Applied Surface Science 212213 (2003) 866871

Relation between surface stress and (1
2) reconstruction

for (1 1 0) fcc transition metal surfaces
Stephane Olivier*, Andres Saul, Guy Treglia
Centre de Recherche sur les Mecanismes de la Croissance Cristalline, CNRS, Campus de Luminy, Case 913, 13288 Marseille Cedex 9, France

Abstract
In this work we question the validity of surface stress relief as a driving force for surface reconstruction in the particular case
of the (1 1 0) face of fcc transition metals. To this aim, we calculate within tight-binding second moment potential, both surface
energy and surface stress before and after the (1
2) missing row reconstruction. Doing that, one indeed checks that
reconstruction is energetically favourable for Au and Pt and not for Ni and Cu as experimentally seen, but we also find that it
enhances surface stress along the dense direction for all the elements and along the less dense direction for those which
reconstruct. Therefore, surface stress relief is definitely not the driving force for this reconstruction.
# 2003 Elsevier Science B.V. All rights reserved.
PACS: 62.20.Dc; 68.35.Bs; 68.35.Md
Keywords: Surface stress; Surface relaxation and reconstruction; Molecular dynamics; Low index single crystal surfaces; Transition metals

1. Introduction
It is well known that clean surfaces of some pure
materials undergo reconstructions, which can be classified into three categories: those which just involve
displacements of the surface atoms (e.g. Si(1 0 0)(1
2) [1], Ge(1 0 0)-(1
2), Si(1 1 1)-(7
7),
W(1 0 0)-(1
2) [24]), and those for which surface
density either increases due to the addition of atoms
(e.g. Ir,
p Pt, Au(1 0 0)-(1
5) [5] or Au(1 1 1)(22
3) [6,7]) or decreases due to the removal of
atoms (e.g. Ir, Pt, Au(1 1 0)-(1
2)). Obviously, all
these reconstructions only occur if they lead to a
decrease of the surface energy, but their physical
origins can be manifold. For Si and Ge(1 0 0), for
example, the (1
2) reconstruction minimises the
*
Corresponding author.
E-mail address: olivier@crmc2.univ-mrs.fr (S. Olivier).

number of surface atom dangling bonds, the buckling

of the surface dimers being closely related to details of
the electronic structure. For the (1
5)-like reconstructions of Ir, Pt and Au(1 0 0) the reconstruction
corresponds to the formation of a quasi-hexagonal
surface layer that increases the compactness of outermost surface layer. A general argument concerning
the stress release produced by the surface rearrangement has been sometimes used. Although this argument is probably sound for the kind of reconstructions
associated to an increase of the number of surface
atoms, recent experiments performed by Bach et al.
[8] have shown that the stress relief for the (1 0 0)
surface of Au is not large enough to cause reconstruction. Previously, Needs and Mansfield [9] have argued
that the surface stress alone does not contain sufficient
information to determine whether a surface is stable to
a change in the density of surface atoms. In the same
way, Filippetti and Fiorentini [10] have supported the

0169-4332/03/$ see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0169-4332(03)00018-7

S. Olivier et al. / Applied Surface Science 212213 (2003) 866871

867

tight-binding potential. In order to get a theoretical

criterion for the stability of reconstruction, alternative
to the experimental one, we compare the surface energy
of systems before and after reconstruction. We then
calculate the surface stress in the same conditions, in
order to see if there exists some correlation between the
signs of the variations in surface energy and surface
stress induced by reconstruction.
1.1. Method
Fig. 1. (1 1 0) fcc surface before (a) and after (b) the missing-row
reconstruction.

