by HREELS along Γ H
700
[97Krö]. (ξ = q||/1.50 Å–1)
0 0.3 0.6 0.9 1.2 0 0.3 0.6 0.9 0 0.2 0.4 0.6
250
Mo(110)p(2×2)0
Fig. 26. Mo(110) p(2x2) O. HREELS
data for the Mo(110) p(2x2)O phase
200 recorded for a crystal temperature T=110
K. The RW, the L-mode and the dipole

active surface resonance are depicted as
150 triangles, circles and diamonds,
respectively. The solid triangles and the
dots along ( Γ H ) were measured with
100
the crystal at room temperature [98Krö1,
98Krö2].
50 ( S Γ :ξ = q||/1.22 Å–1),
( Γ H :ξ = q||/1.50 Å–1)
0 ( N Γ :ξ = q||/1.41 Å–1)
1 0.5 0 0 0.5 1 1 0.5 0
S Γ Γ H N’ N Γ

X [ ξξ ] Γ [ξ 0] M
320
Ni (100) 2
nd
T
nd nd 9
2 2 II
2
nd
+ 2nd R6 T
280
T
II
8
nd
S6 2 T
240 7
st R5 nd R2 R1 S 2
1 II 2 II

nd
200 2 II st 6
1 II
nd
2 T
5
160
R4
R3 1 II
st Fig. 27. Ni(100) Surface phonon
4 dispersion as measured by
120
HREELS [86Roc2]. The solid
S1 3 lines are surface modes, the
80 dashed lines surface resonances
S4 2 according to LDM fit with
modified force constants at the
40 surface. 1 and 2 indicate modes
1
with largest amplitude in first and
second crystal layer, respectively.
0 0
0.5 0.4 0.3 0.2 0.1
0 0 0.2 0.4 0.6 0.8 1.0
[ 12 12 ] [0 0] [1 0]
Ni(100)- C
725
c
700
c II
675
super structure
p4g
400
375
c T
350
b
325 Fig. 28. Ni(100) C. Carbon coverage dependence of the
frequency of the (S4) RW at X (a), of the Ni-C stretch
140 S4 a at Γ (b) and of the frustrated translation of the C
120 atoms parallel to the surface (c) at ξ = 0.3. The crystal
0 0.1 0.2 0.3 0.4 0.5 was annealed to 600 K. [87Roc].
Carbon coverage θ [ML]

Γ 0.2 0.4 X’ 0.6 0.8 X Γ X’ X

800 24 800 24
c II Ni(100) p4g N
700 c II 21 700 N II 21
Ni(100) p4g C

500 15 500 15

N

T
c T
400 12 400 12
R2
300 9 300 9
R4
R3 200 6
200 6
R2 R1
R1
100 S4 3 100 3
RW
Γ 0.2 0.4 0.6 0.8 X Γ X’ X

Red.wavevector coord. ξ Wavevector qII [Å−1]
Fig. 29. Ni(100) p4g (2x2) C. Dispersion of the surface Fig. 30. Ni(100) p4g (2x2) N. Dispersion of the surface
phonons as measured by HREELS. The data are phonons for the p4g reconstructed c(2x2) phase of N
reported for an extended zone scheme, the zone along Γ − X . The experimental points, measured by
boundary being at X ′ [87Roc]. The lines are the result HREELS, are reported for an extended zone scheme,
of a LDM. (ξ = q||/1.26 Å–1) the zone boundary being at X ′ [86Dau, 88Rah]. The
lines are the result of a LDM. The squares denote
surface resonances, the circles surface modes.
For Figs. 31 and 32, see next pages
150
Ni(100) O
ω S (X)
4
100
c(2×2) Fig. 33. Ni(100) O. Oxygen coverage dependence of

the RW frequency at X for a surface which was
annealed to 400 K after oxygen adsorption (crosses)
50 p(2×2) c(2×2) and for the non annealed system (triangles and circles).
The dashed line indicates the expected reduction of
ωS 4 ( X) given by mass loading. The solid lines are
guides to the eye. The coverage regions giving ordered
superstructures are shown, too [85Roc].
0 15 30 45 60
Oxygen coverage θ [%]

