Corrosion Science 73 (2013) 18–31

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Corrosion Science
journal homepage: www.elsevier.com/locate/corsci

Early stage oxidation of Ni–Cr binary alloy (1 1 1), (1 1 0) and (1 0 0)

surfaces: A combined density functional and quantum chemical
molecular dynamics study
Nishith Kumar Das a,⇑, Tetsuo Shoji b
a
Nuclear Safety Research Center, Japan Atomic Energy Agency, 2-4 Shirakata-shirane, Tokai-mura, Naka-gun, Ibaraki-ken 319-1195, Japan
b
Frontier Research Initiative, New Industry Creation Hatchery Center, Tohoku University, 6-6-10, Aoba, Aramaki, Aoba-ku, Sendai 980-8579, Japan

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

Article history: First-principles and tight-binding quantum chemical molecular dynamics were used in this study. The
Received 5 November 2012 chemisorption energies of O and OH on the Ni–Cr (1 1 0) surface are lower than those of other surfaces.
Accepted 12 March 2013 The oxygen 2p orbitals hybridise with Ni 3d, 4s and small amounts of p orbitals for the (1 0 0) surface
Available online 3 April 2013
while Ni p orbitals have no contribution for the (1 1 0) surface, which might reduce the adsorption energy.
Additionally, oxygen acquires the maximum depth into the Ni–Cr (1 1 0) surface. Applied strain increases
Keywords: the oxygen diffusivity. This study reveals that the Ni–Cr (1 1 0) surface is easier for oxygen diffusion
A. Alloy
accordingly oxidation accelerates.
B. Modelling studies
C. Oxidation
Ó 2013 Elsevier Ltd. All rights reserved.
C. Interfaces
C. Stress corrosion

1. Introduction Nickel-based alloys are widely used in the energy industry,

The interaction of water with solid surfaces is of great impor-
tance in chemistry, materials science, electrochemistry, corrosion
and biophysics. The dissociation process of water on metal pro-
vides the basis of an understanding of these fundamental reactions.
Therefore, water adsorption and dissociation has been studied
extensively on metal surfaces using various techniques [1–4].
The interaction of water with metal in high temperature environ-
ments leads to the dissolution of metallic atoms and the diffusion
of elements. Subsequently, oxidation takes place at the surface.
Oxidation is an indispensable process of alloys that can occur prior
to crack initiation. In relation to the role of the oxide film in stress
corrosion cracking (SCC), Engell observed that almost all metal–
electrolyte systems with SCC form films [5]. SCC is composed
two parts: initiation and propagation. A crack may propagate into
a material when it is initiated. Thus, metal surface oxidation is an
important step for the early stage of crack initiation. The process
requires a supply of oxygen and metal atoms with sufficiently high
mobilities on the surface [6]. The oxygen–metal interaction is an
essential process for surface oxidation initiation, and it is funda-
mentally very important.
⇑ Corresponding author. Tel.: +81 29 282 6473.
E-mail address: ndasbuet@yahoo.com (N.K. Das).
especially for structural components, because they have excellent
corrosion resistance and good mechanical properties. Ni-based al-
loys contain several alloying elements, which in turn may influence
the oxidation behaviour of the alloy, but it might be difficult to sim-
ulate the oxidation behaviour of the alloy using computational
methods. In this alloy, chromium is essential to assure oxidation
resistance. Therefore, the binary alloy or ternary alloy might be
the better option to understand the initial stage of the oxidation
mechanism. Several studies have been conducted on Ni-based al-
loys to understand and quantify their corrosion resistance [7–10].
For example, Jeng et al. performed an Auger electron spectroscopy
(AES) and ion-scattering spectroscopy (ISS) study of single and
polycrystalline Ni–Cr alloy surfaces at 500 °C [11]. They found that
Cr migrated to the near-surface region, where it reacted with NiO to
form Cr oxide. In addition, a X-ray photoelectron spectroscopy
(XPS) study of the polycrystalline Ni–Cr alloy showed that Cr is oxi-
dised preferentially to Cr2O3 initially but that Ni in the alloy is oxi-
dised more rapidly to NiO than Ni metal [12]. Moreover, numerous
studies have been conducted on H2O/Ni (1 1 1), Ni (1 1 0) and Ni
(1 0 0) and O/Ni (1 1 1), Ni (1 1 0) and Ni (1 0 0) systems by first prin-
ciples, molecular dynamics and experimental methods [13–21].
These studies show that the water molecule forms a weak bond
with the metal surfaces while atomic oxygen makes a strong bond.
An electron energy loss spectroscopy (EELS) study of H2O/Ni (1 0 0)
reports water dissociation at 200 K. In addition, a thermal desorp-
tion spectroscopy study showed that water molecules are adsorbed

