Physica B 407 (2012) 698–704

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Physica B
journal homepage: www.elsevier.com/locate/physb

Ab-initio study of the coadsorption of Li and H on Pt(001), Pt(110) and

Pt(111) surfaces
Farida Saad, Mourad Zemirli n, Mouloud Benakki, Said Bouarab
Laboratoire de Physique et Chimie Quantique, Faculté des Sciences, Université Mouloud Mammeri, 15000 Tizi-Ouzou, Algeria

a r t i c l e i n f o a b s t r a c t

Article history: The coadsorption of Li and H atoms on Pt(001), Pt(110) and Pt(111) surfaces is studied using density
Received 21 July 2011 functional theory with generalised gradient approximation. In all calculations Li, H and the two
Received in revised form topmost layers of the metal were allowed to relax. At coverage of 0.25 mono-layer in a p(2  2) unit cell,
25 November 2011
lithium adsorption at the hollow site for the three surfaces is favoured over top and bridge sites. The
Accepted 5 December 2011
Available online 8 December 2011
most favoured adsorption sites for H atom on the Pt(001) and Pt(110) surfaces are the top and bridge
sites, while on Pt(111) surface the fcc site appears to be slightly favoured over the hcp site. The
Keywords: coadsorption of Li and atomic hydrogen shows that the interaction between the two adsorbates is
Density functional calculations stabilising when they are far from each other. The analysis of Li, H and Pt local density of states shows
Adsorption
that Li strongly interacts with the Pt surfaces.
Platinum
& 2011 Elsevier B.V. All rights reserved.
Lithium

1. Introduction First-principles calculations were performed to study the stability

Alkali metals adsorption on simple metallic surfaces is con-
sidered as a model for understanding more complicated systems
[1,2]. So, the structural stability of alkali-atom adsorbed on metal
surface has been studied extensively in the last decade from both
experimental and theoretical point of view. The surface structures
formed by the adsorption of Li on Al(110), at room temperature,
have been studied by low energy electron diffraction (LEED) and
core-level photoemission spectroscopy (CLS) [3]. The Al(110)-
c(2  2)-Li structure formed by adsorption of one-half monolayer
(ML) Li is shown by analysis of extensive LEED measurements to
be an ordered surface alloy. The CLS measurements provide
insight to the adsorption geometry at coverages below and above
0.5 ML Li where it is found that the adsorption of Li leads to the
formation of a partially disordered, multilayer surface alloy.
Structural stability of Na and Li adsorbed Al(001) surface at
coverages of 0.25 and 0.5 ML, is studied in terms of a first-
principles plane-wave pseudo-potential approach within the local
density approximation [4]. By comparing the adsorption energy
between the different coverages, the results show that the
relative stability between the hollow site and substitutional
adsorption gets closer when the coverage goes from 0.5 to
0.25 ML in both Al(001)-Na and Al(001)-Li. In particular, it is
found that the Li atom on the hollow site tends to make more
localised bonding with Al substrate, preferring less coverage.
n
Corresponding author. Tel.: þ213 775975680.
E-mail address: zemirlimourad@mail.ummto.dz (M. Zemirli).
of the alkali-atom adsorbed surface structure in Cu(001)-Li,
Al(001)-Na and Ag(001) systems [5]. Calculations predict that,
at an alkali-atom coverage of 0.5 ML, a substitutional (2  1)
structure is achieved in Cu(001)-Li, whereas the substitutional
c(2  2) structure is the most stable structure in Al(001)-Na and
Ag(001)-Na systems. Recently, alkali atoms Li, K, and Na adsorp-
tion on Co(0001) surface and surface-substitutional were studied
based on periodic density-functional theory calculations [6] and
the calculated results indicate that top, bridge and hollow sites
are degenerated with almost identical adsorption energies for all
considered cases. In addition, calculations of the work function
change upon Li adsorption on Ru(001) surface were performed for
a variety of Li coverages [7]. The calculations with FLAPW-DFT
method for slab geometries give perfect agreement with new
experimental results for that system. Due to their extensive
application in catalysis, platinum surface, in particular, have been
subject of extensive experimental and theoretical investigations.
So, accurate calculations of Pt surfaces played an important role in
the behaviour of the solid metal for technical applications.
Platinum is a catalyst in many processes, including the hydro-
genation of olefins [8,9] and the aim of this work is to study the
adsorption of Li on Pt surfaces in order to determine the
difference between the ability of Pt and Li/Pt systems to adsorb
the atomic hydrogen. Initially, we explore the adsorption of H on
the clean Pt surfaces then we study the coadsorption of Li and H
on Pt(001), Pt(110) and Pt(111) in order to determinet the
influence of Li on Pt surfaces.
The paper is organised as follows. In Section 2, we present the
computational method employed. Results for the clean Pt(001),