view that no unique quantity can be invoked as a

general driving force for surface reconstruction of
metals. In order to analyse the applicability of a
surface stress relief criterion to a different kind of
reconstruction, we present in this paper calculations of
surface energy and surface stress for the missing row
(1
2) reconstruction which occurs on the (1 1 0)
surface of fcc 5d transition metals Ir, Pt and Au.
The (1 1 0) surface of fcc is anisotropic with two
inequivalent main directions. Along the [
1 1 0] xdirection there is a higher density of atoms than along
the [0 0 1] y-direction (see Fig. 1(a)). Themissing
row reconstruction consists in removing one over
two [
1 1 0] dense row, leading to a succession of
(1 1 1) microfacets (see Fig. 1(b)). This reconstruction
has been extensively studied experimentally [1114]
and theoretically [1518].
We have considered in this work the seven fcc
transition metals: two 5d metals Pt and Au which
reconstruct and three 4d metals Rh, Pd and Ag, and
two 3d metals Cu and Ni, which do not. Ir which
reconstructs experimentally has not been considered
because we were unable to get a satisfactory parameterisation with our semi-empirical potential. The calculations have been performed using a semi-empirical

The semi-empirical potential used here is derived

from a tight-binding description of the electronic
structure within the so-called second moment approximation (SMA) [19,20]. In this scheme the contribution of the i atom to the total energy writes as a sum of
a pair-wise repulsive part and a many-body attractive
band contribution:
s
X
X
Ei A
epdij =d0 1  x
e2qdij =d0 1 (1)
j

j runs over the neighbours of the atom i, dij is the

interatomic distance, and d0 is the first neighbour bulk
equilibrium distance. The four parameters p, q, A and x
are determined (see Table 1) by fitting the experimental cohesive energy Ec, lattice parameter a, and some
elastic constants (bulk modulus B, shear constants C44
or C 0 ). The calculations have been performed with
interactions calculated up to third neighbours using (1)
and then linked to zero at the distance of the fourth
neighbour using a fifth-order polynomial.
We have used a slab with periodic boundaries along
the two surface directions [1 1 0] and [0 0 1]. The slab
thickness of 15 layers has been chosen in order to
avoid interactions between the two surfaces. All the
atoms of the slab were allowed to move and we have
fully relaxed the system using a quenched molecular dynamics procedure.

Table 1
Parameters (p, q, A (eV) and x (eV)) of the SMA potential used in this work

p
q
A
x

Ni

Cu

Rh

Pd

Ag

Pt

Au

11.34
2.27
0.0958
1.5624

10.55
2.43
0.08938
1.2799

14.92
2.38
0.09357
1.9159

10.90
3.72
0.17099
1.7134

10.85
3.18
0.10309
1.1895

10.47
3.935
0.29453
2.6929

10.145
4.03
0.20967
1.8184

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S. Olivier et al. / Applied Surface Science 212213 (2003) 866871

1.2. Surface energy and surface stress

Using a slab geometry the surface energy can be
calculated as:
g

1
EN  NEb
2A

(2)

N is the number of atoms in the slab unit cell, A the

surface area, EN the total energy of the slab, and Eb
the energy of bulk atom (i.e. the opposite of the
cohesive energy). The surface stress is a symmetric
tensor with elements:
sij

1 @Ag
A @Eij

(3)

where Eij is element of the strain tensor and

i; j x; y; z. Note that a positive (negative) value of
s means a tensile (compressive) surface stress. After
full energy relaxation all the szj components are zero.
The simple development of this equation leads to the
Shuttleworth [21] relation:
sij gdij

@g
;
@Eij

i; j x; y

(4)

There are two contributions to the surface stress, the

first one is the surface energy and the second one is its
strain derivative.

of relaxation is minor (from 0.5% for Ni to 9% for Pt).

