Surface Review and Letters, Vol. 23, No.

3 (2016) 1650015 (8 pages)

c World Scientic Publishing Company
DOI: 10.1142/S0218625X16500153

THERMODYNAMIC PROPERTIES
p pOF THE METALLIC

SYSTEM Au(111)-( 3
3)R30 -Pd

R. CHADLI* and S. KHEFFACHE

Laboratory of Physics and Quantum Chemistry,
Mouloud Mammeri University,
B.P. 17, Tizi-Ouzou 15000, Algeria
by THE UNIVERSITY OF NEW SOUTH WALES on 04/13/16. For personal use only.

*rabah_abo@yahoo.fr

A. KHATER
Institute of Molcules and Materials of Le Mans,
Surf. Rev. Lett. Downloaded from www.worldscientific.com

Maine University Av. Olivier Messiaen, Cedex 09,

Le Mans 72085, France
Received 20 November 2015
Revised 31 December 2015
Accepted 4 January 2016
Published 16 February 2016

This work constitutes anpanalysis

p of the thermodynamic properties in the ordered metallic surface
alloy system Au(111)-( 3
3)R30  -Pd. The equilibrium structural characteristics as well as the
thermodynamic functions are examined by the matching method, associated with real space Green's
function formalism, evaluated in the harmonic approximation. Our numerical results, for this me-
tallic system of surface alloy, show in particular a signicant dependence between the thermody-
namic properties and the coordination number and the values of the force constants.

Keywords: Ordered surface alloy; vibration frequencies; LDOS; thermodynamic properties.

1. Introduction Furthermore, it is known that, accurate and reliable

It has been widely established that a solid's surface
(in particular a surface alloy) representing the inter-
face with the surrounding environment introduces
dierences in properties from those of the bulk form.
During the last two decades, studies relating to sys-
tems of surface alloy have attracted a considerable
part of attention of researchers.15 In practice, the
formation of such systems of surface occurs when a
metal of high surface energy (such as Pd) is deposited
onto another metal substrate of lower surface energy
(such as Cu and Au).6 In particular, PdAu system,
due of its interesting catalytic properties, has been
the subject of several studies.711
calculations of the thermodynamic functions consti-
tute an approach to understand the thermal properties
of systems of surface alloy. In particular, the structure
stability of these systems of surface, the tendency to
disorder and the ability to undergo morphological
changes and phase transitions are among some of the
characteristics that may be explored from a knowledge
of thermodynamic properties.12,13
Indeed, for example, it has been reported by Kara
et al. that in materials undergoing martensitic phase
transition, vibrational contribution to the entropy is
dominant. Also, vibrational entropy has been found
to be of signicance in the self-diusion of Si involving

*Corresponding author.

