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15 MAY 2004
INTRODUCTION
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0021-9606/2004/120(19)/9286/11/$22.00
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From high resolution electron energy loss spectroscopy HREELS and infrared absorption spectroscopy
IRAS it has been concluded that the linear bond of
adsorbed CO is retained at all coverages.3,10 Specifically, a single band has been reported which shifts
continuously from 2030 to 2060 cm1 as CO increases 0.330.68 ML.
Complex LEED patterns (2)2))R30 or (5)
5))R30 overstructures suggest that the arrangement of CO molecules within the large unit cells and
their local binding geometry must be nonuniform.13,7
2004 American Institute of Physics
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Vibrational frequencies are known to display characteristic shifts in the vicinity of extra species, structural defects,
or upon substrate lattice strain.6,25,26 In this work IR spectroscopy of naturally abundant 13C16O 1.1% has been used
to accurately and sensitively probe such chemical shifts of
CO vibrational-modes. The term chemical shift summarizes
interactions due to electron correlations among the coadsorbates, either directly adsorbateadsorbate or mediated by
the substrate adsorbatesubstrateadsorbate. What makes
things complicated in dense layers is that, besides static
chemical shifts, adsorbateadsorbate interactions and their
influence on vibrational modes may also have a dynamic
origin.27 Such a dynamical interaction of two oscillators by
means of their oscillating dipole fields displays a 1/r 3 dependence and additionally requires a resonance condition to
be fulfilled which is naturally the case for identical species
with identical binding geometries. In nondilute layers specific information on the chemical environment of adsorbates
is difficult to extract from vibrational modes subject to strong
dynamical coupling, i.e., associated with the majority 12C16O
species. Lateral coupling quite naturally leads to the formation of delocalized vibrational modes;28,29 local variations of
the chemical environment of a surface species then will be
completely averaged out. The standard procedure to distinguish static and dynamic influences on the vibrational frequency therefore is to determine the respective line positions
of two isotopically labeled species with identical binding
geometry, the one being strongly dilute minority species,
surrounded by molecules of the majority type.29 For CO the
1.1% natural abundance of 13C16O represents an ideal admixture to determine chemical frequency shifts largely independent from dynamical shifts, which predominantly affect the
majority regular 12C16O molecules. The extraction of specific information on the chemical environment of adsorbates
requires vibrational modes to be localized. This is easily obtained in weakly heterogeneous systems, produced either by
adding chemical impurities or, as in this work, using iso-
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topic labeling. For homogeneous systems dynamic localization may be attained through anharmonic coupling among
vibrational modes.30,31
Strictly speaking, dynamical dipole coupling for the isotopically labeled minority species is not exactly zero. First,
their spatial separation is large but not infinite, so that resonant coupling among identical minority molecules does occur producing a weak blueshift; second, and more important, decoupling of the minority species from the vibrational
motion of the surrounding majority species is complete only
for very large isotopic shift factors, which is usually not
achievable. This is why the vibrational bands of the minority
13 16
C O species are in fact slightly influenced by the surrounding regular CO molecules15 causing i an intensity
transfer 29 in favor of the modes of the majority 12C16O
molecules, and ii a slight redshift of the 13C16O derived
band due to antiphase motion of neighboring regular 12C16O
molecules when 13C16O is vibrationally excited. These effects are larger the closer the two CO isotopic species, both
spatially and spectrally.
EXPERIMENT
Infrared absorption spectroscopy IRAS has been performed in an UHV chamber base pressure 5
1011 mbar) equipped with additional facilities for low
energy electron diffraction LEED, thermal desorption spectroscopy TDS, and x-ray photoemission spectroscopy
XPS. The Fourier transform IR spectrometer Bruker IFS
66v used in conjunction with a MCT mercury cadmium
telluride, cutoff at 600 cm1 or an InSb indium antimonide,
cutoff at about 1800 cm1 detector is highly stable and
evacuable. For IR measurements, the sample was placed in a
specially designed cell which allows simultaneous gas dosing via a microcapillary array and IRAS data taking. In addition, a titanium sublimator has been installed in the IR cell
in order to keep contaminations low. The Ru crystal was
oriented within 0.1 of the 0001 direction. The surface
was cleaned by Ar ion-sputtering and oxygen cleaning
cycles. The sample could be cooled to 30 K and heated resistively to 1570 K using a computer controlled power supply.