Γ X’ X
Ni(100) - p(2×2)O
700 21
O II
600 18

O T
400 12
R
200 6 Fig. 31a, b. Ni(100) p(2x2) O. Surface phonon
dispersion measured by (a) HREELS and (b) HATOF.
The HREELS data are reported in an extended zone
scheme, the zone boundary of the p(2x2) structure
100 3
S4 being at X ′ [84Sze]. The lines are the result of a
LDM. In (a) the backfolded branches are reported as
dashed lines. Reference [84Sze, 91Ber, 86He]. Further
references [90Col, 85Sze].
0 0.5 1.0
a Wavevector qII [Å−1]
[110] [001]
Ni(100) - p(2×2)O
15
100
10
50
5
Γ 0.1 0.2 0.3 0.4 0.5 X’ M’ 0.8 0.7 0.6 0.5 0.4 0.3 0.2 0.1 Γ

500 15
Ni(100) - c(2×2)O
400 12

300 9
200 6
Fig. 32a, b. Ni(100) c(2x2) O. Surface phonon
dispersion measured by (a) HREELS and (b) HATOF.
The different symbols in (a) denote the different
surface modes and resonances. The solid lines are the
result of a LDM model including the surface stress
100 3 field. Apart from the Rayleigh wave an additional mode
(dashed curve) is observed by HATOF along both
crystallographic directions which shows very little
dispersion. Such mode is ascribed to the high
concentration of oxygen vacancies on the studied
surface. Main references [83Leh, 84Rah, 91Ber].
Further references [86Leh, 90Yan]
0 0.5 1.0
Γ X
a Red.wavevector coord. ξ
[110] [100]
15
Ni(100) - c (2×2)O
100
10
50
5
0.2 0.4 0.6 0.8 1.0 1.2 0.8 0.6 0.4 0.2
Γ X M’ Γ

400 12 Geometric structure of Ni(110)/CO(2×1)p2mg

Ni(100) - c(2×2)S S
R = 1.45 Å
T ω T
Unit cell First Brillouin zone
ωS
g ∆Y
T
ω IIS
ω IIS X S
−1
4.98Å
300 9 Cs
0.63Å
[110] Γ Y

3.52Å −1
ω S6
[001] 0.893Å
200 6
ω S4
100 3
0 0.5 1.0
Fig. 34. Ni(100) c(2x2) S. Surface phonon dispersion

measured by HREELS. Crosses denote the RW,
triangles and squares the parallel and the vertical Fig. 36. Ni(110) p2mg (2x1) CO. The (2x1)p2mg
vibration of the adsorbate, respectively. The open adsorption geometry is shown, together with the
circles stay for a surface resonance at 4.5 THz and for relevant lattice parameters and symmetry elements and
the S6 mode above 6 THz. The shaded area is the SBZ [90Voi2]. The CO coverage is 1ML.
projection of the bulk phonon bands on the SBZ. The
lines are the result of a LDM calculation. References
[85Leh, 86Leh, 90Yan]. (ξ = q||/1.26 Å–1)
For Fig. 35 and 37, see next pages
[110]
Ni(110)H [001]
1 1
[110] 2
[001]
cS
x
y
g cS
a b species II
Fig. 38a, b. Ni(110) H. Models for (a) the (2x1) H and (b) the reconstructed (1x2) H covered surfaces. Open and
closed triangles indicate the two H adatom moieties.

Γ [ξ 0] X Γ [0 ξ] Y
320 320
Ni(110) 9 9
280 280
8 8
240 S7 240
7 7

MS 7 MS 7

200 6 200 6
160 5 160 5
4 4
120 120
S1 S3
3 3
80 80
2 S1 2
40 1 40 1
0 0 0 0
0 0.2 0.4 0.6 0.8 1.0 0 0.2 0.4 0.6 0.8 1.0
[0 0] Red.wavevector coord. ξ [1 0] [0 0] Red.wavevector coord. ξ [1 0]
a b
Fig. 35. Ni(110). Surface phonon dispersion for clean Ni(110) [87Leh2].
2000
1800 Ni(110)/CO(2×1) p2 mg
[001] [110]
Γ10
X S
Γ Y
600
Fig. 37. Ni(110) p2mg (2x1) CO. Surface phonon

400 dispersion as measured by HREELS [90Voi2] reported
for an extended zone scheme. Only modes symmetric
with respect to glide reflection are observable in the
200 first SBZ along Γ − X , and the antisymmetric ones in
the second.
( Y Γ : ξ = q||/0.893 Å–1), ( Γ Γ10 ξ = q||/0.63 Å–1).
1.0 0.8 0.6 0.4 0.2 0 0.5 1.0 1.5 2.0
Y Γ X Γ10