0921-4526/$ - see front matter & 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.physb.2011.12.005
 F. Saad et al. / Physica B 407 (2012) 698–704 699

Pt(110) and Pt(111) surfaces are presented in Section 3.1. The
results of Li adsorbed on Pt surfaces are presented in Section 3.2,
followed by those of H adsorption in section 3.3. The coadsorption
of the two atoms is studied in Section 3.4. In Section 3.5 we
discuss how the work function and LDOS change after adsorption
and coadsorption of Li and H. The Section 4 is devoted to the
conclusion.
2. Computational methods
The quantum chemical calculations were conducted using
Dacapo package [10]. This programme is based on density func-
tional theory (DFT). It uses a plane wave basis set. Ionic cores are
described by Vanderbilt ultrasoft pseudopotentials [11]. The Kohn
Sham one-electron equations are solved self-consistently within
the generalised gradient approximation (GGA) by using the
parameterisation of Perdew-Wang (PW91)[12]. Brillouin-zone
integration was carried out using a (8x8  1) k-points Monkhorst-
Pack grid for Pt(110) and (6x6  1) for Pt(001) and Pt(111)
surfaces. A high energy cut-off of 400 eV was used for the plane
wave set in all calculations. A Fermi broadening corresponding to
kBT¼0.1 eV was employed to speed the convergence process. All
total energies have been extrapolated to T¼0 K. We have used the
well known supercell technique consisting of a periodical repeti-
tion of a five layers slab of Pt, with a p(2  2) surface unit mesh
and a coverage of 0.25 ML for Li and H atoms. The images of the Pt
slabs are separated by a vacuum space equivalent to seven
interlayer spaces for Pt(110) slab and to five interlayer spaces
for Pt(001) and Pt (111) slabs. These numbers of vacuum layers
are sufficient to cancel any interaction between two consecutive
slabs. The minimisation of the total energy procedure yields a Pt
bulk lattice constant a0 of 4.004 Å, which is somewhat higher than
the experimental value of 3.924 Å [13], but in good agreement
with other theoretical estimations using similar methods
(4.005 Å) [14,15,16,17,18]. In all calculations Li, H atoms and the
two topmost layers of Pt were allowed to relax. Maximum force
criteria of 0.01 eV/Å was considered for convergence. The dipole
correction was used and the work function is obtained from the
difference between the vacuum energy level and the Fermi level.
Adsorption energies were computed by subtracting the energies
of the adsorbate atoms and the slab from the energy of the
adsorbates/slab system as shown in the following equation [19]:
Ead ¼ EadsorbateðsÞ=slab EadsorbateðsÞ 2Eslab
With this definition, a negative Ead corresponds to a stable
adsorption on the slab. In the case of atomic hydrogen adsorption,
the reference gas state was ½ H2 [18]. The energy of the isolated
adsorbate was determined from calculations performed on a
single molecule in a cubic cell with an edge of 12 Å.
Spin polarised DFT is used to characterize hydrogen atom and
diffusion energetics on the Fe(110) surface [22]. The results
compare well with both experiment and recent DFT studies and
show that the Fe(110) surface is basically bulk-terminated, with
only very small relaxation and no reconstruction. So we have
studied Li adsorption on the unreconstructed Pt surfaces. In order
to check the relaxation phenomenon of clean Pt surfaces, we have
tested how many layers are required to evaluate the relaxation of
the two topmost layers of Pt with a reasonable accuracy. We
found that five layers slabs are sufficient to describe the three
surfaces. The changes in the interlayer spacings are presented
with respect to the unrelaxed interlayer
pffiffiffi spacing d0, i.e., Ddi,j
¼100(di,jpffiffiffi d0)/d0, where d0 is a0/ 3 for Pt(111), a0/2 for Pt(001)
and a0/2 2 for Pt(110). The results are summarised in the Table 1
together with other values taken from literature for a comparison.
For Pt(111), our calculations yield an expansion of the top
most interlayer spacing of þ0.87%, while the second layer
contracts by  0.51%. First principle calculations, using a linear
combination of atomic orbitals and the same exchange-correla-
tion functional [23] as in the present work obtained a similar
expansion and contraction of the first and second interlayer
spacing ( þ0.87% and  0.5%, respectively), while LDA based
calculations [23] give rise to 0.88% and 0.22% expansion and
contraction, respectively.
For Pt(001), we find a contraction of the top most and second
interlayer spacing of  2.21% and  0.34%, respectively. The
contraction of the top most interlayer spacing is in good agree-
ment with FLAPW calculations (  1.9%) [24] while an expansion
of the second layer spacing (þ 0.3) was reported in contrast to the
small contraction obtained in the present work.
For Pt(110), there is an important contraction of the top most
interlayer spacing of -15.32%, while the second interlayer spacing
expands by 7.85%. The contraction of the top most interlayer
spacing is in good agreement with FLAPW [24] and PW(91) [25]
calculations, which predict a slightly smaller first layer contrac-
tion (  14.0% and  13.81%, respectively). For the second layer,
the FLAPW [24] calculations predict a slightly greater second
layer expansion ( þ8.3%), while the PW(91) [25] calculations
report a similar comparative expansion of the second layer
spacing ( þ7.38%) to our result of 7.85%.
3.2. Li adsorption on the unreconstructed surfaces
The high-symmetry sites considered in the present work for
the adsorption of Li and H on Pt surfaces are shown in Fig. 1, and
Table 1
Percentage change in the interlayer spacing, Ddi,j ¼ 100(di,j - d0)/d0, for low index
surfaces of Pt. Other values from the literature are shown for a comparison. ‘‘ þ’’
and ‘‘  ’’ indicate expansion and contraction of the interlayer spacing, respectively.
Pt(001) Pt(110) Pt(111)