1650015-1
 R. Chadli, S. Kheache & A. Khater
the concerted exchange mechanism. Moreover, in
considerations of stability of surface structures, vi-
brational entropy is expected to play a smaller, yet
critical role.14
On the other hand, systems of surface alloys often
are the central participants in processes occurring at
the surface. A detailed knowledge of the thermody-
namic properties, of these systems of surface, is of
importance in fundamental considerations of a vari-
ety of physical and chemical phenomena, taking place
at or near the surface, such as epitaxial growth,
chemical reactivity and equilibrium shapes of surfaces
and nanocrystals.15
by THE UNIVERSITY OF NEW SOUTH WALES on 04/13/16. For personal use only.
Thus, one of the basic issues in surfaces science is
the analysis of structural, dynamical and thermody-
namical properties of these systems of surface alloys
and understand how they dier from those in the
Surf. Rev. Lett. Downloaded from www.worldscientific.com
bulk. It is the aim of this work, in which we are
interested to study the thermodynamic properties
inpthepordered
metallic surface alloy Au(111)-
( 3
3R30  -Pd. In particular, we examine how
can these properties dier from those in the bulk and
in the clean surface Au(111). We shall see also how
such properties are inuenced by the coordination
number and the values of the force constants.
In what follows we rst give, in Sec. 2, a structural
description of the system of interest. In the next
section, a theoretical calculation method of the ther-
modynamic properties, in surface alloy systems, is
presented. Our results and their discussions are
summarized in Sec. 4. Finally, in the last section, we
conclude our work.
2. Description of Studied System
Surface alloy is a mixture of metals on a consistent
substrate, commonly an atomically at surface of a
monometallic single crystal. One or more guest metals
are deposited onto this crystal and blended with each
other or with the host metal. This is often inten-
tionally promoted by thermal annealing. Generally, a
surface alloy is limited to a few atomic layers and
from a surface science perspective, the relevant
properties can usually be broken down to features of
the rst 13 layers.16
In particular, mixtures of metals of Pd and Au
have received a large part of attention of researchers
because they are frequently used in applications in-
cluding hydrogen fuel cells, as catalysts for a
1650015-2
number of reactions and in controlling pollution.17
Palladium atoms can be evaporated on gold surface
substrates, the occurrence of ordered surface struc-
tures has been reported.18 However, the detailed
morphology of these ordered structures varies
strongly as a function of the deposition techniques,
the concentration of evaporated Pd atoms and the
annealing temperatures.
A vapor deposition of Pd atoms, on the surface
substrate Au(111) in ultrahigh vacuum (UHV), fol-
lowed by annealing over a substrate temperature
range from 150 K to 650 K lead to an ordered surface
alloy system.3,19 In their studies, Koel et al., have
indicated that the growth process of Pd atoms, in-
vacuum, on Au(111) depends strongly on the sub-
strate temperature.20,21 The evolution of AES signals
suggested that, at a substrate temperature of 150 K, a
pure Pd over layer is formed on the clean surface
Au(111). Thereafter, and when the growth tempera-
ture is raised to 500 K, a specic intermixing of the
gold and palladium atoms is indicated by LEIS
data.22 However, it should be noted that the PdAu
alloy formation has been observed and detected even
at the room temperature (RT).
Furthermore, Baddeley et al.,23 Chen et al.24 and
Atanasov and Hou 18 have reported, in their results,
that an ordered
p psurface
alloy Pd/Au (111), which
exhibits ( 3
3R30  periodicity, as it is shown in
Fig. 1. Representationpof p
the
ordered metallic surface
alloy system Au(111)-( 3
3R30  -Pd.

Thermodynamic Properties of the Metallic SYSTEM Au(111)-( 3
3)R30 -Pd
Fig. 1, appears for appropriate annealing tempera-
tures of the gold substrate (T & 500 K).
Note that this system of ordered surface alloy
presents a stable structure between 500 and 600 K,
where the concentration of palladium atoms is
1/3 ML, which then correspond to an intermixed
layer composed of an Au rich alloy. This enrichment
is due to the alloying tendency between the palladium
and gold atoms and also to the dierence in the sur-
face free energies, since the surface free energy for Au
(1.626 J/m2) is lower than that of Pd (2.043 J/m2).
3. Theoretical Details
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Surface phonons and their contribution to the ther-
modynamic properties are subjects of many con-
tributions in surfaces science in the last few
Surf. Rev. Lett. Downloaded from www.worldscientific.com
decades.14,2527 Vibrational surface states are lattice
vibrations of the solid, which are localized at its sur-
face. Habitually, the amplitude of a surface vibration
is located within a few layers of the substrate surface.
The quanta of these surface vibrations are called
surface phonons. In many cases, a classical treatment
is sucient because of the large atomic masses and
small vibration energies involved.
Furthermore, the Bloch theorem is inapplicable
along the direction perpendicular to the surface, due to
the absence of translation symmetry along this direc-
tion. This make dicult the resolution of the equation
systems of vibrational motion of a semi-innite solid.
Thus, it becomes necessary to use new theoretical
methods in order to achieve a coupling between equa-
tions of motion of an atomic layer to another. These
new adapted methods permit either to solve innite
systems of equations or limit, in a valid approximation,
the number of equation and the number of unknowns.
In the theoretical treatment of lattice dynamics at
surfaces, two dierent methods have been often used
in the past, the Green's function method and the slab
method.28,29 Here, in this work, we propose to use
another method, namely the matching method,
to investigate the thermodynamical properties in
the
p ordered
p metallic surface alloy system Au(111)-
( 3
3R30  -Pd.
3.1. The matching theory
This method was introduced initially by Feuchtwang
in 1967.30 At the beginning of its introduction, the
1650015-3
p p
method has not been favored by the fact that it has
been thought not well suited to resonance calcula-
tions, i.e. resonance modes whose frequencies fall in
the bulk spectrum and thus hybridize with bulk
modes and which deeply penetrate into the bulk re-
gion. After, in 1987, the method was reviewed and
developed as a basic theoretical tool by Szeftel and
Khater.31 Their results allow us to give a general
denition of the resonance concept as well as a
transparent analysis of the surface displacement
spectral density, presented within a scattering bulk
phonon surface interaction. Thereafter, in the last
two decades, the method has been used extensively by
several authors to study the properties of phonons
and magnons in crystalline solids presenting defects,
such as surfaces, interfaces, adsorbates, nano con-
tacts, etc.3236
The basic principle of this method consists to
match the properties of bulk phonons with the eva-
nescent vibrational modes, according to the direction
perpendicular to the ordered surface alloy system. To
do this, the studied system needs to be divided into
three regions having the same periodicity along in one
subdomain of the system. These regions are surface
region, bulk region and an intermediate region
allowing the matching of surface states to bulk states.
3.2. Vibration frequencies
Our study begins by the determination of the eva-
nescent vibrational modes. The dynamics vibration of
an Au atom, located at the site in the bulk region, is
governed, in the harmonic approximation, by the
following general equation of motion37:
X X r
r
MAu ! 2 U
; !  K; 0
0 6 
r2