90 140
Ni(110) H A1(S3) Phonon at Y
B1(S1) Phonon at Y

80 130
70 120
60 110
0 0.5 1.0 1.5 0 0.5 1.0 1.5
a H coverage θ [ML] b H coverage θ [ML]
140
S1 Phonon at X
135
130
125
120 Fig. 39a-c. Ni(110) H. Hydrogen coverage

dependence of the phonon frequencies of:
(a) S1 and (b) A1 at Y ; (c) of the S1 mode at
115
X . References [89Voi, 87Leh1].
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
c H coverage θ [ML]
Ni(110) p2mg(2×1) H
1200 36
H
900 27
H II
600 18
Fig. 40. Ni(110) p2mg (2x1) H.
Surface phonon dispersion
300 9 measured by HREELS at 1ML
coverage [89Voi].
S3 ( Y Γ : ξ = q||/0.893 Å–1)
S1 ( Γ Γ10 : ξ = q||/1.26 Å–1).
1.0 0.8 0.6 0.4 0.2 0 0.2 0.4 0.6 0.8 1.0
Y Γ X
Red.wavevector coord. ξ Γ10

Ni(110) (1×2) H
1200 36
900 27

600 18
Fig. 41. Ni(110) (1x2) H. Surface

300 9 phonon dispersion measured by
HREELS for the reconstructed phase
100 3 obtained at H saturation coverage
(1.5 ML) [89Voi, 87Leh1, 87Iba].
( Y Γ : ξ = q||/0.893 Å–1)
( Γ X : ξ = q||/1.26 Å–1).
1.0 0.8 0.6 0.4 0.2 0 0.2 0.4 0.6 0.8 1.0
Y Γ X
Γ01 Red.wavevector coord. ξ
Ni(110) - (2×1) O Γ [ξ0] M

800 24 40
Ni(111)
35
700 21 30 S2
25
X‘
R1
20
15
S1
300 9
10
5
200 6
0
0 0.2 0.4 0.6 0.8 1.0
[00] Red.wavevector coord. ξ [10]
100 3
Fig 43. Ni(111). Surface phonon dispersion for the bare
Ni(111) surface [90Men1, 90Men2]. The solid and
dashed lines are the result of a LDM assuming the bulk
1.0 0.8 0.6 0.4 0.2 0 0.2 0.4 0.6 0.8 1.0 value for the force constants between surface atoms and
modified constants, respectively.
Y Γ X
Fig. 42. Ni(110) p(2x1) O. Surface phonon dispersion

determined by HREELS [90Voi2, 91Yan]: open circles
data recorded at T=120 K, filled circles at T=300 K.
( Y Γ : ξ = q||/0.893 Å–1) ( Γ X : ξ = q||/1.26 Å–1).

80
Ni(111) p(2×2) O
70
60

50 final parameters
experimental data
40 data regression
New position of oxygen

bonded atoms
30
Original position of the
first nickel layer 20
New position of non - oxygen 10

bonded atoms
0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0
a
Fig. 45. Ni(111) p(2x2) O. Surface phonon dispersion
measured by HREELS. [94Tis].
Γ M’ M
Fig. 44a, b. Ni(111) p(2x2) O. (a) Schematic views of

Ni(111) p(2x2) O: upper panel from above; lower
panel: cut through the crystal along the dashed line. The
arrows indicate that the three nickel atoms bonded to
the oxygen atom are shifted by 0.07 Å along the arrow
direction. (b) SBZ [90Gri].
15
Pb (111) d-octane
10 AOP 1
FTz
5
Fig 46. Pb(111) d-octane. Surface phonon spectrum as

RW measured by HATOF [96Fuh]. FTz and AOP1 are the
frustrated translation vertical to the surface, and an
0 internal vibration of d-octane, respectively.
K Γ M
Wavevector q

Γ Σ M Σ‘ K T Γ
Pt (111) (1×1) H
24
20
16
12
Fig. 47. Pt(111) (1x1) H. Surface phonon

4 dispersion on Pt(111) (1x1) H was
measured by HATOF. Filled circles are
HATOF data points, lines are the result of
0 LDM calculations [89Bor].
0 0.4 0.8 1.2 2.0 1.6 1.2 0.8 0.4 0
Γ M0 Γ M0
12 12
Pt(111) p (2×2) O
10 10
8 8
6 6
4 4
2 2
0 0
0 0.2 0.4 0.6 0 0.2 0.4 0.6
Wavevector qII [Å−1] Wavevector qII [Å−1]
Fig. 48. Pt(111) p(2x2) O. Surface phonon dispersion of the p(2x2) overlayer as measured by HATOF along Γ − M .
Open circles refer to data recorded in the first Brillouin zone, while filled circles are for events detected in the second
Brillouin zone. The backfolded mode at 10 meV is observed only in the first zone. The result of a LDM is reported in
the right panel. Reference [86Ker1, 86Ker2, 87Sze, 87Ker].