3. Results and discussion d0(A1) 2.002 1.416 2.332

2.339d
Dd1,2 (%) This work  2.21  15.32 þ 0.87
3.1. Relaxation of clean Pt surfaces GGAa þ 0.87
LDAa þ 0.88
The creation of a surface alters the electron density of the FLAPWb  1.90  14.00 þ 1.30
PW(91)c  13.81
topmost surface layers, and modifies their atomic positions. The
Dd2,3 (%) This work  0.34 þ 7.85  0.51
clean (001) of Pt exhibits complex reconstructions. The outermost GGAa  0.50
surface layer forms a quasi-hexagonal structure on top of the LDAa  0.22
square substrate lattice structure, which is highly complex [20]. FLAPWb þ 0.30 þ 8.30 þ 0.30
However, this reconstruction restructures to the regular bulk PW(91)c þ 7.38

terminated square (1  1) phase upon adsorption of CO, NO, and a

Ref. [23].
several other adsorbates [21]. This suggests that the (1  1)- b
Ref. [24].
Pt(100) surface corresponds to the stable configuration when c
Ref. [25].
the surface is considered in interaction with its environment [15]. d
Ref. [17].
700 F. Saad et al. / Physica B 407 (2012) 698–704

Table 3
Adsorption energy (eV) of H on high symmetry sites of Pt surfaces together with
other available result.

Pt(001) Pt(110) Pt(111)

Hollow (fcc)  0.295a  0.002a  0.461a

 0.223d  0.490b
 0.477g
(hcp)  0.446a
 0.450b
 0.450g
Fig. 1. Representation of the high-symmetry sites for the adsorption of Li and H
Bridge  0.647a  0.548a
on (a) Pt(001) surface, (b) Pt(110) surface, (c) Pt(111) surface: top (t), bridge (b),
 0.610c  0.640e
long bridge (lb), short bridge (sb), hollow (h), fcc and hcp.
 0.575d  0.590f
Top  0.424a  0.505a  0.344a
Table 2  0.390c  0.450g
Adsorption energy (meV) of Li on the low-index surfaces of Pt calculated for high-  0.371d
symmetry sites: hollow, bridge and top.
a
Present work.
b
Pt(001) Pt(110) Pt(111) Ref. [17].
c
Ref. [18].
d
Hollow (fcc)  1.003  0.965  0.907 Ref. [26].
e
(hcp)  0.905 Ref. [27].
f
Bridge (lb)  0.849  0.913  0.776 Ref. [28].
g
(sb)  0.715 Ref. [29].
Top  0.667  0.585  0.586