0010-938X/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.corsci.2013.03.020
 N.K. Das, T. Shoji / Corrosion Science 73 (2013) 18–31
molecularly on the Ni (1 1 1) surface from 165 K at low coverage to
170 K at saturation, and the surface can absorb up to 260 K when
oxygen-predosed on the surface [19]. Several theoretical and exper-
imental studies have been conducted to determine the adsorption
energy, the geometrical features, the electronic structures and the
bonding mechanism. Carrasco et al. demonstrated the two orbital
overlap between water and metal surfaces [22]. The metal s state
is found to hybridise with the d state, resulting in hybridised s–d
orbitals projecting on water 3a1 and 1b1 orbitals. However, most
studies focused on the interaction between a clean Ni surface or
oxygen pre-adsorbed Ni surface with other molecules or atoms. It
is well known that the dilute impurities alter the geometry and
electronic structures of bulk system. One theoretical study found
that the chemisorption energy of carbon is altered by substitution-
ally embedded Cu atoms on the Ni (1 1 1) surface [23]. The Cu sub-
stitute nickel surface also increased the activation energy barrier for
CH. The substitution of chromium into the nickel surface increased
the oxygen and water chemisorption energies, which might reduce
the oxygen mobility on the surfaces [24]. Moreover, a multiscale
modelling study found that the stress intensity significantly in-
creases the oxygen diffusivity on the Ni and Ni–Cr surfaces; subse-
quently, it can intensify the primary stage of oxidation initiation
[25]. Therefore, surface oxidation is a process of that is a precursor
to the early stages of cracking initiation. In order to address this is-
sue, it is desirable to get better description and deeper insight into
the basic features of chemical reaction of water with metal surface.
Moreover, the oxygen diffusivity and the nature of oxygen bonding
with the elements of the metal surface are important in studying
the corrosion and passivation phenomena. Computational chemis-
try is a very powerful and reliable tool in obtaining detailed infor-
mation on atomic scale for understanding the oxidation initiation
process. The present theoretical study has been undertaken to shed
light in the interaction between oxygen, OH and H2O and the Cr-
doped Ni (referred to as Ni–Cr here) surfaces as a first step for
understanding the early stage of oxidation mechanism. At present,
it is a demanding task to simulate by a computational approach. In
this paper, the density functional theory (DFT) method is consid-
ered for nickel and Cr-doped nickel surfaces with oxygen, OH and
H2O interactions, and a tight-binding quantum chemical molecular
dynamics (QCMD) method is employed to understand the early
stage oxidation of the Ni–Cr (1 1 1), (1 1 0) and (1 0 0) surfaces.
2. Computational details
The DFT and tight-binding QCMD methods were used in this
study. DFT is an accurate method to calculate the geometry, the
structure, the energetics and the orbitals interaction. These proper-
ties are very important to understand the fundamental phenome-
non of alloy surfaces and different interfaces. The DFT method
considers a small atomic model, but it can give us fruitful informa-
tion from the fundamental point of view. For instance, the higher
chemisorption of atomic oxygen on a metal surface may lead to
less movement on the surface. In contrast, the tight-binding QCMD
method is a tool that can consider reaction dynamics and large
models at high temperature. These two methods were used to ana-
lyse the oxidation initiation phenomenon at the atomic level.
The DFT study intends to investigate the adsorption energy and
detailed bonding nature of clean and oxygen, OH and water ad-
sorbed Ni (1 1 1) and Ni–Cr (1 1 1) surfaces; all calculations were
performed using DFT [26] within the generalised gradient approx-
imation (GGA), as implemented in the DMol3 module of the Mate-
rials Studio packages [27–29]. The exchange–correlation energy
was described using the spin polarisation form of the Perdew
and Wang 91 functional (PW91) [30,31]. A numerical basis set,
which describes the orbitals in the valence shell with double
19
numerical functions (DNP), was employed; it is comparable in
quality to a Gaussian 6-31G basis set [32]. A 2  2 unit cell was
employed. The (1 0 0) and (1 1 0) metal surfaces were modelled by
a periodical array of four layer slabs and separated by a 12 Å vac-
uum region, where the top three layers allowed free interaction
and the bottom layers were fixed. The atomic oxygen, OH and
water molecule interactions were not expected beyond the first
three layers. We calculated a five layer slab model. The calculated
adsorption energy difference was 9 and 7 meV for oxygen adsorp-
tion on the Ni (1 0 0) and Ni (1 1 0) surfaces, respectively. Thus, the
choice of four layers is believed to be quite adequate. Each layer
consists of four nickel atoms. Brillouin zone sampling was per-
formed using a Monkhorst–Pack grid. We performed several k-
points calculations, which showed that a 5  5  1 k-points mesh
for surfaces was sufficient. The calculated energy differences be-
tween 5  5  1 and 6  6  1 and 7  7  1 k-points meshes were
less than 10 meV. The selected set of k-points calculations is suffi-
cient for the present study. A previous study is also in good agree-
ment with this calculation [24]. The self-consistent field
convergence tolerance was permitted up to 1.0  105 and a max-
imum force of 0.04 Ha/Å. The double optimisation of the unit cell
was performed. First, the structure and atomic positions were fully
optimised, and then the optimised structure opted for further cal-
culations. For the bimetallic Ni–Cr surfaces, one Ni atom was re-
placed by a Cr atom in the top layer, and two nickel atoms in the
top and second layers were replaced by Cr atoms. Fig. 1 was con-
sidered for the geometrical optimisation of the surfaces. Initially,
water molecules were situated parallel to the surface, and OH mol-
ecules were placed parallel and perpendicular to the surface. The
OH perpendicular to the surface was more preferred than OH par-
allel to the surface. Thus, the OH parallel to the surface was not
considered for further study. The oxygen atoms, OH and water
molecules were placed on top, bridge, or hollow sites.
The adsorption energies for atomic oxygen, hydroxyl and water
molecules were calculated with the following formula:
Ead ¼ EðNi=Ni—Cr surfacesÞ þ EðO=OH=H2 OÞ
 EðNi=Ni—Cr surfaces þ O=OH=H2 OÞ
where E(Ni/Ni–Cr) is the total energy of a similar supercell repre-
senting the Ni or Ni–Cr clean surfaces; E(Ni/Ni–Cr + O/OH/H2O) is
the calculated total energy of the O/Ni, OH/Ni, H2O/Ni, O/Ni–Cr,
OH/Ni–Cr, or H2O/Ni–Cr systems; and E(O/OH/H2O) is the energy
of atomic oxygen or OH or H2O molecules in a cube with dimen-
sions 12  12  12 Å3.
For tight-binding QCMD, we designed a set of parameters to ana-
lyse the reaction dynamics of binary or ternary nickel-based alloys or
austenitic stainless steels. Diatomic calculation performed followed
by the bulk systems by considering several parameters such as bind-
ing energy, equilibrium bond distance, cohesive energy and lattice
constant. The set of parameters were quite consistent with the
experimental and first principles calculated data; for example, the
calculated cohesive energy of nickel is 4.42 eV, and the experimental
value is 4.44 eV. More details about the parameterisation can be seen
elsewhere [33]. The tight-binding QCMD code ‘colors’ developed by
Tohoku University was employed for the water dissociation and
adsorption on the Ni–Cr (1 1 1), Ni–Cr (1 1 0) and Ni–Cr (1 0 0) binary
alloy surfaces in high temperature environments. This code is five
thousand times faster than conventional DFT and can handle the
reaction dynamics of metal surfaces efficiently. Ni–Cr surface crystal
structure was created by using the software Material Studio. First,
DFT calculations were performed for the optimisation of a small
Ni–Cr surface; then, we built the slab surface based on the optimised
surface. Fig. 2 shows the models of the Ni–Cr binary alloy slab sur-
faces. The models consist of 84 atoms (71 of Ni and 13 of Cr atoms)
with a monolayer of four water molecules embedded on the sur-
20 N.K. Das, T. Shoji / Corrosion Science 73 (2013) 18–31

Fig. 1. (a) Side view (different colours indicate the layer), (b) top view of the possible adsorption sites of Ni (1 1 0), (c) one chromium atom doped, (d) two chromium atom
doped Ni (1 1 0), (e) side view (different colours indicate the layer), (f) top view of the possible adsorption sites of Ni (1 0 0) and (g) one chromium atom doped and (h) two
chromium atom doped Ni (1 0 0) surfaces for DFT calculations. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of
this article.)

faces. Thirteen nickel atoms, at chosen random, were substituted by
chromium atoms for all slab models. Water molecules were placed
3 Å away from the surfaces. The metal surfaces were modelled by a
periodical array of seven layer slabs where the top layers allowed
free interaction and the bottom layer was fixed. One percent (1%)
uniaxial tensile strain was applied along the x-axis on the z-plane
of the slab model. The bulk length along the x-axis was extended
1% over the initial length. The applied strain for the perfect crystal
surface should be elastic. A total of 8000 simulation steps were car-
ried out, where each step was 0.2 femto second (fs), with the Verlet
algorithm. The advantage of this algorithm is that it requires less
computer memory because only one set of positions, forces and
velocities need to be carried at any one time. The ensemble for this
simulation was constant volume and constant temperature (NVT),
and the temperature was controlled by using scaling the atom veloc-
ities. The temperature considered was 325 °C, which represents the
PWR condition, and atmospheric pressure was used.
3. Results and discussion
3.1. DFT results
Previously, we studied the oxygen and water adsorption on Ni
(1 1 1) and Ni–Cr (1 1 1) surfaces [24]. Here a combined DFT and
 N.K. Das, T. Shoji / Corrosion Science 73 (2013) 18–31 21

Terrace site Water

Ni

Cr

(a) (b) (c)

Fig. 2. Slab model surfaces for simulation: (a) Ni–Cr (1 1 1), (b) Ni–Cr (1 1 0) and (c) Ni–Cr (1 0 0).