12
12 Pt(111) (1×1) O
10
10 k12 = 1.1k

8
8
k12 = 0.8k
6
6
4
4
2 clean Pt(111)
2
Pt(111)”oxide”
0 0
0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 0 0.2 0.4 0.6 0.8 1.0 1.2
Γ Wavevector qII [Å−1]
b
M K Γ Wavevector qII [Å−1]
a
Fig. 49a, b. Pt(111) (1x1) O. Surface phonon dispersion of the (1x1) O phase [87Neu, 86Ker2], along (a) Γ Κ and
(b) Γ Μ open symbols: bare surface, filled symbols oxygen saturated phase. In (b) the dashed and solid curves are
the result of a LDM implying an increase of 10% and a decrease by 20% of k12, respectively.
Γ X‘ Γ Y‘
10 10 Fig. 50a, b. Rh(110)(2x2) O.
Rh(110) (1×2) Surface phonon dispersion, as
8 8 measured by HATOF
[93Bel], for: (a) the bare

(1x2) reconstructed surface;
6 6 and (b) for the oxygen
covered Rh(110) surface. The
oxygen coverage is 0.5 ML.
4 4
2 2
0 0
0 0.2 0.4 0.6 0 0.2 0.4 0.6
a Wavevector qII [Å−1] Wavevector qII [Å−1]
Γ Y‘ Γ X‘ Γ S‘
10 10 14
Rh(110) (2×2)O 12
8 8
10
6 6 8
4 4 6
4
2 2
2
0 0 0
0 0.2 0.4 0.6 0 0.2 0.4 0.6 0 0.2 0.4 0.6 0.8
b Wavevector qII [Å−1] Wavevector qII [Å−1] Wavevector qII [Å−1]

Γ 〈110〉 K M 〈112〉 Γ
35
Rh(111)
30
25
LR LR
20 B
15
10 〈110〉
RW K RW
M
M
5 Γ 〈112〉
0
a 0 0.5 1.0 1.56 1.35 1.0 0.5 0
Γ 〈110〉 K M 〈112〉 Γ
35
Rh(111)H(1×1)
S2 S2
30
25
LR LR
20
B’ B’
15
10 RW RW
0
0 0.5 1.0 1.56 1.35 1.0 0.5 0
Fig. 51a, b. Rh(111) (1x1) H. (a) Surface phonon spectrum for the bare
Rh(111) surface. The dashed lines represent the limits of the projection of
the vertically and longitudinally polarised bulk phonons on the surface
[95Wit]. (b) The surface phonon dispersion in presence of the (1x1) H
overlayer as measured by HATOF [95Wit1]. The inset reports the SBZ.

M [112] Γ [110] K
20
Rh(111)(2√3×3)C 6 H6
15
10
H H
C C
5
Fig. 52. Rh(111) (2√3 x 3) C6H6. The
phonon dispersion curve as measured by
HATOF [93Wit1, 93Wit2]. See inset for
0 the adsorption geometry.
-2.0 -1.5 -1.0 -0.5 0 0.5 1.0 1.5 2.0
Γ [ξ 0] M
12
W(100) T = 450K
10
280K
2
Fig. 54. W(100). Surface phonon dispersion of bare
W(100) as measured by HATOF at two surface
0 temperatures [87Ern, 89Ern].
0 0.2 0.4 0.6 0.8 1.0
[0 0] Red.wavevector coord. ξ [1 0]

Γ [1120] K M [1100] Γ
35
Ru(0001)
30
25
20
LR LR
15
10 [1120]
K
RW M RW
M
5 Γ [1100]
0
a 0 0.5 1.0 1.55 1.35 1.0 0.5 0
Γ [1120] K M [1100] Γ
35
Ru(0001)(1×1)H
30
S2
25 S2
20
15
10 RW RW
0
0 0.5 1.0 1.55 1.35 1.0 0.5 0
Fig. 53a, b. Ru(0001) (1x1) H. (a) Surface phonon dispersion

[97Bra]. The lines are the result of a LDM calculation with bulk
force constants. (b) Surface phonon dispersion curve in presence of
the (1x1) H overlayer as determined by HATOF. The lines are the
result for surface phonon and resonances of a LDM fitting the bulk
phonon dispersion [97Bra]. LR denotes the longitudinal resonance.
The SBZ is reported in the inset in (a).