Table 4
the results for the adsorption energies at 0.25 ML of Li coverage H-Pt distances (in Å) for H adsorbed on the Pt surfaces (in the most stable
are summarised in Table 2. configurations) together with other theoretical and experimental results.
It can be seen from the calculated energies (Table 2) that the
Pt(001) Pt(110) Pt(111)
interaction between Li and Pt surfaces is important and the
hollow site is found to be the lowest in energy for the three Pt Hollow (fcc) 1.87a
surfaces. The hollow site differs geometrically from one surface to 1.87f
another. On the Pt(111) surface, Li is coordinated to three Pt 1.88g
surface atoms, whereas on Pt(110) and Pt(001), it is bonded to (hcp) 1.85a
1.87f
four Pt atoms. It is known that alkali atoms usually prefer hollow 1.88g
sites when adsorbed on fcc(001) metal surface [5,6,7]. The results 1.78 70.08h
for adsorption energies suggest that the lithium was chemisorbed Bridge 1.76a 1.77a
on the three surfaces of Pt on the hollow site and the adsorption is 1.76b
Top 1.57a 1.58a 1.57a
energetically more favourable on the Pt(001) surface. Lithium
1.57b 1.56d
produces significant deformation in the two upmost Pt layers. For 1.57c 1.56e
the open surfaces Pt(001) and Pt(110), and in contrast to the clean 1.57f,g
Pt(001) and Pt(110) surfaces, the first layers are now relaxed
a
outward and the adhesion of Li reduce the contraction of Pt(110) Present work.
b
to Dd1,2 ¼ 11.4% and to Dd1,2 E  1.5% for Pt(001). For Pt(111) Ref. [18].
c
Ref. [26].
surface, the expansion of the interlayer spacing between the first d
Ref. [30].
layers has increased (Dd1,2 ¼ þ1.9%) after the Li adsorption. e
Ref. [31].
f
Ref. [32].
g
3.3. H adsorption on Pt(001), Pt(110) and Pt(111) Ref. [29].
h
Ref. [33].

The adsorption energies of the hydrogen atom on the three

Pt surfaces are reported in Table 3. We note that the bridge sites
are clearly preferred on Pt(001) and Pt(110) ( 0.647 eV and
0.548 eV, respectively) against the top site (  0.424 eV and
0.505 eV, respectively). The hollow site was found unstable on
these two surfaces. Very close values were calculated [18] for
H/Pt(001) adsorption on bridge and top sites (  0.610 eV and
0.390 eV, respectively). Others values calculated [26] for the
three high symmetry sites (hollow, bridge, and top) on Pt(001) are
in close agreement with our results (  0.223 eV,  0.575 eV, and
0.371 eV, respectively). For bridge site on Pt(110) surface [27], a
comparable value with our result (  0.640 eV) was reported. This
last result is in good agreement with the experimental value
(  0.590 eV) [28]. For H/Pt(111) [15] similar values with our
result for fcc and hcp adsorption sites( 0.490 eV and -0.450 eV,
respectively) were reported. These results are in reasonable
agreement with the theoretical study [29] that used five layer
slab and obtained  0.477 eV,  0.450 eV, and  0.450 eV for the
fcc, hcp, and top sites, respectively, in agreement with our five
layer calculations, while they found the top site to be the most
stable when they used three layer slab.
From Table 4, we note the H Pt bond lengths. We find 1.57 Å
and 1.76 Å for top and bridge sites, respectively, on Pt(001);
1.58 Å and 1.77 Å for top and bridge sites, respectively,
on Pt(110). Theoretical calculations using similar method for
H/Pt(001) [18] found the same result for top and bridge sites
(1.57 Å and 1.76 Å, respectively). DFT calculations, using VASP
package [26], obtained a similar H  Pt bond length for adsorption
of H on-top of Pt(001) (1.57 Å). For H/Pt(111) we find the height
of the H atom above the Pt surface for fcc, hcp, and on-top site
adsorption to be 0.91 Å, 0.86 Å, and 1.57 Å, respectively, with
H Pt bond lengths of 1.87 Å, 1.85 Å and 1.57 Å. Our results are in
good agreement with previous theoretical calculations [30,31],
which found the height of H above Pt surface to be 0.93 Å, 0.93 Å,
and 1.56 Å [30] and 0.91 Å, 0.91 Å, and 1.56 Å [31] for fcc, hcp and
on-top adsorption, respectively. Other first principles calculations
found 1.87 Å, 1.87 Å, and 1.57 Å [32] and 1.88 Å, 1.88 Å and 1.57 Å
 F. Saad et al. / Physica B 407 (2012) 698–704 701