tight-binding QCMD methods have been considered. The DFT
method applied to study atomic oxygen, OH, and water adsorption
on Ni and Ni–Cr (1 1 0) and (1 0 0) surfaces and OH adsorption on Ni
(1 1 1) and Ni–Cr (1 1 1) surfaces.
3.1.1. Ni (1 1 1) and Ni–Cr (1 1 1) surfaces
The calculated results found that the highest absorption energy
for oxygen was 6.86 eV for the Ni–Cr (1 1 1) surface, followed by
the hcp site, whereas the absorption energy was 5.56 eV for the
Ni (1 1 1) surface [24]. The result concerning the Ni–Cr surface im-
plied that the bond distances were 1.93–1.95 Å and 1.75 Å for Ni–O
and Cr–O, respectively. The oxygen atoms preferred to bond with
Cr rather than Ni atoms. However, we calculated OH adsorption
properties on the Ni (1 1 1) and Ni–Cr (1 1 1) surfaces. The OH
adsorption energies were 3.28 eV and 3.73 eV for the Ni and Ni–
Cr surfaces, respectively. The most stable adsorption sites were
fcc hollow and on top Cr site for the Ni and Ni–Cr surfaces, respec-
tively. The OH adsorption energy was significantly increased due to
the substituted Cr on top of the nickel surface. The previous theo-
retical study found an OH adsorption energy on the Ni (1 1 1) sur-
face of 3.71 eV [34]. They considered the cluster model of the Ni
(1 1 1) surface, which might give us a different energy value. The
bond distance of the nickel and the oxygen of the OH was 2.01 Å
for the pure nickel surface, which is very close to the value found
in the previous study [34,35]. In the case of the Ni–Cr surface,
the chromium and oxygen bond distance was 1.79 Å. The oxygen
of OH preferentially bonds with chromium. The adsorbed OH was
approximately 5° tilted relative to the surface normal, and the O–H
bond length was 0.97 Å. The results are in agreement with the
observations of Yang et al. [35]. The OH adsorbed surface metallic
atoms have slightly (2%) outward movement between the first
and second layer.
3.1.2. Energetics and geometries of oxygen, OH and H2O adsorbed on
Ni and Cr-doped Ni (1 1 0) surfaces
We investigated the site preference of O, OH and H2O on Ni
(1 1 0) and Ni–Cr (1 1 0) surfaces. The calculated adsorption ener-
gies are shown in Tables 1–3. Oxygen was found to adsorb on short
bridge (SB) site of the unreconstructed p(2  2) Ni (1 1 0) surface
with an adsorption energy of 5.22 eV. Long bridge (LB) site was
the next most stable site with an adsorption energy of 5.10 eV.
Oxygen chemisorption on Ni (1 1 0) surface has been extensively
studied by various methods. One theoretical study concluded that
the short bridge site is the most preferential site for oxygen
adsorption. Moreover, a low-energy electron diffraction (LEED)
study demonstrated that the adsorbed oxygen atoms were located
in the short-bridge sites of the unreconstructed Ni (1 1 0) surfaces
[36]. The Ni–O bond distance was found to be 1.77 Å, which is
the same as the value found in the previous study [37]. The oxygen
adsorption energies were increased to 6.55 and 6.60 eV for one and
two chromium atom doped Ni (1 1 0) surfaces, respectively. Fur-
thermore, the adsorption energy was significantly decreased for
the surface with a chromium atom doped into the second and third
layers. For instance, the first and third layer chromium doped sur-
face is 1.2 eV less stable than the one chromium atom doped Ni
(1 1 0) surface. A previous DFT study found that the oxygen adsorp-
tion energy increased for the Ni–Cr (1 1 1) surface, which agrees
very well with the present study [24]. Chromium substituted on
the top layer had a considerable effect on the oxygen adsorption
energy while the effect is insignificant for the second and third lay-

Table 1
Oxygen adsorption on Ni (1 1 0) and Cr-doped Ni (1 1 0) surfaces.

Surface Sites Ead (eV) Ni–O distance Cr–O distance

Ni (1 1 0) Hollow 5.11 2.10
Long-bridge 5.05, 5.29a 1.93
Short-bridge 5.22, 5.35a 1.77
Top 4.14 1.66
Ni-top1Cr (1 1 0) Hollow 6.05 1.92 1.68
Long-bridge 6.05 1.96 1.69
Short-bridge 6.55 1.91 1.68
Top 6.38 1.59
Ni-top2Cr (1 1 0) Hollow 6.10 2.3 1.89
Long-bridge 6.01 1.94 1.70
Short-bridge 6.60 1.92 1.68
Top 6.33 1.59
a
Ref. [35].
22 N.K. Das, T. Shoji / Corrosion Science 73 (2013) 18–31
Table 2
OH adsorption on Ni (1 1 0) and Cr-doped Ni (1 1 0) surfaces.
Surface Sites
Ni (1 1 0) Hollow
Long-bridge
SB (inclined)
SB (perp.)
Ni-top1Cr (1 1 0) Hollow
Long-bridge
SB (inclined)
SB (perp.)
Ni-top2Cr (1 1 0) Hollow
Long-bridge
SB (inclined)
SB (perp.)
Table 3
H2O adsorption on Ni (1 1 0) and Cr-doped Ni (1 1 0) surfaces.
Surface Sites Ead (eV) Ni–O distance
Ni (1 1 0) Hollow 0.48
Long-bridge 0.37
Short-bridge 0.48
Top 0.70 2.14
Ni-top1Cr (1 1 0) 0.99
Ni-top2Cr (1 1 0) 0.98
ers. It is evident that chromium atoms on the top layer are very ac-
tive for oxygen adsorption. The Cr–O and Ni–O bond distances
were 1.68 and 1.92 Å for Ni–Cr (1 1 0) surfaces, respectively. A clus-
ter model study found a bond distance of 1.61 Å for Cr–O in Cr2O3
[38]. The X-ray adsorption near-edge structure (XANES) structure
showed a bond distance of 1.60 Å for Cr–O in Cr(IV) [39]. The short-
est distance between chromium and oxygen corresponds to strong
binding. Oxygen bonds favourably with chromium, which might
increase the adsorption energy.
Hydroxyl species are often formed on metal surfaces. The LEED
analysis showed the OH formation on an oxygen preadsorbed Ni
(1 1 0) surface below 360 K [40]. A angle resolved ultraviolet photo-
emission spectroscopy (UPS) and ESDIAD study also found OH on
the Ni (1 1 0) surface at 350 K [41]. The most preferential site was
SB of OH inclined to the normal of the surface, and the oxygen
was always at the bottom. The adsorption energy of the most sta-
ble structure was 3.66 eV. The adsorption energy of OH on SB site
with perpendicular to the surface was 3.39 eV, which is smaller
than that of the most stable SB site. One experimental study dem-
onstrated that OH molecules were inclined with respect to the sur-
face normal [42]. The calculated adsorption energy is marginally
higher than that of the previous ab initio study [43]. The small size
of the cluster and the different method may affect the value. The
DFT study of OH adsorption on Ni28 cluster gave 3.77 eV for the
Ni (1 1 1) surface [34]. The O–H bond distance was found to be
0.98–0.99 Å, which is very close to the calculated gas phase value.
It indicates that OH is molecularly adsorbed on the surface and that
the adsorption is weaker than that of atomic oxygen, with a Ni–O
bond distance 1.93 Å. The absence of reconstruction of the Ni (1 1 0)
surface upon OH adsorption is attributed to the weaker bonding
interaction between the O and Ni atoms in the case of OH chemi-
sorption compared to O chemisorption [40]. The adsorption energy
of the Ni–Cr surface was increased to 4.30 eV. The most preferable
site was SB with inclined to the surface normal. It appears that the
doping of chromium did not change the adsorption sites. The OH
adsorption energy on the two chromium atom doped surface did
not increase compared to that of the single chromium doped sur-
face. The higher chromium concentration on the Ni (1 1 0) surface
had less effect on the OH adsorption energy. The Cr–O bond dis-
Ead (eV) Ni–O distance Cr–O distance
2.87 2.28
3.36 1.99
3.66 1.93
3.39 1.90
3.46 2.25 2.09
3.68 2.13 1.91
4.30 2.01 1.89
4.08 1.97 1.88
3.50 2.38 2.16
3.72 2.08 1.96
4.26 2.01 1.88
4.03 1.99 1.87
tance was 1.87 Å while Ni–O bond distance was 1.99 Å, which re-
veals that the Ni–O bond distances were slightly increased due to
the chromium doped into the surfaces. The Cr–O bond distances
Cr–O distance were smaller than those of Ni–O, corresponding to the preferential
binding between the oxygen of the OH molecule and the Cr of the
Cr-doped alloy surface.
For H2O/Ni (1 1 0), the calculated absorption energy was 0.70 eV,
which is the highest among all low-index nickel surfaces. The top
2.135
site was the most stable site. The value is slightly higher than
2.133 the previous results (0.58 eV) [44]. However, surface roughness in-
creased the adsorption energy. Experimental observation demon-
strated that the more open (1 1 0) surface adsorbs H2O more
strongly [41,45]. Our findings are in agreement with the previous
theoretical and experimental results. The calculated O–H bond dis-
tance and HOH angle were 0.98 Å and 103.5°, respectively. Water
was molecularly adsorbed via the oxygen atom, and the orienta-
tion of the hydrogen atoms was parallel to the surface. Several
experimental studies observed that H2O is bound through the oxy-
gen and that the hydrogen atom is parallel to the Ni (1 1 0) surface
[42]. The Ni–O bond distance was 2.14 Å. The X-ray absorption
fine-structure technique (SEXAFS) analysis showed that the water
molecules occupied top sites with Ni–O bond lengths of
2.06 ± 0.03 Å [46]. In addition, a previous DFT calculation (2.20 Å)
and surface X-ray diffraction observation (2.24 Å) found identical
values [24,47,48]. With the doping of chromium into the surfaces,
the adsorption energy increased to 0.98 eV for the one and two
chromium doped surfaces. The water adsorption energy was not
increased due to the doping of two chromium atoms. The tendency
is very similar to that of OH adsorption. The O–H bond distance
and the HOH angle of the adsorbed water molecule were 0.98 Å
and 103°, respectively, which is close to those of the gas phase
water molecule. The calculated Cr–O bond distance of 2.14 Å is
compatible with the previous study [24].
The interlayer spacing was significantly modified for the bare Ni
(1 1 0) surface. The present study demonstrated a 9% contraction in
the first interlayer and a 4% expansion in the second interlayer dis-
tance. The dynamical LEED study confirmed that the first interlayer
spacing is contracted by 9.8 ± 1.8% and that the second interlayer
spacing is increased by 3.8 ± 1.8% [49]. Another LEED study demon-
strated an 8.7 ± 0.5% contraction and a 3 ± 0.6% expansion in the
first and second interlayer spacing, respectively [50]. Several
experimental and theoretical studies reported the contraction of
the first interlayer spacing and the expansion of the second inter-
layer spacing [51]. The Cr-doped surfaces showed 11.5% inward
and 5.25% outward movement of the first and second interlayer
spacing, respectively. The doping of chromium slightly increased
the surface structure modification compared to that of the pure
nickel surface. The adsorption of oxygen on the Ni (1 1 0) surface
led to expansion (4%) between the first and second layers and
contraction (1.11%) between the second and third layers. Gunn
 N.K. Das, T. Shoji / Corrosion Science 73 (2013) 18–31 23