U 0 ; !  U ; !; 1
where
;  denotes the space directions, U
; ! the
vibrational amplitudes according to the
direction,
r
the corresponding Cartesian component of the
radius vector between and 0 , where r is the distance
between and 0 , and K; 0 symbolizes the force
constant between any given sites and 0 . Note that,
in our study, the x- and y-axes are considered in the
plane of the ordered metallic surface alloys, whereas
the z-axis is in the normal direction to the surface
plane of the x- and y-axes, as it is shown in the Fig. 1.
 R. Chadli, S. Kheache & A. Khater
Table 1. Calculated force constants obtained from
the results given by Wu et al.38
Length
Force constants
Type of pair of bond (

A) (J.m 2 )
Au  Au 1 2.88 35.9
Pd  Pd 1 2.75 44.1
Au  Pd 1 2.82 51.2
Au  Au 2 4.08 3.2
Pd  Pd 2 3.89 3.6
Au  Pd 2 3.98 4.3
The force constants, for the purposed system
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model, are determined from the numerical results
given by the rst principal calculations of Wu et al.38
The dierent obtained results, for the bond lengths of
rst neighbors (AuAu)1, (PdPd)1, (AuPd)1, and
Surf. Rev. Lett. Downloaded from www.worldscientific.com
second neighbors (AuAu)2, (PdPd)2,(AuPd)2, are
grouped in Table 1.
The application of Eq. (1) to an atom Au, inside
the bulk region, allows to have a system of linear
equations given by the following matrix form:
! 2 I  De ix ; e iy ; ; 1 ; 2 jUi 0; 2 the rst layer at the surface alloy boundary. The
where 1 and 2 constitute the ratios of the force
constants (rst and second neighbor) to the atomic
mass of gold,  is a generalized phase factor according
to the direction z andpx and y arepfactors given
respectively by kx a=2 6 and ky a=2 2, where kx
and ky are the Cartesian components of the wave
vector k. The term jUi symbolizes the displacements
vector for the irreducible sites of the basic unit cell in
the bulk region.
The resolution of Eq. (2) leads to a secular equa-
tion, which may be expressed in general as a poly-
nomial given by
X alloy boundary, expressed in the form
As  s 0: 3
s Dm jU; Ri 0:
Here As are functions of the dynamic variables !;
x ; y and of the structural and elastic properties of
the considered system.
Once Eq. (3) is solved, we obtain the ensemble of
propagating (jj 1) and evanescent modes (jj < 1)
in the various frequency intervals of the bulk propa-
gating bands.
Now, with the determination of the propagating
and evanescent modes, we have nished with the
dynamic vibrational in the bulk, we will go to the
dynamic vibrational of the ordered surface alloy
1650015-4
p p
system Au(111)-( 3
3R30  -Pd. The application
of Eq. (1), to atoms situated in the three regions
dened by the matching theory, generates a system of
equations having number of unknowns greater than
the number of equations. We can reduce this system
of equations, by applying the matching formalism,31
to get a nite square dynamic matrix. This can be
done by the describing of the displacement vibration,
for each set of dynamic variables !; x ; y , as a
linear combination of the bulk eigenmodes, whether
propagating or evanescent, along the direction nor-
mal to the mixed surface PdAu going into the bulk
crystal. For a mode propagating in the plane of the
surface with wave vector k kx ; kx , the displace-
ment eld U
; !; k for bulk atoms in the neigh-
borhood of the surface alloy boundary may be hence
expressed in the following form:
X
U
; !; k  sp W
; s; kRs : 4
s
In this equation, the number p, for site , is an integer
which identies the location of the corresponding
atomic plane along the z-direction with reference to
ensemble fRs g symbolizes the component vectors
that span the Hilbert space, corresponding to the
complete set of solutions for the factors f;  1 g.
However, the coecients W
; s; k are the relative
weighting factors associated with the vibrational
amplitudes U
for the eigenmode s propagating in the
surface with wave vector k.
If the basis vectors in the constructed Hilbert
space are denoted by jRi  jfRs gi, the use of Eq. (4)
with the transformations mapping the two vectors
jUi and jRi gives a nite square dynamic matrix
Dm , representing the dynamics of the surface
5
Finally, the diagonalization of the obtained square
matrix Dm  allows to determine the vibration
frequencies of phonons of the considered system of
ordered surface alloy and those will be used, as we will
see, in the determination of the thermodynamic
properties.
3.3. Local vibrational density of states
As we know, the local vibrational densities of states
(LDOS) are used in the calculation of the
 p p
Thermodynamic Properties of the Metallic SYSTEM Au(111)-( 3
3)R30 -Pd