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FIG. 1. IR absorption spectra obtained from a well-ordered ()))R30 12C16O/Ru(0001) layer, a, which has been exposed to 0.01 ML 12C16O at T
35 K, b. Annealing to about 400 K desorbs postadsorbed CO so that the original spectrum is regained, c. The CO stretch mode of the 12C16O majority
species is displayed in panel A. Panel B shows the spectral region of the 13C16O minority species 1.1% natural abundance at an enlarged vertical scale. In
panel B the ratio of spectrum b and those at CO0.33 ML have been calculated in order to highlight the spectral changes associated with extra CO within
the perfect ()))R30 CO overlayer d. All spectra were obtained at T35 K at a spectral resolution of 2 cm1 using an InSb detector cut off at about
1800 cm1.
cm1, depending on the distance and nature of the neighboring species.34,35 For altered adsorption site geometries the
associated frequency shifts are much larger.
In Fig. 1, a well-ordered ()))R30 CO/Ru0001
layer, a, has been exposed to an additional small amount of
12 16
C O ( CO0.01 ML) at T35 K, b. The layer then
has been annealed to about 400 K to desorb CO in excess of
0.33 ML, so that the original layer is restored, c.20 Panel A
shows the CO stretch mode of the 12C16O majority species
FIG. 2. IR absorption spectra obtained from a well-ordered ()))R30 12C16O/Ru(0001) layer, a, which has been exposed to 0.0150.02 ML 12C16O at
T35 K, b. The original layer in a contained a 10% fraction of 13C16O so that the associated bands at about 1941 cm1 become more prominent. Annealing
to about 400 K desorbs postadsorbed CO in excess of 0.33 ML, c. The CO stretch mode of the 12C16O majority species is displayed in panel A. Panel B
shows the spectral region of the 13C16O minority species at an enlarged vertical scale. In panel B the ratio of spectrum b and those at CO0.33 ML has been
calculated in order to highlight the spectral changes associated with extra CO within the perfect ()))R30 CO overlayer d. All spectra were obtained
at T35 K at a spectral resolution of 2 cm1 using an InSb detector.
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intensity loss of the 1941 band with respect to the gain of the
1925 cm1 band is independent of the absolute 13C16O content. It is therefore concluded that a conversion from 1941
cm1 associated with 13C16O in a ()))R30 environment to 1925 cm1 ( 13C16O modified by extra 12C16O, most
likely at nearest neighbor sites occurs. From a quantitative
analysis of the intensity loss of the 1941 cm1 band versus
the amount of extra CO in excess of 0.33 ML from TDS we
find that 0.02 ML CO converts about 0.08 ML of the original
()))R30 CO layer to the modified state, i.e., one
postadsorbed CO molecule seems to affect about four preadsorbed CO molecules.
Next we look into the postadsorption of small amounts
of 13C16O with an 11% fraction of 13C18O) into a ()
))R30- 13C16O/Ru(0001) layer at 115 K. For this set of
spectra the spectral resolution was 4 cm1 and the splitting
of the 13C18O minority band due to 13C18O pairs could not
be resolved. Adding 0.03 or 0.06 ML 13C16O to a wellordered ()))R30 13C16O layer Fig. 3a leads to the
spectra in Figs. 3b and 3c, respectively. The characteristic
modes and spectral changes are similar to those of Fig. 2,
e.g., the band at 1878 cm1 equivalent to 1925 cm1 in Fig.
2b is due to 13C18O in the neighborhood of extra 13C16O
molecules. This band is barely visible in Fig. 2d 1881
cm1 band which contained a mere 1% fraction 13C18O in
the original ()))R30 layer. The mode at 1917 cm1 is
assigned to 13C16O of the original ()))R30 layer close
to postadsorbed 13C16O and it is equivalent to the band at
1961 cm1 in Fig. 2. Note that the 1917 cm1 band in Fig.