et al. previously noticed a 2.66% expansion between the first and an adsorption energy of 3.37 eV. The OH was adsorbed perpendic-
second layers and a 0.24% expansion between the second and third ular to the surface with a Ni–O bond distance of 2.14 Å. The calcu-
layers [52]. Adsorption sites may be attributed to this difference. lated distance between the oxygen and the nearest nickel was
The OH adsorbed surface had a 2.5% expansion and a 2% contrac- found to be 2.16 Å by Yang et al. [66]. They found that the adsorp-
tion between first and second and second and third layers, respec- tion energy is slightly higher than that in the present study. Differ-
tively, while the H2O adsorbed surface had no significant ent methods might provide different results while the adsorption
expansion between first and second inter layer. The adsorption of site and OH adsorption axis to the surface is consistent. The Ni–
oxygen on the Cr-doped surface led to a 2.2% expansion between Cr bridge site was found to be the most stable adsorption site for
the first and second layers. There is a negligible contraction be- one Cr-doped nickel surface, and the hollow site was 0.03 eV less
tween the second and third interlayer spacing. Additionally, the stable. The hollow site adsorption energy is very competitive.
OH and H2O adsorbed surfaces showed a very small (1.5%) expan- The OH adsorption energy on the hollow site was 4.15 eV for the
sion between the first and second layers. two Cr-doped Ni–Cr (1 0 0) surface. The energy of the Ni–Cr bridge
site was 0.20 eV smaller than that of the hollow site. It seems that
hollow site is the most stable for OH and oxygen adsorption. The
3.1.3. Energetics and geometries of oxygen, OH and H2O adsorbed on
Cr–O bond distances were smaller than the Ni–O bond distance
Ni and Cr-doped Ni (1 0 0) surfaces
for one and two chromium doped Ni–Cr (1 0 0) surfaces. The OH
Tables 4–6 show the calculated adsorption energies. The
distances varied from 0.97 to 0.98 Å. Water molecules were ad-
adsorption energy was calculated with the spin polarisation in
sorbed on the top site of the Ni (1 0 0) surface and remained parallel
the 2  2 unit cell with a coverage of 0.25 ML. The oxygen adsorp-
to the surface with an adsorption energy of 0.56 eV. The O–H bond
tion energy on the Ni (1 0 0) surface was 5.69 eV, and the most
distance was 0.98 Å, and the HOH angle was 103.46°. It reveals that
favourable adsorption site was the fourfold hollow site. One exper-
the water was absorbed molecularly on the bimetallic alloy sur-
imental study measured a value of 5.64 eV, which is in good agree-
faces. The previous DFT calculated adsorption energy of water on
ment with the present study [55]. A previous DFT study found a
the Ni (1 0 0) surface was 0.51 eV, which is compatible with this
wide range of adsorption energies from 4.81 eV to 6.7 eV [56]. Nev-
study [44]. A few theoretical and experimental studies on the Ni
ertheless, the adsorption energy of this study is in agreement with
(1 1 1) surface showed that the water absorption energy was
the experimental results. However, the four fold hollow site is the
0.52 eV and 0.43 eV, respectively [24,67]. The adsorption energy
most stable site for oxygen adsorption on the Ni (1 0 0) surface [57].
increased to 0.90 eV for one chromium doped on the top layer,
The Cr-doped surfaces increased the adsorption energies. The max-
but the adsorption energy decreased to 0.67 eV for the two chro-
imum adsorption energy was attained by the surface with two
mium atom doped alloy surface. The geometrical structure showed
chromium atoms doped on the Ni (1 0 0) surface with 6.82 eV.
that the Cr–O bond distances were 2.14 and 2.17 Å for one and two
The fourfold hollow site was the most favourable while the top site
chromium atom doped surfaces, respectively, and the hydrogen
was the most unfavourable. The bridge site was the next most sta-
atoms of the water molecules remained on the hollow site while
ble site. The oxygen adsorption energy of the Ni–CrNi–Cr (1 0 0)
one hydrogen atom was on the bridge and another one was on
surfaces were higher than that of the pure nickel surfaces, as
the hollow site. These two features may affect the adsorption en-
shown in Fig. 3, which reveals that oxygen bonds strongly with
ergy. The molecularly adsorbed water made a weak bond with me-
Ni–Cr surfaces. The oxygen adsorbed surfaces did not show recon-
tal surfaces.
struction. This observation is in agreement with the previous stud-
The clean Ni (1 0 0) surface showed an approximately 1% inward
ies [58–60]. The oxygen adsorption energy on the (1 0 0) surface is
relaxation between the first and second layers, and the value is
the highest among the low-index nickel surfaces. A higher adsorp-
perfectly consistent with the experimental observation [59]. The
tion energy indicates the lower oxygen mobility on the surface. As
clean surface is well-known to be unreconstructed. Top layer Ni
a result, the process might decelerate the oxygen movement on the
atoms moved slightly outward (0.08 Å) to adsorb the oxygen atom.
Ni (1 0 0) surface. The calculated Ni–O bond distance was 1.96 Å.
The LEED analysis also found a 0.07 Å elongation for the p(2  2)
The value is exactly same as that according to the surface extended
structures [68]. The top layer nickel atoms had a small (>1%) out-
X-ray absorption fine structure (SEXAFS), LEED and normal photo-
ward relaxation for the OH and H2O absorption. The Ni–Cr surface
electron diffraction (NPD) studies and in fair agreement with the
showed a slightly higher (2%) elongation between first interlayer
high-resolution electron energy loss spectroscopy (HREELS,
compared to the nickel surface due to oxygen adsorption. The Cr–O
1.98 Å) studies [61–65]. The Ni–O bond distances were increased
preferential bond might help to increase the metallic bond. The OH
to 2.05 Å in the presence of Cr on the Ni–Cr surface while the
and H2O adsorption had a small effect (1%) on the Ni–Cr bond dis-
Cr–O bond distances varied from 1.80 to 1.82 Å. The shorter Cr–O
tance. Molecular adsorption had less effect on the interlayer
bond distance implies that the oxygen has some affinity to chro-
spacing.
mium. For OH, the fourfold hollow site was the most stable with