30
W (100) (1×1) H
20
Set Ι
10 RW RW
L
Fig. 55. W(100) (1x1) H. HATOF data for

the surface phonon dispersion [92Ern]. The
0 lines are the result of a LDM calculation.
Γ M X Γ
Wavevector qII
250
W (110)
200
150
100
50
0
0 0.5 1.0 1.5 2.0 1.0 0.5 0 0 0.5 1.0
Γ H N’ N Γ Γ S
Fig. 56. W(110). Surface phonon dispersion for the clean W(110) surface [94Bal1, 92Hul1, 92Hul2]. HREELS data
are reported by open symbols, HATOF data are given by the small filled dots. Different symbols for the HREELS
data denote different phonon branches.

W (110)p (2×1) H
200 25
20
150
15
100
10
50
5
0 0
200 (2×2) H 25
20

150
15
100
10
50
5
0 0
(1×1) H
200 25
20
150
15
100
10
50
5
0 0
1.0 0.5 0 0 0.5 1.0 1.5 2.0 1.0 0.5 0
S Γ Γ H N’ N Γ
Fig. 57. W(110) H. Phonon dispersion curves for the different H phases, measured along ( Γ − S ) ( Γ − Η ) and
( Γ − Ν ). The data were recorded at T=110 K. The data for the (1x1) H phase along ( Γ − Η ) show evidence for the
phonon instability. No temperature dependent frequency shifts were observed. HREELS data are reported as open
symbols, HATOF data as filled circles. Main references [92Hul1, 92Hul2, 96Bal, 94Bal1, 94Bal2].

W (110) (1×1) H
[001] W(110)(1×1) H
H
[111]
Phonon energy hω
P -1
0.9 Å P
N N
Γ [110]
Fig. 58. W(110) (1x1) H. Position of the critical

wavevectors at which the phonon anomaly is observed.
The dotted lines indicate the directions along which
HATOF data were recorded.
Γ H N
Wavevector qII
W (110) H (2×1)H Fig. 59. W(110) (1x1) H. Experimental HREELS (dots)

off-spec and HATOF (diamonds) data are compared with the
1252
768
result of first principle calculations for the substrate

0.5 modes of the (1x1) H phase [96Bun].
111
546
×7
0
1323
(2×2)H
Intensity I [1000 c/s]
2 off-spec
750
1223
885
113
644
1056
×20
0
(1×1)H
850
off-spec
1306
2000
×2000
0
850
1306
(2×1)H
1 off-spec
Fig. 60. W(110) H. HREELS spectra showing the
×40 anomalous line shape of the H- and D-induced energy
0 losses for the different phases [94Bal2].
0 500 1000 1500 2000
Energy loss E loss [cm−1]

1300 1400
W(110)p(2×1)H W(110)(2×2)H
1300
1200

1200
800
800
700
700
600
600
500 500
0 0.5 1.0 1.5 2.0 0 0.2 0.4 0.6 0.8 1.0
a Γ Wavevector qII [Å−1] H b Γ Wavevector qII [Å−1] H‘
1400
W(110)(1×1)H Fig. 61a-c. W(110) p(2x1) H. Dispersion of the
H induced modes for: (a) p(2x1) H phase, three
1300
modes are observed, corresponding to the three
degrees of freedom of the adsorbate; (b) (2x2)
1200 H phase and (c) (1x1) H phase. The stretch

vibration is at 163 meV and displays a stronger
dispersion than for the other H phases [96Bal].
800
700
600 Fig. 62a, b. C(100) H. Optimised surface

structures for (a) C(100) (2x1) H and (b)
500 C(100) (1x1) H and surface Brillouin zones.
0 0.5 1.0 1.5 2.0
c Γ Wavevector qII [Å−1] H
C(100)(2×1)H C(100)(1×1)2H
H H H H
C C C
ky ky
H H H r H
CH ϑ
rCH ϑ
Γ2×1 J 2×1 Γ1×1 J 1×1 C
C C d12
kx d12 rCC kx d23
J ‘2×1 K2×1 J ‘1×1 K 1×1
a b

C(001)(2×1)H Sa
90
360
Ss
80
320
Bs+ B s1 S TOΓ Br1 B a1

40
160
B s- STOX
30 120
B s2
20 80 Fig. 63. C(100) (2x1) H. Calculated
surface phonon dispersion at 1 ML
RW coverage [96San]. Shaded area:
10 R TAX 40 projection of bulk phonon bands;
R TA
solid curves dispersion of surface
B a2 B a2 modes and resonances.
0 0
Γ2×1 J’2×1 K 2×1 J 2×1 Γ2×1
Wavevector q
C(001)(1×1)H
90 Sa
360
Ss
80
320
Bs+ Bs
40 160
BΓ
30 B s-
120
B a+
B sr
20 80 Fig. 64. C(100) (1x1) H. Calculated
surface phonon dispersion at 2 ML
coverage [96San]. Shaded area:
10 40 projection of bulk phonon bands;
B a- RW solid curves dispersion of surface
0 0 modes and resonances.
Γ2×1 J’2×1 K 2×1 J 2×1 Γ2×1
Wavevector q