[29] for fcc, hcp and on-top adsorption, respectively, which are Table 6
also in good agreement with our results. However, comparative Li–Pt and H-Pt distances for Li and H coadsorbed on Pt(111) (in Å).
H  Pt bond length (1.78 70.08 Å) was estimated [33] by using
Li  Pt surface H  Pt surface
the LERS (Low-Energy Recoil Scattering) measurement to deter-
mine the position of light adsorbates on monocrystalline surfaces. Li-fcc, H-fcc 2.66 1.85
2.68n 1.87n
Li-fcc, H-hcp 2.68 1.85
3.4. Coadsorption of Li and H on Pt surfaces 2.68n 1.85n

n
The coadsorption of Li and H on Pt surfaces was investigated Li–Pt and H-Pt distances in the case of single Li and H adsorption on Pt(111).

using a (2  2) unit cell where the adsorption of lithium is

considered only in its stable hollow site. We report on the Pt(001) and Pt(110) is favourable in the cases where the interac-
Fig. 2a the three coadsorption sites of H on Pt(111): top (t), hcp tion between H and Li is less repulsive.
(h) and fcc (f) and on the Fig. 2b the five explored coadsorption We report on Table 6 the geometrical parameters of Li and H
sites of hydrogen atom on Pt(001) and Pt(110). For the hollow site coadsorbed on Pt(111). The distance between the lithium adsor-
on these two last open surfaces, we have two distinct sites: Hh1 bate and the Pt(111) surface in the case of Li-fcc and H-hcp
and Hh2 and for the bridge site there are also two coadsorption adsorption is in line with single Li atom adsorption on Pt(111). So,
sites of H; the Hb1 and the Hb2 and we have only one site Ht for when the two coadsorbates are in two different sites (Li-fcc,
the top site. The Li-H distance and the number of Li neighbours H-hcp), the H-Pt surface distance is the same than for H/Pt
for each site were reported in Table 5. system. It corresponds to the case where the repulsion between
The results of coadsorption energies reported in Table 5 show the two coadsorbates is less. In contrast, when the two atoms are
that the hollow sites (Hh1 or Hh2) remain unfavourable for the in the same site (Li-fcc, H-fcc); the Li Pt and H  Pt bond lengths
adsorption of hydrogen atom even after the adhesion of the decrease after the coadsorption of Li and H. In this situation, the
lithium, indicating the absence of energy minima for the H-hol- repulsion between the two atoms is the strongest and this can be
low site. However, we can note that, among the two hollow explained by a simple electrostatic model where a charge transfer
configurations, the most favourable is the site where H is located from the adatoms towards the Pt surfaces gives rise to the
at the greater distance from Li. We have the same situation for the formation of dipole moment, which in turn, leads to an electro-
bridge coadsorption sites; the Hb2 site is more stable than Hb1 static repulsion between the adsorbates. The repulsion is stronger
(we can see on the Fig. 2b that in Hb2 site, H is located at a large for the Pt(111) surface than for the Pt(110) and Pt(001) surfaces.
distance away from the lithium). For the most stable site (Hb2),
the lithium and hydrogen are still at their preferred hollow and 3.5. Electronic Properties
bridge sites, indicating that, the coadsorption of Li and H on
3.5.1. Work function
The quantity, which is affected by the adsorption of Li and the
coadsorption of Li and H is the work function F. The work
function is the minimum energy required for an electron to
escape from a solid through a certain surface and it is crystal-
lographic orientation dependent. In particular, the work function
changes are an important source of information in the study of
adparticles on surfaces [23]. Compared with other metals [34],
polycrystalline Pt is found to be poor in thermionic stability and
the work function F ranges widely from 5.28 to 5.75 eV depend-
ing on both specimens and preliminary processing. The calculated
values 5.711, 5.297 and 5.747 eV, respectively, for clean Pt(001),
Pt(110) and Pt(111) surfaces, which consist of five layer slab are
Fig. 2. Representation of the coadsorption sites of Li and H: (a) on Pt(111) surface: in agreement with this experimental value. Our results are in
top (t), hcp and fcc; (b) on Pt(110) and Pt(001) surfaces: Hh1; H on hollow site agreement with FP-LAPW-LDA calculations [24], which found