3.1.4. Density of states analysis

Table 4 Mulliken and Hirshfeld charge analysis suggested that oxygen
Oxygen adsorption on Ni (1 0 0) and Cr-doped Ni (1 0 0) surfaces. atoms were receiving electrons from the metal surfaces while me-
Surface Sites Ead (eV) Ni–O distance Cr–O distance tal atoms were donating electrons from their outer orbitals. The
oxygen atoms were receiving 0.58 and 0.66e from the nickel and
Ni (1 0 0) Hollow 5.69, 5.63a, 5.00b 1.96
Bridge 5.12 1.78 Ni–Cr surfaces, respectively. We attempted to elucidate the nature
Top 3.98 1.67 of bonding between the bare metal and the oxygen, OH and H2O
Ni-top1Cr (1 0 0) Hollow 6.33 2.05 1.80 adsorbed surfaces. The top most layer nickel and the adsorbed oxy-
Bridge 6.31 1.94 1.67 gen, OH and water molecules were projected to calculate the par-
Top 6.15 1.60 tial density of states (pDOS), as shown in Fig. 4. The pDOS of the Ni
Ni-top2Cr(1 0 0) Hollow 6.82 2.37 1.82 (1 1 1) surface has been published elsewhere [24]. The Ni (1 0 0) and
Bridge 6.22 1.91 1.69 Ni (1 1 0) bare surfaces showed that the 3d orbitals were highly
Top 6.04 1.59 localised at the Fermi level. The Ni 4s orbitals had a small contribu-
a
Ref. [53]. tion below the Fermi level. There was a small overlapping between
b
Ref. [54]. the Ni s and p orbitals near the Fermi energy, as shown in Figs. 4a
24 N.K. Das, T. Shoji / Corrosion Science 73 (2013) 18–31

Table 5
OH adsorption on Ni (1 0 0) and Cr-doped Ni (1 0 0) surfaces.

Surface Sites Ead (eV) Ni–O distance Cr–O distance

Ni (1 0 0) Hollow 3.37 2.14
Bridge 3.22 1.92
Top 2.97 1.81
Ni-top1Cr (1 0 0) Hollow 3.88 2.25 1.91
Bridge 3.91 1.98 1.88
Top 3.79 1.79
Ni-top2Cr (1 0 0) Hollow 4.15 2.28 2.06
Bridge 3.95 1.95 1.92
Top 3.82 1.79

Table 6
H2O adsorption on Ni (1 0 0) and Cr-doped Ni (1 0 0) surfaces.

Surface Sites Ead (eV) Ni–O distance Cr–O distance

Ni (1 0 0) Hollow 0.36 3.17
Bridge 0.39 2.98
Top 0.56, 0.51a 2.21
Ni-top1Cr (1 0 0) Top 0.90 2.15
Ni-top2Cr (1 0 0) Top 0.67 2.17
a
Ref. [40].

was observed between the Ni p and oxygen 2p orbitals. Earlier the-

8
oretical studies on O/Ni (1 0 0) demonstrated similar bonding be-
tween Ni and oxygen [70]. Soft X-ray emission spectroscopy
Oxygen adsorption energy, Ead (eV)

Two Cr-doped Two Cr-doped
7 (100) One Cr-doped (110)
One Cr-doped (110)
(100)
6 orbitals were more pronounced for the two chromium doped sur-
Ni (100)
Ni (110)
5
4 oxygen 2p and chromium 3d orbitals; concurrently, metal s–p orbi-
Surfaces
Fig. 3. Comparison of the oxygen adsorption energies between two different
surfaces.
and b. These peaks are less pronounced for the top layer atoms. It
seems that the 3d orbitals are mainly dominant in the bonding
while the s and p orbitals contribute a little for bare metal surfaces.
The DFT study of nickel clusters demonstrated the similar orbitals
interactions [69]. The Ni–Cr surfaces showed a strong interaction
between the Ni 3d and Cr 3d orbitals and the Ni s small peak hybri-
dised with the Cr 3d orbitals. With further increase in the chro-
mium concentration on the top layer, the orbital interactions
changed slightly due to the increasing contribution from the Cr d
and s orbitals. However, the Cr-doped surface bonds were mainly
influenced by 3d orbitals. The pDOS of Ni and Ni–Cr surfaces were
modified to adsorb atomic oxygen. The oxygen 2p orbitals and Ni
3d and 4s orbitals were interacting for the Ni (1 0 0) surface while
a strong interaction was observed between the oxygen 2p and Ni
3d orbitals of Ni (1 1 0). A small Ni p peak appeared at 5.9 eV
for the oxygen adsorbed Ni (1 0 0) surface, as shown in Fig. 4i. In
the case of Ni (1 1 0), the Ni p orbitals had no effect on the bonding
process. These orbitals bonding might affect the oxygen chemi-
sorption energy. However, the Ni 3d orbitals were hybridised with
the oxygen 2p orbitals, and the Ni s orbitals also showed a peak be-
low the Fermi energy at 5–6 eV. In addition, a small interaction
(SXES) analysis demonstrated the hybridisation between the oxy-
gen 2p and Ni 3d states [71]. The oxygen 2p states were also ob-
served to interact with the metal s-p states. The bonding nature
changed when Cr was doped onto the nickel surfaces. The Cr 3d
face, as shown in Fig. 4j. The strong hybridisation between the Cr
3d and oxygen 2p orbitals was clearly observed while a small
amount of donation was due to the Ni d and s, and Cr s and p orbi-
tals. A single chromium doped nickel surface demonstrated the
interaction between the oxygen 2p and Cr 3d, Ni 3d and 4s orbitals.
The pDOS analysis suggests the strong hybridisation between the
tals donated a small amount electrons, which might increase the
adsorption energy. Upon OH adsorption, the electrons were trans-
ferred from the metal surface to the oxygen of the OH. The OH 3r
and 1p orbitals were found below the Fermi energy. The OH ad-
sorbed on Ni surfaces showed the bonding between Ni d and s
and oxygen 2p orbitals. A clear small Ni p peak was also found at
5.86 eV. The hydrogen 1s orbitals were not interacting with the
metal atoms. The Ni 3d and 4s orbitals were the main contributors
while the p orbitals were less significant. Moreover, the Cr 3d and
Ni 3d and 4s orbitals interacted with the oxygen 2p orbitals for the
OH adsorbed surfaces. UPS studies have led to the assignment of
levels 5.5 and 9.2 eV below the Fermi energy as p-bonding and
r-bonding levels for OH adsorption on Ni (1 1 0) [42]. Avdeev
et al. found the admixture of Ni 3d and 4s with oxygen 2p orbitals
[72]. We also found the hybridisation between the oxygen 2p and
Ni 3d and 4s orbitals. Additionally, a small Ni p orbitals peak was
found in this study. A small amount of charge was transferred from
the water molecule to the metal surface. Water donated a small
amount of charge (0.07e) to the surface. A DFT study demon-
strated that the 0.03e charge was transferred from water to the
surfaces [22]. Water adsorption on the Ni and Ni–Cr surfaces had
three peaks below the Fermi energy, corresponding to the 1b2,
3a1 and 1b1 orbitals, respectively. The pDOS curves for the nickel
surfaces were slightly modified after adsorbing water molecules.
The Ni 4s and 3d orbitals were the main contributors in the bond-
ing process. In addition, Ni p orbitals also showed a little contribu-
 N.K. Das, T. Shoji / Corrosion Science 73 (2013) 18–31 25

250 250
Ni of 4s Ni of 4s
Ni of 3p Ni of 3p
Ni of 3d Ni of 3d
200 200

pDOS (electrons/eV)

pDOS (electrons/eV)
150 150

100 100

50 50

0 0
-10.0 -7.5 -5.0 -2.5 0.0 2.5 5.0 7.5 10.0 -10.0 -7.5 -5.0 -2.5 0.0 2.5 5.0 7.5 10.0
Energy (eV) Energy (eV)
(a) (b)
Ni of 4s
Ni of 4s

pDOS (electrons/eV)
Ni of 3p
pDOS (electrons/eV)

Ni of 3p
Ni of 3d
40 Ni of 3d
40 Cr of 4s
Cr of 3p
Cr of 3d

20 20

250 250
-7.5 -5.0 -2.5 0.0 Ni of 4s -7.5 -5.0 -2.5 0.0 Ni of 4s
Ni of 3p Ni of 3p
Energy (eV) Ni of 3d Energy (eV) Ni of 3d
200
pDOS (electrons/eV)

200
pDOS (electrons/eV)