C(111)(1×1)H
90 370
S
80 330
50
200
B1 B 2

40
160
R1 R1
B3 B3
30
120
S6
S8
20 80
S’8
RW
10 40
0 0
Γ M K Γ
a Wavevector q
70
C(111)(1×1)D
S 270
60
230
50
200
B1 B 2
40
160
R1 R1
30
120
S6
B3 S8
20 B3 80 Fig. 65a, b. C(111) (1x1) H. (a) Calculated
S’8
surface phonon dispersion for the
hydrogenated surface and HATOF data
RW [98Gle]; (b) same as (a) for the deuterated
10 40 surface and HATOF data [98Gle]. Shaded
area: projection of bulk phonon bands;
solid curves dispersion of surface modes
0 0 and resonances.
Γ M K Γ
b Wavevector q

15
60
Ge(001)(1×1)S
50
10
40

30
5 Fig. 66. Ge(100) (1x1) S. Surface

20 phonon dispersion predicted by theory.
No experimental data are available at
the moment [92Pol]. Shaded area:
10 projection of bulk phonon bands; solid
curves dispersion of surface modes.
Surface resonances are reported as
dashed lines.
0 0
K Γ J’ K J Γ
Wavevector q
80
Si(100)(2×1)
70
60
50
40
30
20 Fig. 67. Si(100). Surface phonon

dispersion of bare Si(100) (2x1).
10 Shaded area: projection of bulk phonon
bands; solid curves dispersion of
0 surface modes and resonances
Γ J’ K J Γ K [98Tüt2].
Wavevector q

Si(100)(2×1) Ge Si(100)(2×1) Sb
2.38 2.87
18.5° Ge Sb
0.76
2.35 1.48 2.38 1.58
Si 0.81 Si
2.41
1.20 1.27
2.31
2.34 2.37 0.14
3.72 3.95 3.83
Si Si
2.26
Ge 2.21 1.96
3.83 3.83 Sb
1.94
a b
Fig. 68. Si(100)(2x1)As. Top view, side view and structural parameters of Si(100)(2x1) Ge and Si(100)(2x1) Sb. The
structure for Si(100) (2x1) As [99Tüt] is similar to the one of Sb [98Tüt2].
Si(100)(2×1)Ge
70
60
50
40
30
20 Fig. 70. Si(100)(2x1)Ge. Surface phonon

dispersion according to ref. [98Tüt2].
Shaded area: projection of bulk phonon
10 bands; solid curves dispersion of surface
modes and resonances. The dashed lines
indicate selected modes of the bare
0 Si(100)(2x1) surface.
Γ J’ K J Γ K
Wavevector q

20 Si(100)(2×1)As
80
S2 S2
15
S1 S1 S1 60

S0 S0
Da Da
10
40
Ds Ds
Db
Ds
Dt Dt
5 Ds 20
A3
D1
A1
A2 A4
0 0
Γ J’ K J Γ
Wavevector q
Si(100)(2×1)As J‘ K
Γ J
70
60
50
40
30
Fig. 69a, b. Si(100)(2x1)As. Surface
phonon spectrum (full lines) and
20 projection of the bulk phonon bands
(vertical lines) according (a) to ref.
[98Grä] and (b) to ref. [99Tüt].
10 Prominent modes have been labelled
according to their origin and nature. In
(b) the dashed lines indicate selected
0 modes of the bare Si(100)(2x1) surface.
Γ J’ K J Γ K
Wavevector q

Si(100)(2×1)Sb
70
60
50
40
30
Fig. 71. Si(100)(2x1)Sb Surface
20 phonon dispersion according to ref.
[98Tüt1, 98Tüt2]. Shaded area:
projection of bulk phonon bands; solid
10 curves dispersion of surface modes and
resonances. The dashed lines indicate
selected modes of the bare Si(100)(2x1)
0 surface.
Γ J’ K J Γ K
Wavevector q
65
Si(100)(2×1)H
Sa
260
Ss
60
20 Bs Ba
80
Ba Bs
Db2
15
60
Da Ds
Ds
10 40
Db1
Dt
5 20
Fig. 72. Si(100)(2x1)H. Surface phonon

RW
dispersion [96Grä1]. Localised and
resonant modes are shown by solid
0 0 lines.
Γ J’ K J Γ
Wavevector q