We then plot in Fig. 2 the energy balance Dg in both
the not relaxed (a) and relaxed cases (b). Note that a
negative Dg means that the reconstructed structure is
energetically favorable. Satisfactorily we do find, in
agreement with experiments, that the 5d metals Au
and Pt reconstruct (Dg < 0) whereas the 3d metals Ni
and Cu do not (Dg > 0). Moreover, the behaviour of
the 4d metals is found intermediate between the 3d and
5d ones since Dg is negative for Ag and Pd and positive
for Rh. This is also consistent with experiments since
these elements, even though they do not reconstruct
under perfect conditions, are found to reconstruct
when submitted to external constraints (epitaxial
stress [22] or adsorption of alkali atoms [23,24]).
Let us recall that our aim here is to correlate surface
stress and reconstruction in the framework of a common potential. Therefore, in view of the overall consistency between our energetic calculations and
experimental observations, and being aware of the
limitations related to the use of semi-empirical
many-body potentials such as SMA, but also EAM
[25] or others, we will define in the following as
reconstructing elements those which do it according
to the energetic criterion (Ag, Pd, Au and Pt) and as
not reconstructing ones the others (Ni, Rh and Cu).
2.2. Surface stress

2. Results
2.1. Surface energy
In Table 2, we give the calculated surface energies
for the unreconstructed (1
1) and reconstructed
(1
2) surfaces of fcc transition metals, both before
and after atomic relaxation. As can be seen, influence

Table 2
Surface energy of the not reconstructed (g1
1 ) and the reconstructed (g1
2 ) surfaces in erg/cm2 for a not relaxed (NRel) and a
fully relaxed (Rel) slab

g1
1
g1
1
g1
2
g1
2

NRel
Rel
NRel
Rel

Ni

Rh

Cu

Ag

Pd

Au

Pt

1943
1933
2005
1992

2250
2242
2305
2295

1370
1358
1405
1391

766
744
763
741

981
923
957
904

699
611
668
589

1347
1222
1299
1186

The next step was the calculation of surface stress

before and after reconstruction. The results are given
in Table 3 along the two directions. Let us first remark
that, as expected with such a potential from the effect
of bond breaking, we find that the surface undergoes a
Table 3
Surface stress along the dense x- and less dense y-directions with
and without reconstruction in erg/cm2 for a not relaxed (NRel) and
a fully relaxed (Rel) slab

sxx;1
1
sxx;1
1
sxx;1
2
sxx;1
2
syy;1
1
syy;1
1
syy;1
2
syy;1
2

NRel
Rel
NRel
Rel
NRel
Rel
NRel
Rel

Ni

Rh

Cu

Ag

Pd

Au

Pt

1620
1183
1630
1268
2171
1433
1697
1108

1787
1329
1798
1403
2342
1538
1861
1183

1417
980
1426
1036
1739
1045
1421
825

1490
872
1493
884
1424
606
1329
532

2895
1453
2892
1462
2470
805
2448
791

3114
1194
3106
1236
2499
580
2556
665

5116
2218
5105
2258
4189
1126
4241
1205

S. Olivier et al. / Applied Surface Science 212213 (2003) 866871

869

Fig. 2. Reconstruction induced variations of surface energy (solid line) and surface stress along the dense x-direction (dashed line) and less
dense y-direction (dotted line) for the seven fcc metals, for a not relaxed (a) and for a fully relaxed slab (b), and also as a function of the unique
parameter q (c). In (c) the energetic and stress quantities were divided by the energetic parameter x [20].

tensile stress (positive value) for all the elements along

both directions. We will come back on this point in
Section 3.
From these values, we are then able to calculate the
variation of surface stress induced by reconstruction
along one or the other direction: Dsxx and Dsyy . These
lead to the general trends which appear in Fig. 2. The
first general result is that, whatever the element Dsxx is
positive at least in the relaxed situation. It means that
the stress along the dense direction increases under
reconstruction, which could be guessed from simple
bond breaking elements, when going from 3D bulk to
2D surface and now to a dense 1D row. The situation
along the less dense direction is more complex.

Indeed, one finds that syy decreases for the elements

which do not reconstruct whereas it increases for those
who do it. In other words, the occurrence of reconstruction is linked to an enhancement of the tensile
stress along this non dense direction. These results
invalidate definitely any argument based on surface
stress relief to understand the physical origin of the
missing row reconstruction.
It is worth noticing that, contrary to what occurs for
surface energy and in agreement with what could be
guessed from elastic properties, the atomic relaxation
quantitatively modifies the absolute value of surface
stress. Thus, in the case of Ni for instance, relaxation
modifies surface stress by about 30% along the dense

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S. Olivier et al. / Applied Surface Science 212213 (2003) 866871

direction and by about 50% along the less dense one.