with two second-nearest Li neighbours, Hh2; H on hollow site with four second-
nearest Li neighbours, Hb1; H on bridge site with one nearest neighbour of Li,
6.52, 6.19 and 6.53 eV, respectively, for clean Pt(001), Pt(110)
Hb2; H on bridge site with two next-nearest Li neighbours, Ht; H on top site with and Pt(111) surfaces. The LDA functional [23] predicts larger work
one nearest Li neighbour atom. Li is shown in its most stable hollow sites. function than the PBE functional for Pt(111) (6.06 and 5.69 eV,
respectively). By comparing the Gaussian and plane wave (GPW)
calculations to the standard plane wave (PW) simulations [35],
Table 5
very close values to our results of the work function of Pt(111)
Adsorption energy (eV) of H and Li coadsorbed on high symmetry sites of Pt
and Pt(001) surfaces (5.70 and 5.32 eV, respectively) were
surfaces with Li-H distance (in Å) and the number of Li neighbours for each
coadsorption site on Pt(001) and Pt(110). reported. The dependence of the work function on crystallo-
graphic orientation indicate that F(111) 4 F(001) 4 F(110). This
Pt(001) Pt(110) Pt(111) Li-H number of neighbours sequence is supported by many other theoretical or experimental
results achieved with face-centred cubic metals such as Pt, Al, Ni,
Li-fcc, H-h1  0.278  0.009 2.830 2b
Li-fcc, H-h2  0.320  0.009 4.004 4b
Cu, Rh, Pd, Ag, Ir, and Au [34]. These results follow strictly the
Li-fcc, H-b1  0.429  0.596 1.415 1a Smoluchowski rule that the decrease in packing density of surface
Li-fcc, H-b2  0.659  0.646 3.160 2b atoms leads to a reduction in F(h k l). We report on Table 7 the
Li-fcc, Htop  0.468  0.622 2.002 1a relative work function DF with respect to the clean Pt surfaces of
Li-fcc, H-fcc  0.362
(2  2)-Li/Pt surfaces. Adsorbates that have higher electronegativ-
Li-fcc, H-hcp  0.433
ities than the substrate atoms typically increase the work func-
a
nearest neighbours. tion, while those with lower electronegativities have the opposite
b
next-nearest neighbours. effect [22]. Theoretically [34], the work function of the p(1  1)
702 F. Saad et al. / Physica B 407 (2012) 698–704
Table 7
Work function change relative to pure Pt surfaces DF (in eV).
Pt(001) Pt(110)
Li-fcc  2.557  1.293
Li-fcc, H-b1  2.860  1.220
 0.303n þ 0.073n
Li-fcc, H-b2  2.577  1.217
 0.020n þ 0.076n
Li-fcc, Htop  1.709  1.294
þ 0.848n  1.001n
Li-fcc, H-hcp
n electron counting is obtained by integrating in a sphere of radius
Contribution of the adsorption of H for the work function change on the Li/Pt
systems.
oxygen ML on Pt(001) is calculated to be 7.1170.06 eV, which is
larger than 5.9270.09 eV evaluated for clean Pt(001)(1  1). This
increase is mainly due to the charge transfer from top-layer
platinum atoms to adsorbed oxygen atoms. Similarly, oxygen
chemisorption on Pt(001) and Pt(111) with saturation coverage at
room temperature increases F by 0.5 and 0.45 eV, respectively.
The study of the chemisorption of N on and below Fe(110) and
Fe(001) surfaces [36] shows that the work function increases with
amount of 0.21 eV for Fe(110) and 0.23 eV for Fe(001) after
adsorption of nitrogen 0.25 ML; the calculations showed also that
the work function increases with the concentration of N.
Adsorbed K on Pt(111) [37] causes a large decrease in work
function from the initial value of the clean Pt(111). Calculated
work function changes upon Li, Na and K adsorption on Co(0001)
[6] show that the work function decreases strongly; as for Li
adsorption, the DF increases from 1.9 eV to 2.3 and 2.8 eV with
the coverage from 0.11 increasing to 0.16 and to 0.25 ML. The
results reported in Table 7 show that the work function changes
increase by 2.557, 1.293 and 3.347 eV upon adsorption of Li on
Pt(001), Pt(110) and Pt(111), respectively. This trend compares
well with DFT-LDA calculations [7] for Li adsorption on Ru(001),
which obtain that DF increase by 2.79 eV at a coverage of
0.25 ML. We have also examined the evolution of the work
function in the case of the coadsorption of Li and H atoms and
found similar trends, i. e, negative DF. One notes the weak
contribution of H to the change in the work function. We find
even that the work function increases by 0.073 eV for (Li-fcc,
Hb1)-configuration on Pt(110), and by 0.848 eV for (Li-fcc,
H-top)-configuration on Pt(001). Closer results to the value of