65
Si(110)(1×1)H
Sa 2100
Ss
60 2000
700
20 Bo Bi
600
Bi Bo

Cs
15 500
Cx Cy 400
10 Ct2
300
C t1
200
Fig. 73. Si(110) (1x1) H. Surface phonon
5
dispersion of hydrogenated Si(110). The
100
vertically dashed areas represent the
projection of the bulk phonon bands.
Localised and resonant modes are shown
0 0 by solid lines [97Grä].
Γ J’ K J Γ
Wavevector q
20
80
Si(111)(1×1)As
15 S4 S4
60
R3
S3 K4
L1 L1
10 40
L2 L2
K3
K2
Fig. 74. Si(111) (1x1) As. Surface phonon
K1 spectrum of Si(111) (1x1)As: filled circles
5 20 HREELS data [94Sch], open circles
HATOF data [92San1], solid lines surface
modes and surface resonances calculated
with ab-initio methods [98Grä]. The shaded
region is the projection of the bulk phonon
0 0 bands.
Γ M K Γ
Wavevector q

75
Si(111)(√3×√3)Ga
500
Phonon wavenumber ν [cm −1 ]
50

250
25 Fig. 75. Si(111) (√x√3) Ga. Surface
phonon dispersion curve. The shaded
area is the projection of the bulk
phonon bands on the SBZ. Triangles
and circles denote HATOF [89Doa]
and HREELS [95Sch] data,
respectively. The solid lines are the
calculated phonon dispersion curves
0 0
[99Fri2].
Γ M K Γ
Wavevector q
For Fg. 76, see next page
40
GaAs(110)
30
20
Fig. 77. GaAs(110). Surface phonon

dispersion predicted for the clean
surface [95Fri1]. The shaded area
10 represents the projection of the bulk
bands on the SBZ. The surface
phonon mode above the bulk optical
band splits into two modes along
X‘ M
Γ − X . The uppermost mode is
Γ X
0 marked by the dashed line.
X Γ X‘
Wavevector q

Si(111)(1×1)H
500
LM
400 50

300 S6
S8 S8
S’8
200 25
100
RW
0 0
Γ M K Γ
a Wavevector q
Si(111)(1×1)H
2100 S 260
2000
B 80
600
500 R3
60
400 LM
R1
R2 R1
40
300
S6
S8 S’8
200 Fig. 76a-c.
20
Fig. 76a, b.
100 RW
For Fig. 76 c and the figure caption,
see next page
0 0
Γ M K Γ
b Wavevector q

47 Si(111)(1×1)D
S
180
42
20
80
Fig. 76a-c. Si(111) (1x1) H. (a)
HATOF data [90Doa3] and theoretical
B1 B2
prediction [88Mig]. (b) HREELS data:
15
60 filled circles [92Stu], open circles

[92Dum]. The solid lines are the
B3 theoretical prediction according to ref.
[95San1]. The mode marked LM in (a)
R1 B3 B3 R1 and (b) is the Lucas mode. It is absent
10 40 in experimental data being shear
S6
horizontally polarised. Surface
S’8 resonances are denoted by dashed lines.
S8 (c) Surface phonon dispersion as
forecasted for the deuterated Si(111)
5 20 surface [96Grä2, 97Maz]. In (b) and (c)
the symbols S, B and R refer to
RW adsorbate stretching, bending and
rotational motions. Substrate surface
modes are denoted by Sn.
0 0
Γ M K Γ
c Wavevector q
40
GaAs(110)(1×1)H
30
20
Fig. 78. GaAs(110) (1x1) H. Surface

10 phonon dispersion curve predicted for
the hydrogenated surface by ab-initio
linear response formalism [95Fri1]. The
X‘ M
shaded area represents the projection of
the bulk bands on the surface Brillouin
Γ X
0 zone.
X Γ X‘
Wavevector q

GaP(110)H
stretching modes
272.1
271.9
224.0
223.6
223.2
bending modes
74
70
66
50
40
30
20
10
X‘ M
Γ X
0
X 〈110〉 Γ 〈001〉 X
Wavevector q
Fig. 79. GaP(110) (1x1) H. Surface phonon dispersion predicted

from first principles calculation [99Fri1]. The shaded area represents
the projection of the bulk phonon bands on the SBZ. The solid lines
are the dispersion curves for surface modes and resonances. The
dashed curves indicate the dispersion of selected surface modes of
the clean surface. The dots report the position of these modes for the
unrelaxed bulk geometry.