thermodynamic functions. The direct manner to cal- Note that, according to the x-, y- and z- directions of
culate the LDOS, in the domain of surface alloy displacement, the equation of motion for each atom is
boundary, is via the matched dynamics matrix decomposed into three independent equations, hence
Dm  associated with the real space Green's func- the n atoms of solid will be equivalent to 3n harmonic
tion formalism.39 The general expression of this oscillators, each one vibrating independently at fre-
LDOS is given by quency !E .
X X ;
N! 
;
x ; y ; !
x ;y

2! X X 4. Results and Discussion
 lim
 ; ;
" 0 4.1. Lattice heat capacity C
x y

ImG

 x ; y ; !
2
i"; 6 In Fig. 2, we have presented the calculated heat ca-
pacities Cpv associated
p to the ordered surface alloy
where G

 is the matrix of Green's function associ- Au(111)-( 3
3R30  -Pd, clean surface Au(111)
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ated with site at the locality . systems, together with those for the bulk Au atoms.
The rst remark which we can note is that the three
curves have a similar behavior as a function of the
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3.4. Thermodynamic functions temperature.

The local thermodynamic functions can be deter- Furthermore, as a second remark, we can see from
mined easily through the vibration frequencies of the gure that for temperatures beyond T 15 K, the
phonons and the calculated LDOS, corresponding to specic heat rises sharply and it becomes constant at
the ordered surface alloy system. These functions are higher temperature. Indeed, when the temperature
given, in the harmonic approximation, by40 increases further, the lattice heat capacity approaches
Z 1    the classical value, i.e. 24.9 J/K.mol.41
}! However, we nd that the lattice heat capacity, at
Fvib 3kB T ln 2sinh N!d!; 7
0 2kB T a xed temperature, depends on the eective coordi-
Z 1  nation and on the values of the force constants. In-
}! 2 1
Cv 3kB   N!d!; 8 deed, we can note the increasing of the lattice heat
0 2kB T sinh 2 2k}!
BT capacity, between the bulk and the clean surface, due
Z 1   
}! }!
Svib 3kB coth
2kB T 2k T
0   B
}!
ln 2sinh N!d!; 9
2kB T
Z 1  
} 1 }!
hu 2
i coth N
!d!; 10
2M 0 ! 2kB T

where Fvib , Cv , Svib , hu 2
i and N! represent, re-

spectively, the free energy of vibration, the lattice
heat capacity, the entropy of vibration, the mean-
square atomic displacements along the Cartesian di-
rection
and the determined LDOS at the ordered
surface alloy system.
Note that our numeric calculations were carried
out by using the Einstein's model proposed in 1907, in
which every atom is oscillating independently at a
Fig. 2. Lattice heat capacity as a function of the temper-
same frequency !E . This last one depends on the ature: solid line for the clean surface Au(111); dashed and
strength of the restoring force acting on the atom (i.e. dash-dotted lines represent the bulk and the ordered surface
the strength of the chemical bonds within the solid). alloy atoms, respectively.

