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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).
0169-4332/03/$ see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0169-4332(03)00018-7
867
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
868
1
EN NEb
2A
(2)
1 @Ag
A @Eij
(3)
@g
;
@Eij
i; j x; y
(4)
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 (g11 ) and the reconstructed (g12 ) surfaces in erg/cm2 for a not relaxed (NRel) and a
fully relaxed (Rel) slab
g11
g11
g12
g12
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
sxx;11
sxx;11
sxx;12
sxx;12
syy;11
syy;11
syy;12
syy;12
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
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].
870
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
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.
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