Moreover, the effect is sufficiently important to modify qualitatively the trend followed by Dsxx along the
transition series (see Fig. 2(a) and (b)).

3. Discussion
Our main result is that, within SMA, elements
which reconstruct in the missing row model undergo
a general increase of surface stress, which means that
this reconstruction is by no means driven by a tendency to release this stress. However, things are
different along the two directions. Let us recall that
the (1
2) reconstruction consists in removing one
dense [
1 1 0] row over two in the surface. Therefore,
the atoms in the remaining rows have lost neighbours
with respect to the unreconstructed surface so that they
would like to increase the in-row bonding to
compensate this. This could be done by enhancing
their orbital overlap by increasing close-packing along
the row. Unfortunately, these atoms are strongly
bonded to the substrate which forbids them to do that.
This competition, which is already at the origin of the
tensile character of surface stress, obviously enhances
this character for the in-row stress.
The behaviour along the [0 0 1] less dense direction
is more difficult to understand. We have shown in
Fig. 2(a) that the more the element reconstructs (Dg
decreases), the more the difference of surface stress
along the less dense [0 0 1] direction increases. In
order to get more insight on this argument, we have
extended to the case of surface stress, the simple
model previously used to interpret the evolution of
surface energy under reconstruction [20]. The main
ingredient is to assume that the reconstruction is
mainly driven by the q parameter of the SMA potential, which characterises the range of its attractive part
(see Section 1.1). We have then plotted in Fig. 2(c) the
variation of surface energy and stress, normalised to x,
as a function of this unique q parameter, having fixed p
(which drives the repulsive part) to the mean value of
10.55, d0 (the first neighbour bulk equilibrium dis (see Section 1.1). As can be seen, we
tance) to 2A
indeed recover the essential features of Fig. 2(a).
The intermediate behaviour of the 4d elements
previously mentioned is quite consistent with this
analysis. Indeed, Guillope and Legrand [20] have

shown that a small compression (1%) can favour

the reconstruction in Ag. This is confirmed from
the experimental point of view in the case of Ag/
Cu(1 1 0) [26]. In the same spirit, Filhol et al. [22]
have shown that deposition of Pd on Ni(1 1 0), with a
compression of Pd to the lattice parameter of Ni, leads
to a reconstruction of Pd.
Finally, we can wonder if is it possible to get some
local view of the microscopic mechanism responsible
of this puzzling variation of stress under reconstruction along the less dense direction. To answer this
question, we give in Fig. 3 the local contributions to
the variation of this stress induced by reconstruction,
for two elements presenting opposite behaviours: Au
which reconstructs and Cu which does not. The main
feature is that, in both cases, if one averages stress
variation per plane parallel to the surface, one finds
that reconstruction has some compressive effect in the
outer layer, a tensile one just below, and almost no
effect in the third plane. Note that when adding all
these contributions one indeed recovers the variations
derived from the values given in Table 3: 85 erg/cm2
for Au and 225 erg/cm2 for Cu. There is a small
difference coming from the lower planes not shown in
Fig. 3. If one now looks more quantitatively to these
values, one sees that the results are almost reversed
between both elements: the decrease of the tensile
stress at the surface is more pronounced than the
increase in the first underlayer (1013 erg/cm2 versus
778 erg/cm2 ) for Cu, whereas the opposite is observed
for Au (718 erg/cm2 versus 872 erg/cm2 ). The net
result is that tension increases for Au and decreases for
Cu, due to the different balance between the two layers
for both elements.

Fig. 3. Local contributions to the variation of stress along the less

dense direction y induced by the reconstruction for Cu (left) and Au
(right).