1650015-5
 R. Chadli, S. Kheache & A. Khater
the diminution of the coordination number, which
passes from 18 to 12. This is due to the fact that a
particle with a higher coordination has less space to
roam, in comparison to one with a lower coordina-
tion. However, an increase of the values of the force
constants, rst and second neighbors between the
bulk and the surface alloy (as appearing in Table. 1),
provokes a decrease in the value of the lattice heat
capacity.
4.2. Vibrational free energy Fvib
The vibrational free energies, Fvib , for the
pordered
p
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metallic surface alloy system Au(111)-( 3
3
R30  -Pd, the clean surface Au(111) and the bulk
atoms Au are presented in Fig. 3. A general analysis
of this gure shows, as a rst remark, that the three
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curves have similar behavior as a function of the
temperature, in which the Frib decreases with the
increasing of this one.
From this gure, one can note also that the local
contribution of the phonons to the free energy for the
surface atoms diers from that of the bulk atoms, in
such a way that the largest dierence appears on the
ordered metallic surface alloy atoms followed by that
of atoms in the clean surface Au (111), reecting the
direct consequences of the coordination number and
the values of the force constants. In particular, we can
Fig. 3. Local vibrational free energy as a function of the
temperature: solid line for the clean surface Au(111);
dashed and dash-dotted lines represent the bulk and the
ordered surface alloy atoms, respectively.
1650015-6
associate the decrease in the vibrational free energies
between the bulk system and the clean surface
Au(111) to the decrease of the coordination number
which is 18 for the bulk and 12 in the clean surface
system. However, the increase in the free energy be-
tween the ordered surface alloy and the bulk Au
system can be associated to increase of the values of
the force constants, rst and second neighbors which
are f4:3 J:m 2 , 51:2 J:m 2 g for the ordered metallic
surface alloy and f3:2 J:m 2 , 39:5 J:m 2 g in the bulk
(see Table. 1). These results point to the strong de-
pendence of the vibrational contribution to the free
energy on the coordination and the force eld.
4.3. Vibrational entropy Svib
The local contributions of gold and palladium atoms
in the considered systems, cited earlier, to the vibra-
tional entropy in the temperature range 0300 K are
presented in Fig. 4. At rst, we note that for the
entire temperature range, for the three considered
systems, the contribution is largest for the gold atoms
in the clean surface Au(111), followed by that of gold
atoms in the bulk and then that of the gold and
palladiump atoms
pin
the ordered metallic surface alloy
Au(111)-( 3
3R30 -Pd. 
For example, at 300 K, Au atoms contribute about
0.43 meV/K to the entropy of the bulk and about
0.45 meV/K to the clean surface Au(111). However,
Fig. 4. Local vibrational entropy as a function of the
temperature: solid line for the clean surface Au(111);
dashed and dash-dotted lines represent the bulk and the
ordered surface alloy atoms, respectively.

Thermodynamic Properties of the Metallic SYSTEM Au(111)-( 3
3)R30 -Pd
on the ordered surface alloy, Au and Pd atoms con-
tribute about 0.41 meV/K. The increase in the con-
tribution value to the vibrational entropy, between
the bulk and the clean surface, is due essentially to
the reduction of the coordination number (from 18 to
12). However, the decrease in the contribution value
in the ordered surface alloy system in comparison
with the two other systems is due certainly to the
increase of values of the force constants, rst and
second neighbors.
Furthermore, we can see that the three curves
have a similar behavior at low temperatures, in
which, for a temperatures ranging 022 K, the vi-
by THE UNIVERSITY OF NEW SOUTH WALES on 04/13/16. For personal use only.
brational entropy, Svib , increases very slowly with
temperature T, in such a way that the value of Svib in
this interval is almost near to zero. Beyond 22 K, the
vibrational entropy Svib rises sharply. Furthermore,
Surf. Rev. Lett. Downloaded from www.worldscientific.com
we can note a similar behavior as the lattice heat
capacity, with respect to the variation as a function of
the coordination number and the values of the force
constants.
5. Conclusion
In summary, we have presented calculations of ther-
modynamic properties of the system
p pof
ordered
metallic surface alloy Au(111)-( 3
3R30  -Pd
formed by evaporating Pd atoms onto a clean surface
Au(111). In particular, the examination action of the
vibrational contribution to the local thermodynamic
properties of atoms on the considered system of sur-
face alloy, by comparison with bulk and clean surface
systems, shows that the thermodynamic functions are
very sensitive to the local eective coordination
number and to the values of the elastics force con-
stants. Taking the specic example of the vibrational
free energy, Fvib , the given results show that the dif-
ference between the vibrational free energy of the
surface alloy atoms, with that of the clean surface
atoms, increases with increasing of the temperature.
This establishes, particularly, that Pd atoms have a
signicant vibrational contribution to the local vi-
brational free energy.
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