DF found for the (2  2)  2H / Fe(110) structure (  0.077 eV)
[22]. Thus, there is displacement of electron density from Li and H
toward the substrate, which gives rise to an adsorbate(s)-induced
surface dipole. This means that electrons at the Fermi level of the
substrate need less energy in order to reach the vacuum. We can
anticipate that, due the packing of Li, H and Pt atoms, the change
in the work function will be larger for Pt(111) than for Pt(001)
and Pt(110) surfaces. The work function is expected to decrease
[24] as the surface becomes more open due to the smoothing of
the modulation of the electronic density of the surface. The
change in work function after Li and H coadsorption is due to
charge redistribution, which induces a surfaces dipole moment,
which in turn affects the work function. The standard way to
describe alkali adsorption on metals was reported in the pioneer-
ing works of Langmuir [38] and Gurney [39], where it is found
that isolated alkali adatoms lose part of their valence charge in
favour the metal substrate. The recent overview of hydrogen on
metals concludes that the structural influence of hydrogen is
accompanied by a redistribution of electronic charges within the
surface leading to unforeseen changes of the electronic work
function [40].
3.5.2. LDOS discussions
The charge transfer is not sufficient to understand the adsor-
bate(s)-substrate interaction because it results a significant
Pt(111)
change in the substrate surface electron density. We also note
 3.347 that the metal screening charge is largely located in front of the
metal, i.e., between the adsorbate(s) and the substrate. As a
consequence, the adsorbate(s)-induced electron density change
cannot be divided directly into adsorbate(s) and metal contribu-
tions. In order to further shed light on the interaction between Li
and Pt surfaces, we have calculated the evolution of electronic
 3.443 system, looking at the local density of states (LDOS) as obtained
 0.096n
by projection of the wave functions on an atomic basis. The
1.4 Å centred on each of Li, H and Pt atoms. The Li orbital have
been invoked to explain the preference of hollow sites on the Pt
low-index surfaces. Fig. 3 shows the 2sp resolved local density of
states (LDOS) for an adsorbed Li at the preferred hollow site on
Pt(001). It is similar with the LDOS calculated in the case of the
two others Pt surfaces. The LDOS of bulk Li also presented for
comparison. The adsorption of Li leads to noticeable changes of its
LDOS as compared to its corresponding in bulk lithium. The
hybridisation between the Li-sp and Pt-spd states gives rise to
the disappearance of the states in the vicinity of the Fermi level
and the LDOS is reduced in the lower energy region.
For H adsorption we present in Fig. 4 the H 1 s LDOS for an
adsorbed H on Pt(110) surface for the top and the bridge site. We
can see that the states of the LDOS for bridge site are more
stabilized than for top site. For the two H 1 s LDOS, the state
situated at  4 eV initially is found dispersed on a largest domain
of energy (  12 eV). The H 1 s band has a strong interaction with
Pt bands, as seen by the significant change of the Pt s, pz and dzz
LDOS for the top site and the Pt s and px for the bridge site (Fig. 5).
Several peaks of resonance appear on the Pt pz LDOS, the peaks
increase in intensity and width on Pt px band and we can see in
Fig. 5b the strong shift of dzz centre of gravity. The same
observation was done [22] for the dzz of top site; the only
stabilizing shift observed when H adsorbs in top site is the
Fe(110) 3 dzz band. This is clearly due to the hybridisation
between 1 s states of H and s-p-d Pt states after H adsorption
on top and bridge site on Pt(001) and Pt(110). It should be noted
that the Pt(001) and Pt(110) undergo the similar effect after H
adsorption on top and bridge sites. For H/Pt(111), the H 1 s
essentially interacts with the Pt s and py band.
For the coadsorption of the two atoms we present in Fig. 6 the
Pt bands of the most stable configurations of the adsorbates. For
Fig. 3. LDOS of sp orbital of adsorbed Li at the hollow site on Pt(001) [thin line]
and LDOS of Li bulk [dashed line]. The zero energy corresponds to the Fermi level.
 F. Saad et al. / Physica B 407 (2012) 698–704 703