S. Olivier et al. / Applied Surface Science 212213 (2003) 866871

In conclusion, using a semi-empirical SMA potential, we find as expected that reconstruction is energetically favorable for Pt and Au but not for Ni and Cu,
in agreement with experiments. Moreover, we have
shown that surface stress is enhanced due to reconstruction along the dense direction whatever the element, and along the less dense one only for elements
which do reconstruct, relaxation having to be taken
into account to get reliable results. This behaviour,
which definitely invalidates a surface stress relief
criterion for this reconstruction, has been analysed
locally and interpreted in terms of the essential parameters of the interatomic potential.
Acknowledgements
We wish to thank P. Mu ller for fruitful discussions.
References
[1] G.P. Srivastava, Rep. Prog. Phys. 60 (1997) 561;
J.E. Northrup, Phys. Rev. B 47 (1993) 10032.
[2] D.A. King, Phys. Scr. T 4 (1983) 34.
[3] G. Tre glia, M.-C. Desjonque`res, D. Spanjaard, J. Phys. C:
Solid State Phys. 16 (1983) 2407.
[4] B. Legrand, G. Tre glia, M.-C. Desjonque`res, D. Spanjaard, J.
Phys. C: Solid State Phys. 19 (1986) 4463, and references
therein.

871

[5] M.A. Van Hove, R.J. Koestner, P.C. Stair, J.P. Bibe rian, L.L.
Kesmodel, I. Bartos, G.A. Somorjai, Surf. Sci. 103 (1981)
218.
[6] J.V. Barth, H. Brune, G. Ertl, R.J. Behm, Phys. Rev. B 42
(1990) 9307.
[7] A.R. Sandy, S.G.J. Mochrie, D.M. Zehner, K.G. Huang, D.
Gibbs, Phys. Rev. B 43 (1991) 4667.
[8] C.E. Bach, M. Giesen, H. Ibach, T.L. Einstein, Phys. Rev.
Lett. 78 (1997) 4225.
[9] R.J. Needs, M. Mansfield, J. Phys.: Condens. Matter 1 (1989)
7555.
[10] A. Filippetti, V. Fiorentini, Surf. Sci. 377 (1997) 112.
[11] W. Moritz, D. Wolf, Surf. Sci. Lett. 163 (1985) L655.
[12] C.-M. Chan, M.A. Van Hove, Surf. Sci. 171 (1986) 226.
[13] P. Fery, W. Moritz, D. Wolf, Phys. Rev. B 38 (1988) 7275.
[14] M. Shu, H. Bu, J.W. Rabalais, Phys. Rev. B 42 (1990) 2852.
[15] M.S. Daw, Surf. Sci. Lett. 166 (1986) L161.
[16] D. Toma nek, H.-J. Brocksch, K.H. Bennemann, Surf. Sci.
Lett. 138 (1984) L129.
[17] K.-M. Ho, K.P. Bohnen, Europhys. Lett. 4 (1987) 345.
[18] M. Garofalo, E. Tosatti, F. Ercolessi, Surf. Sci. 188 (1987)
321.
[19] V. Rosato, M. Guillope , B. Legrand, Phil. Mag. 59 (1989)
321.
[20] M. Guillope , B. Legrand, Surf. Sci. 215 (1989) 577.
[21] R. Shuttleworth, Proc. Phys. Soc. A 63 (1950) 444.
[22] J.-S. Filhol, D. Simon, P. Sautet, Surf. Sci. 472 (2001) L139.
[23] Z.P. Hu, B.C. Pan, W.C. Fan, A. Ignatiev, Phys. Rev. B 41
(1990) 9692.
[24] C.J. Barnes, M.Q. Ding, M. Lindroos, R.D. Diehl, D.A. King,
Surf. Sci. 162 (1985) 59.
[25] S.M. Foiles, Surf. Sci. 191 (1987) L779.
[26] T.N. Taylor, A.W. Denier van der Gon, J.F. van der Veen,
Phys. Rev. B 41 (1990) 7474.