3b is different from the 1925 cm1 band observed in Fig.
2b, despite their closeness in frequency and both originating from 13C16O molecules: While the 1917 cm1 mode is
associated with a layer containing 90% 13C16O, the 13C16O
entity amounts to only 10% or less with 90% 12C16O)
when the 1925 cm1 band is observed. The different frequencies are due to a dissimilar dynamical lateral coupling of
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13 16
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FIG. 5. Possible arrangements of CO, postadsorbed into a well-ordered ()))R30 CO/Ru0001 layer indicated by light gray dots. In A the extra
molecule dark gray dot is located in the center of three CO molecules medium gray dots; in B it is assumed that one of these three off-center CO has moved
to a neighboring site due to the impact of postadsorbing CO. In A B one extra CO affects three four CO of the ())) lattice.
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FIG. 6. Arrangements of CO at CO
0.33 ML CO according to Fig.
5A. The sites of the individual CO
isotopes have been chosen according
to the layer compositions in Figs. 1 or
2 and 4 in A and B, respectively. In
A an extra 12C16O molecule has been
added to the ()))R30 CO/
Ru0001 layer close to a minority
13 16
C O, whereas in B the extra species in the center of three 12C16O molecules is 13C16O. Coloring as in Fig. 5.
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FIG. 7. IR absorption spectra obtained from saturated CO/Ru0001 layers. The three spectra were obtained from layers with different isotopic compositions:
a 99% 12C16O1% 13C16O; b 95% 12C16O5% 13C16O; and c 89% 13C16O11% 13C18O. Panel A shows the dominant modes of the respective
majority species. Panel B shows the modes of the respective minority species vertical scale enlarged by 17. All spectra were obtained at T30 35 K at
a spectral resolution of 2 cm1. The vibrational bands of spectrum c are somewhat broader due to tiny admixtures of 12C16O, with dynamical dipole coupling
producing a relatively strong high frequency tail. Also, a relatively high content of the heavier isotopic species leads to broadening of the various vibrational
bands. The base line distortion in spectrum b is due to the usage of an InSb detector with cutoff at about 1800 cm1.
APPENDIX
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Regarding the second question I like to state that a homogeneous distribution of different species in dense layers
will render all but one of them virtually invisible due to the
strong dynamical coupling; this has been verified for dense
layers similar to the ones in Fig. 7 using 50%: 50% mixtures of different CO isotopic species data not shown. A
dense striped phase arrangement of CO, as suggested by Biberian and van Hove,41 on the other hand, would be in agreement with the present spectroscopic data, since screening of
vibrational dipole moments is less pronounced for extended
one-dimensional structures.
ACKNOWLEDGMENTS
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P. Jakob
to the surrounding 12C16O of the ()))R30 layer is much larger for
13 16
C O than for 12C16O, the associated additional redshift of CO( 13C16O)
at about 1925 cm1 ( 2 cm1 ) as well as the associated intensity
transfer will be relatively weak.
39
K.-M. Schindler, Ph. Hofmann, K.-U. Wei et al., J. Electron Spectrosc.
Relat. Phenom. 6465, 75 1993.
40
A. Eichler, Surf. Sci. 526, 332 2003.
41
J. P. Biberian and M. A. Van Hove, Surf. Sci. 138, 361 1984.
42
P. Piercy and H. Pfnur, Phys. Rev. Lett. 59, 1124 1987.
43
M. Gsell and P. Jakob unpublished results.
44
K. Meinel, H. Wolter, Ch. Ammer, A. Beckmann, and H. Neddermeyer, J.
Phys.: Condens. Matter 9, 4611 1997.
45
Our IR data related to saturated CO/Ru0001 layers now exist for about 9
years. So far we restrained from publishing them because there still existed some open questions regarding the structural arrangement of the
various species and details of their binding geometry. In order to avoid
confusion in the literature and to straighten up a few points related to these
layers, we decided to publish them along with a less detailed interpretation
of our observations.
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