Fig. 4. LDOS of H-1 s orbital (a) on top site, (b) on bridge site [thin line]. The dashed curves indicate the LDOS of H-1 s orbital before adsorption. The zero energy
corresponds to the Fermi level.

0.8
0.08
Pt (Htop)_d-zz LDOS
Pt (Htop)_p-z LDOS
(Arbitrary units)

0.6
0.06

0.4
0.04

0.02 0.2

0 0
-10 -5 0 5 -10 -5 0 5

0.07
Pt (Hbridge)_p-x LDOS

0.25 0.06
Pt (Hbridge)_s LDOS

0.05
0.2
0.04
0.15
0.03
0.1
0.02
0.05 0.01

0 0
-10 -5 0 5 -10 -5 0 5
Energy (eV) Energy (eV)

Fig. 5. LDOS of Pt band after H adsorption on Pt(001): (a) pz for H on top site, (b) dzz for H on top site, (c) s for H on bridge site, (d) px for H on bridge site [thin line]. The
dashed curves indicate the Pt orbitals before adsorption of H. The zero energy corresponds to the Fermi level.

Pt(001) (and/or Pt(110)); the bands, which undergo the most
change are s and px for the site Li-Hb2 configuration, indicating
that the H-Pt interaction dominate the Li–Pt interaction, but by
comparing with Li-Hb1 configuration, we noted that the shift of
LDOS is largest in the second case. For Pt(111), we present in
Fig. 6c the LDOS of Pt in Li-fcc, H-fcc configuration, which
is slightly more modified than the corresponding LDOS of Pt in
Li-fcc, H-hcp configuration. LDOS shows important changes of Pt
LDOS for the configurations where Li is close to the hydrogen,
traducing the important repulsion between the two atoms.
4. Conclusion
The adhesion of Li on Pt(001), Pt(110) and Pt(111) surfaces has
been investigated using density functional theory calculations
704 F. Saad et al. / Physica B 407 (2012) 698–704
Fig. 6. LDOS of Pt band (a) s for Li-Hb2 configuration on Pt(001), (b) px for Li-Hb2 configuration on Pt(001), (c) spd for Li-fcc,H-fcc configuration on Pt(111) [thin line].
The dashed curves indicate the Pt orbitals before adsorption of H. The zero energy corresponds to the Fermi level.
based on plane-wave basis and pseudo-potential. We optimised
Li/Pt systems and the results for adsorption energies suggest that
the lithium was chemisorbed on the three surfaces of Pt in the
hollow site. The nature of the Li–Pt interaction was examined
through the electronic structure changes. The adsorption of
hydrogen and the coadsorption of Li and H were also considered.
From these results, we examined the ability of Pt surfaces to
adsorb H after adhesion of Li. For H adsorption on Pt(110) and
Pt(001), configurations involving both top and bridge are clearly
stabilizing. For H/Pt(111), the fcc site appears to be slightly
favoured over the hcp site. The coadsorption of the two atoms
is favourable when H is at a large distance away from the lithium,
i.e. when the repulsion between H and Li is the smallest. We find
that work function decreases after Li adsorbs and H coadsorbs on
Pt surfaces. The bonding between adsorbates atoms and Pt
surfaces is found to be strongest as displayed by the important
changes of the LDOS.
Acknowledgements
We are grateful to Pierre Légaré and Claude Demangeat for
getting us interested in the subject and for helpful discussions.
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