Cr of 4s
Cr of 3p
Cr of 3d
150 150

100 100

50 50

0 0
-10.0 -7.5 -5.0 -2.5 0.0 2.5 5.0 7.5 10.0 -10.0 -7.5 -5.0 -2.5 0.0 2.5 5.0 7.5 10.0
Energy (eV) Energy (eV)
(c) (d)
Ni of 4s Ni of 4s
pDOS (electrons/eV)
pDOS (electrons/eV)

Ni of 3p Ni of 3p
Ni of 3d Ni of 3d
40 Cr of 4s 40
Cr of 3p
Cr of 3d

20 20

250 250
-7.5 -5.0 -2.5 0.0 Ni of 4s -7.5 -5.0 -2.5 0.0 Ni of 4s
Ni of 3p Ni of 3p
Energy (eV) Ni of 3d Energy (eV) Ni of 3d
200 200
pDOS (electrons/eV)

pDOS (electrons/eV)

Cr of 4s
Cr of 3p
Cr of 3d
150 150

100 100

50 50

0 0
-10.0 -7.5 -5.0 -2.5 0.0 2.5 5.0 7.5 10.0 -10.0 -7.5 -5.0 -2.5 0.0 2.5 5.0 7.5 10.0
Energy (eV) Energy (eV)
(e) (f)
Fig. 4. Partial density of states of (a) all atoms of Ni (1 0 0), (b) all atoms of Ni (1 1 0), (c) top layer atoms of Ni (1 0 0), (d) top layer atoms of one Cr-doped Ni (1 0 0), (e) top layer
atoms of two Cr-doped Ni (1 0 0), (f) top layer atoms of Ni (1 1 0), (g) top layer atoms of one Cr-doped Ni (1 1 0), (h) top layer atoms of two Cr-doped Ni (1 1 0), (i) projected
atoms of oxygen adsorbed Ni (1 0 0), (j) projected atoms of oxygen adsorbed two Cr-doped Ni (1 0 0), (k) projected atoms of OH adsorbed Ni (1 1 0), (l) projected atoms of OH
adsorbed two Cr-doped Ni (1 1 0), (m) projected atoms of H2O adsorbed Ni (1 1 0), and (n) projected atoms of H2O adsorbed two Cr-doped Ni (1 1 0) surfaces.
26 N.K. Das, T. Shoji / Corrosion Science 73 (2013) 18–31

250 250
Ni of 4s Ni of 4s
Ni of 3p Ni of 3p
Ni of 3d Ni of 3d
200 200

pDOS (electrons/eV)
pDOS (electrons/eV) Cr of 4s Cr of 4s
Cr of 3p
Cr of 3p
Cr of 3d Cr of 3d
150 150

100 100

50 50

0 0
-10.0 -7.5 -5.0 -2.5 0.0 2.5 5.0 7.5 10.0 -10.0 -7.5 -5.0 -2.5 0.0 2.5 5.0 7.5 10.0
Energy (eV) Energy (eV)
(g) (h)

Ni of 4s Ni of 4s

pDOS (electrons/eV)
pDOS (electrons/eV)

Ni of 3p Ni of 3p

40 Ni of 3d
O of 2s
40 Ni of 3d
Cr of 4s
O of 2p Cr of 3p
Cr of 3d
O of 2s
O of 2p

20 20

250 250
-7.5 -5.0 -2.5 0.0 Ni of 4s -7.5 -5.0 -2.5 0.0 Ni of 4s
Ni of 3p Ni of 3p
Energy (eV) Ni of 3d
Energy (eV) Ni of 3d
200 200
pDOS (electrons/eV)
pDOS (electrons/eV)

O of 2s Cr of 4s
O of 2p Cr of 3p
Cr of 3d
150 150 O of 2s
O of 2p

100 100

50 50

0 0
-10.0 -7.5 -5.0 -2.5 0.0 2.5 5.0 7.5 10.0 -10.0 -7.5 -5.0 -2.5 0.0 2.5 5.0 7.5 10.0
Energy (eV) Energy (eV)
(i) (j)
250 250
Ni of 4s Ni of 4s
Ni of 3p Ni of 3p
Ni of 3d Ni of 3d
200 200
pDOS (electrons/eV)
pDOS (electrons/eV)

O of 2s Cr of 4s
O of 2p Cr of 3p
H of 1s Cr of 3d
150 150 O of 2s
O of 2p
H of 1s
100 100

50 50

0 0
-10.0 -7.5 -5.0 -2.5 0.0 2.5 5.0 7.5 10.0 -12.5 -10.0 -7.5 -5.0 -2.5 0.0 2.5 5.0 7.5 10.0
Energy (eV) Energy (eV)

(k) (l)
Fig. 4. (continued)

tion, which may not be negligible. The H2O/Ni (1 1 1) theoretical
investigation demonstrated that the Ni p states were involved in
the bonding with oxygen 2p states, which is in line with the pres-
ent study [73]. Moreover, several studies suggested that surface s–
d hybridisation is a general feature in water metal interaction [74].
The Ni d along with the Cr d, s, and p orbitals interacted with water
1b1 orbitals for one chromium doped nickel surface. The Ni s orbi-
tals peak was slightly decreased with increased chromium concen-
tration while the Cr s–p–d orbitals increased the interaction with
water molecules. This study reveals that the transitional metal d
and s orbitals were essentially in bonding with water while the p
orbitals showed little contribution. The metal surface and water
interactions were found to be very weak, resulting in a small
adsorption energy.
 N.K. Das, T. Shoji / Corrosion Science 73 (2013) 18–31 27

Ni of 4s Ni of 4s
Ni of 3p Ni of 3p

pDOS (electrons/eV)

pDOS (electrons/eV)
Ni of 3d Ni of 3d
40 H2O 40 Cr of 4s
Cr of 3p
Cr of 3d
H2O

20 20

250 250
-7.5 -5.0 -2.5 0.0 Ni of 4s -7.5 -5.0 -2.5 0.0 Ni of 4s
Ni of 3p Energy (eV) Ni of 3p
Energy (eV) Ni of 3d Ni of 3d
200 200
pDOS (electrons/eV)

pDOS (electrons/eV)
H2O Cr of 4s
Cr of 3p
Cr of 3d
150 150 H2O

100 100

50 50

0 0
-12.5 -10.0 -7.5 -5.0 -2.5 0.0 2.5 5.0 7.5 10.0 -12.5 -10.0 -7.5 -5.0 -2.5 0.0 2.5 5.0 7.5 10.0
Energy (eV) Energy (eV)
(m) (n)
Fig. 4. (continued)