InAs(110)H
stretching modes
264.0
263.8
204.4
204.0
203.6
bending modes
65
60
55
30
25
20 Fig. 81. InAs(110) (1x1) H. Surface

phonon dispersion curve predicted in ref.
[99Fri1]. The shaded area represents the
15 projection of the bulk phonon bands on the
SBZ. The solid lines are the dispersion
curves for surface modes and resonances.
10 The dotted lines in the gap between the
bulk phonon bands are selected surface
modes of the clean surface. The dashed
5
lines within the bulk bands are weak
X‘ M surface resonances. The dots indicate the
Γ X position of these modes for the unrelaxed
0
bulk geometry of the bare surface.
X 〈110〉 Γ 〈001〉 X‘
Wavevector q

60
GaP(110)(1×1)Sb
50
40
30
Fig. 80. GaP(110) (1x1) Sb. Surface

20 phonon dispersion predicted from first
principles in ref. [99Fri1]. The shaded area
represents the projection of the bulk bands.
10 The solid lines are surface modes and
surface resonances. Above the bulk optical
phonon band two surface modes are
present. The uppermost mode is evidenced
0
by a dotted line.
X Γ X‘
Wavevector q
50
InP(110)(1×1)H
40
30
Fig. 82. InP(110) (1x1) H. Surface phonon

dispersion curve predicted for the
20 hydrogenated surface by ab-initio linear
response formalism [95Fri1]. The shaded
area represents the projection of the bulk
bands on the surface Brillouin zone. The
10 solid lines are the surface modes. The
dotted curves indicate the dispersion of two
surface-localised gap modes of clean
X‘ M InP(110). The diamonds denote the
Γ X frequency of these modes for a bare
0
unrelaxed surface.
X Γ X‘
Wavevector q

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Landolt-Börnstein

Numerical Data and Functional Relationships in Science and Technology

Group III: Condensed Matter

Physics of Covered Solid Surfaces

ISBN 3-540-41224-7 Springer-Verlag Berlin Heidelberg New York

Library of Congress Cataloging in Publication Data

Springer-Verlag Berlin Heidelberg New York

© Springer-Verlag Berlin Heidelberg 2002

Cover layout: Erich Kirchner, Heidelberg

SPIN: 10783464 63/3020 - 5 4 3 2 1 0 – Printed on acid-free paper

Jülich, January 2002 The Editor

III/42 Physics of Covered Solid Surfaces

1 Introduction to physical and chemical properties of adlayer/substrate systems

2 Characterization of adsorbate overlayers: measuring techniques (CH. WÖLL) .......... 2-1

4 Data: Adsorbate-induced changes of substrate properties ............................ 4.1-1

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2.1.1 Comparative information on techniques discussed in this chapter

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Phase Electronic Inter- Vibrations Diffusion Destructive Synchrotron

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2.1.2 List of acronyms used in this chapter

2.2 Direct methods

The adsorption of a molecule on a surface, as schematically illustrated in Fig. 1, leads to changes of a

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Fig. 1. Adsorption of a molecule on a

2.2.1 Monitoring adsorption by calorimetry

2.2.2 Quartz crystal microbalance

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2.2.5 Adsorption-induced changes of surface stress

2.2.6 Adsorption-induced changes in resistivity

2.2.7 Reflectance ellipsometry

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2.2.8 Change of work function

2.3 Techniques based on a mass spectrometer

2.3.1 Determination of sticking coefficients using a molecular beam

An important question concerning a particular adsorbate/substrate combination is whether for a given

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2.3.2 Thermal Desorption Spectroscopy (TDS)

Fig. 3. Schematic illustration of a second order desorption process in thermal

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2.3.3 Laser-induced Thermal Desorption (LITD)

2.4 Techniques for a chemical analysis

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2.4.1 Secondary Ion Mass Spectroscopy (SIMS)

2.4.2 Ion Scattering Spectroscopy (ISS)

3.4.3 Auger Electron Spectroscopy (AES)

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2.4.4 X-ray Photoelectron Spectroscopy (XPS)

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2.5 Structural sensitive techniques

2.5.1 Low Energy Electron Diffraction (LEED)

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2.5.2 Diffuse Low Energy Electron Diffraction (DLEED)

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2.5.3 Photoelectron Diffraction (PED)

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2.5.4 Techniques employing X-ray Standing Waves (XSW)

2.5.5 Extended X-ray Absorption Fine-Structure Spectroscopy (EXAFS)

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Fig. 8. In EXAFS, the absorption of X-ray radiation is determined as a function

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2.5.6 He-Atom Scattering (HAS)

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h fixed Fig. 18. In X-ray emission spectroscopy, or XES, the