3.2. Tight-binding QCMD analysis of the water/metal interfaces
The tight-binding self-consistent field is a worthy method to
describe the reaction dynamics of metal/solution interfaces at high
temperature.
3.2.1. Metal/water interface reaction dynamics
In the case of the adsorption of water molecules, OH and atomic
oxygen, different sites for the Ni (1 1 1), Ni (1 1 0) and Ni (1 0 0) sur-
faces are the energetically most stable sites. Previous studies dem-
onstrated that threefold hollow, short bridge and fourfold hollow
sites are the most stable for atomic oxygen adsorption on Ni
(1 1 1), Ni (1 1 0) and Ni (1 0 0) surfaces, respectively [21,37,75].
OH preferred to stay on fcc hollow, SB and four fold hollow sites
for (1 1 1), (1 1 0) and (1 0 0) surfaces, respectively while the top site
was the most favourable for water molecule adsorption [34,67]. At
the early stage, water molecules rotate from their original position
in which hydrogen atoms are directed toward the surface. Fig. 5
shows the calculated morphology of different Ni–Cr surfaces as a
function of time. The calculated results for other surface morphol-
ogies are similar to those in the figure. Water molecules are placed
at randomly on surface and are free to rotate. At the initial stage,
water molecules were adsorbed by the surfaces, and some of them
dissociated into OH and H ions. Subsequently some of the OH ions
produce O and H. The metal–hydrogen bond strength is stronger
than that of metal–water but weaker than those of metal–hydroxyl
and metal–oxygen. A lower bond strength helps to increase the dif-
fusivity of hydrogen into the structure. Dissociated hydrogen is
small in atomic size and can diffuse into the surfaces through the
hollow sites, and it can be trapped in interstitial sites. Some of
the hydrogen cannot diffuse due to coulombic repulsion with the
surface metallic atoms at the beginning. The interaction of dissoci-
ated oxygen and hydroxyl with metal atoms weakens the metal–
metal bond, leading to the initiation of possible dissolution. The
reaction progress with respect to time showed that the top layer
atoms moved upward, which produced extra space into the struc-
ture. The process helps to diffuse oxygen or hydroxyl ions. The sim-
ulated results showed that the oxygen atom penetrated several
layers of the metal surface. The diffusivity of oxygen into Ni–Cr
(1 1 0) surface is the highest among the all surfaces. One of the dis-
sociated oxygen atoms reached the bottom of the Ni–Cr (1 1 0) sur-
face. We have measured the diffusivity of oxygen along the z-axis,
as shown in Fig. 6a and b. The penetration depth was measured
from the initial position of the top layer metal atoms. One of the
oxygen atoms did not diffuse into the surface, which was not con-
sidered for this plot. The travelling time of the oxygen atoms to ac-
quire the maximum distances were 980 fs, 1020 fs and 1200 fs for
the Ni–Cr (1 1 1), Ni–Cr (1 1 0), and Ni–Cr (1 0 0) surfaces, respec-
tively. The oxygen penetration depth was slightly increased due
to applied uniaxial strain on the surfaces. The applied strain gener-
ates more space in the lattice, promoting the penetration of oxygen
into the slab. The oxygen atom was trapped around the chromium
and created a preferential bond that could help to reduce its diffu-
sivity, which indicates that 1% uniaxial strain increased the oxygen
penetration depth into the structure.
Fig. 6 clearly shows that the depth of the penetration of oxygen
in the Ni–Cr (1 1 0) surface is larger than that of the other surfaces.
The oxygen penetrated a short distance into the Ni–Cr (1 1 1) sur-
face. The larger diffusivity of oxygen reveals that the surface is easy
to oxidise by the oxygen atom; as a result, the metal surface can be
damaged. The analysis of the Ni–Cr (1 1 1) surface shows that the
oxygen atom is trapped around the chromium atom; correspond-
ingly, the process reduces the atomic diffusivity. However, the
Ni–Cr (1 1 0) surface has the terrace site like atomic defect, where
foreign atoms or molecules can be trapped easily. This defect en-
hances the oxygen diffusivity into the structure. Previous QCMD
results showed that the atomic defect increased the oxygen diffu-
sivity in the metal surface [76]. Additionally, the Ni–Cr (1 1 1) and
Ni–Cr (1 0 0) surfaces are more dense than the Ni–Cr (1 1 0) surface,
which may reduce the oxygen diffusivity into the structure [77].
The dense structures do not have sufficient space to adsorb foreign
atoms. Norton et al. demonstrated that the oxygen uptake rate was
in the order (1 0 0) < (1 1 1) < (1 1 0) [78]. This experimental obser-
vation reveals that oxygen can penetrate deeper into the Ni
(1 1 0) surface than other surfaces; subsequently, the process might
increase the surface oxidation rate. Moreover, the DFT study found
28 N.K. Das, T. Shoji / Corrosion Science 73 (2013) 18–31

Cr-O/OH bond Diffused O surface. One can conclude from this study that Ni (1 1 0) is the
weakest surface for oxidation initiation. In addition, the calculated
surface morphologies showed the high oxygen concentration
around the chromium atom, which indicates that chromium is
selectively oxidised during the reaction progress and the oxygen
favourably forms a bond with chromium. This bonding initiates
the localised passive film formation on the metal surface. One of
the experimental studies showed that Cr2O3 is a major product
even for alloys containing as little as 0.1% Cr [79]. The present
study is not be able to quantify the oxide film thickness due to
the limitations of time and the length scale, but the simulated re-
sults qualitatively observe the initiation of passive film formation
on the surface. A short period oxidation study has been carried
200 fs 800 fs 1600 fs out on alloys 600 and 690 [80]. The results showed that a layer
(a) of oxide film is formed very quickly on the bare metal surface.
The oxide film is composed of chromium oxide and hydroxide
O/OH adsorbed on terrace site Diffused O and is covered with a small amount of nickel hydroxide. The XPS
study of Ni–Cr (1 1 0) polycrystalline demonstrated that Cr is oxi-
dised preferentially to Cr2O3 initially [11]. In addition, scanning
electron microscopy (SEM) analysis of alloy 600 showed that chro-
mium and iron are selectively dissolved and nickel remains at the
surface of the matrix [81]. The present results are qualitatively in
good agreement with the experimental observation. The diatomic
energy of Cr–O is higher than the Ni–O energy; therefore, it can
help oxygen to bond preferentially with chromium. The calculated
surfaces found that the chromium had moved upward to the sur-
200 fs 800 fs 1600 fs
face because it dissoluted faster than nickel atoms. The Cr–O bond
(b) helps to move the atoms in the upward direction. In addition, the
cohesive energy of chromium is less than that of nickel, which
Dissociated H2O H remain on the surface might help to dissolute chromium atoms from the surface. The
oxygen chemisorption process weakens the metallic bond; as a
consequence, metal–metal bond breakage and initiates the surface
oxidation. The simulated surfaces showed that the hydrogen is
trapped in the structure. It can diffuse faster than oxygen or any
other species due to its small atomic size. Hydrogen can be ad-
sorbed by the surface as atomic hydrogen or OH. The adsorption
of OH on the metal surface generates metal hydroxides such as
chromium hydroxide or nickel hydroxide [7]. Hydrogen can be
trapped in the interstitial sites of fcc Ni–Cr alloys. Ni–Cr alloys have
numerous octahedral and tetrahedral sites to adsorb hydrogen.
These interstitial hydrogen has detrimental effect on material
200 fs 800 fs 1600 fs properties such as hydrogen embrittlement and hydrogen oxida-
(c) tion. The simulated surfaces demonstrated that the dissociated
hydrogen travelled ahead of the oxygen or OH. These atoms can
Fig. 5. The calculated surface morphologies: (a) Ni–Cr (1 1 1), (b) Ni–Cr (1 1 0) and be able to lessen the strength of metallic bonds. Thus, they can help
(c) Ni–Cr (1 0 0). to increase the oxygen penetration depth in the metal.

that the oxygen chemisorption energy is 5.69 eV, 5.56 and 5.22 eV 3.2.2. Atomic dissolution and diffusion path
for Ni (1 0 0), Ni (1 1 1) and Ni (1 1 0), respectively. It also indicates The dynamical feature of atoms is depicted in Fig. 7. Oxygen, in
that the atomic oxygen make the weakest bond on the Ni (1 1 0) the form of H2O, OH or O, diffuses through the hollow sites. The

-7.0 -7.0
-6.0 111 Ni-Cr(111) 980 fs 111 Ni-Cr(111) 980 fs
-6.0
110 Ni-Cr(110) 1020 fs 110 Ni-Cr(110) 1060 fs
-5.0 Ni-Cr(100) 1200 fs -5.0
100 100 Ni-Cr(100) 960 fs
-4.0 -4.0
Depth (Å)

Depth (Å)

-3.0 -3.0
-2.0 -2.0
-1.0 -1.0 O1
O1
0.0 0.0
O3 O2 O3
O2
1.0 1.0
2.0 2.0
(a) (b)
Fig. 6. Maximum penetration depth of oxygen for different surfaces: (a) surfaces without applied strain and (b) surface with applied uniaxial strain.
 N.K. Das, T. Shoji / Corrosion Science 73 (2013) 18–31
experimental and theoretical studies showed that the hollow site is
energetically the most preferential for oxygen adsorption on Ni
and Ni–Cr surfaces [18,24]. Dissociated oxygen or OH was ad-
sorbed on the hollow sites and formed a strong bond with metal
atoms. The process helps to dissolute metal atoms. However, the
trajectory of oxygen clearly showed that atoms preferred to remain
around the chromium, and the bonding decelerates further diffu-
sion, as we have described in the previous section. Chromium is
selectively oxidised at the initial stage of the oxidation process
and can form a protective passive film. In the case of metal atom
dissolution, chromium atoms attempted to move upward from
their initial position, whereas the nickel segregation rate was slow.
The present results confirm us that the chromium atoms selec-
tively dissolute and the nickel remain at the surface of alloys at
the early stage of oxidation. The AES study of Ni–Cr alloys showed
that chromium depletion occurred in gaseous atmosphere at high
temperature [82,83]. The calculated results are in good agreement
with the AES observation. The process indicated the transport of Cr
to inject vacancies into the base metal, caused by the growth of the
oxide layer.
3.2.3. Atomic charge analysis
The degree of electron transfer is an important issue to under-
stand the bonding nature of atoms. The positively charged atoms
can a donate higher number of electrons to the acceptor, whereas
the highly negatively charged atoms can receive electrons from the
donors. The process helps to form a strong bond between highly
positively charged and highly negatively charged atoms. The atom-
ic charge with diffusion is calculated by using Mulliken population
analysis method, as shown in Fig. 8. The calculated results for other
surfaces agree with this figure, and thus it is not necessary to show
them here. The water–metal bond has been interpreted as a Lewis
acid–base interaction, with the H2O in the role of the electron do-
nor [84]. The electron transfer from water to the nickel substrate is
only 0.1e [34]. Our calculations considered the surface reaction
dynamics at high temperature. The water molecules are adsorbed
by the surface for a very short period of time. Thus, it is difficult
to observe this phenomenon. However, at the elementary stage,
chromium and hydrogen were positive in charge, and oxygen
atoms were negative in charge; in addition, nickel atoms were
not designated to any remarkable charges. The atomic charge
was modified with respect to time evolution. The negative oxygen
atoms increased in value by taking electrons from metals, and me-
tal atoms became positively charged. In particular, chromium
atoms were positive in charge. The calculated oxygen atom average
charge was 0.48e. The net electron flow, as calculated by the
topological method, was from the nickel surface to the oxygen
atoms, amounting to 0.86e per ad-atom [85]. Another theoretical
study found that the oxygen atom received 0.52e from the nickel
surface [86]. Our results agree fairly well with the previous study.
O diffusion path Cr dissolution Ni dissolution
Fig. 7. Atomic trajectories.
29
Negatively charged H
200 fs 600 fs
Cr-O/OH bond
+0.968
0.000
-0.968
1600 fs
Fig. 8. Atomic charge changes with respect to time for the Ni–Cr (1 1 0) surface.
Furthermore, the DFT study confirmed that the oxygen 2p orbitals
hybridised strongly with the nickel 3d orbitals [37]. In the case of
chromium, the orbital bonding nature is slightly different. The
DFT study demonstrated that the charge transfer occurs from the
Cr 3d and 4s orbitals to the oxygen 2p orbitals. The Cr–O orbitals
interaction enhances the electron transfer between them and
makes a strong bond. The top layer atoms played an active role
in the reaction process at the beginning stage, which increased
the electron transfer. The hydrogen atom on top of the surfaces
exhibited positively charged, whereas the penetrated hydrogen
was negatively charged. Negatively charged hydrogen in metal is
interesting but not surprising, and it is quite consistent with our
previous results [33,76]. The calculated average charge of the dif-
fused hydrogen atom was 0.20e. the first principles study shows
that a charge transfer of 0.15–0.20e to the hydrogen atom from the
nickel surface occurs [87]. However, the positively charged hydro-
gen is well known in the literature and causes decohesion. The
hydrogen decohesion mechanism causes embrittlement. According
to the anionic model, hydrogen receives electrons from the metal
and changes to negatively charged [33]. Therefore, the deeply dif-
fused hydrogen interacts with metallic atoms for a comparatively
longer period of time and takes electrons from the metal. The elec-
tron transfer process activates the surface chemically for further
reaction, which makes it easier for oxygen to diffuse, and thus oxi-
dation accelerates.
4. Conclusions
We have studied the adsorption characteristics of atomic oxy-
gen, OH, and water molecules on different Ni and Ni–Cr surfaces
by DFT calculations. The results show that the oxygen adsorption
energy on Ni (1 0 0) is higher than that on the Ni (1 1 1) and unre-
constructed Ni (1 1 0) surfaces. The Cr substituted nickel surface in-
creases the oxygen adsorption energies. The maximum adsorption
energy is attained when two chromium atoms are doped on top of
the Ni (1 1 1) surface. The oxygen and OH adsorption energies of Ni
(1 1 0) and Ni–Cr (1 1 0) surfaces are smaller than those of the other
surfaces. Thus the (1 1 0) surface makes a weak bond with the ad-
sorbed oxygen and OH. The most favourable oxygen adsorption
sites are the fcc hollow, fourfold hollow and SB sites of (1 1 1),
(1 0 0) and (1 1 0) surfaces, respectively. The OH is adsorbed molec-
ularly on the hollow site of (1 1 1) and (1 0 0) and the SB site of
(1 1 0) surfaces. The OH adsorption energies of the Ni–Cr surfaces
30 N.K. Das, T. Shoji / Corrosion Science 73 (2013) 18–31
are also increased. The (1 1 0) bare surface demonstrates a higher
percentage of contraction and expansion between the interlayers
compared to the (1 1 1) and (1 0 0) surfaces while the O, OH and
H2O adsorbed metal surfaces show the outward expansion be-
tween the first and second layers and a slight contraction between
the second and third layers. The bond distances of Cr–O are smaller
than the Ni–O distances for oxygen, OH, and H2O adsorption, which
implies that the oxygen atom has some affinity to chromium. The
Cr 3d orbitals bond strongly with the oxygen 2p orbitals; concur-
rently, the Ni 3d and 4s orbitals bond with the oxygen 2p orbitals.
A small Ni p peak appears at 5.9 eV for the oxygen adsorbed Ni
(1 0 0) surface. In the case of O/Ni (1 1 0), the Ni p orbitals have
no effect on the bonding process. The bonding of those orbitals
might the cause of the reduction of the oxygen chemisorption en-
ergy. The Cr 3d and the Ni 3d and 4s orbitals interact with the oxy-
gen 2p orbitals on the OH adsorbed surfaces. The water adsorbed
surfaces show that the metallic d and s orbitals bond essentially
with water while the p orbitals show little contribution. The metal
surfaces interact very weakly with the water molecules, resulting
in a small adsorption energy.
The QCMD results show that the depth of penetration of oxygen
in the Ni–Cr (1 1 0) surface is the highest among all surfaces. The ter-
race like atomic defects on the Ni–Cr (1 1 0) surface help to trap oxy-
gen or dissociated ions. Thus, oxygen permeates deeper into the
structure through these sites. Moreover, the Ni–Cr (1 1 1) and Ni–
Cr (1 0 0) surfaces are denser than the Ni–Cr (1 1 0), which might
be another reason to increase the oxygen diffusivity into the struc-
ture. In addition, a 1% applied strain increases the oxygen diffusivity
into the surfaces. The surface morphology shows the significantly
high oxygen concentration around the chromium, which indicates
the early stage of passive film formation. The process helps to in-
crease the chromium dissolution rate. Lower nickel segregation
may help to form a nickel enriched inner oxide layer. In addition,
the charge analysis results show that the chromium atoms make
a strong bond with highly negatively charged oxygen atoms, and
the deeply diffused hydrogen is negatively charged. The initially
penetrated hydrogen weakens the metallic bond by taking electron,
and the process makes it easier for oxygen to further permeate the
surface. Finally, this study shows that the atomic oxygen makes the
weakest bond on the (1 1 0) surface; simultaneously, oxygen can
permeate longer distance into the (1 1 0) surface. As a consequence,
the surface is susceptible to the oxidation initiation process.
Acknowledgements
DFT calculation has been performed by supercomputing re-
sources. The authors gratefully acknowledge SR11000 supercom-
puting resources from the Center for Computational Materials
Science of the Institute for Materials Research, Tohoku University.
We also would like express our sincere thanks to the crew of this
center.
References
[1] M. Nakamura, M. Ito, Monomer water structures of water adsorbed on
p(2  2)-Ni(1 1 1)–O surface at 25 and 140 K studied by surface X-ray
diffraction, Phys. Rev. Lett. 94 (2005) 035501.
[2] L. Ollé, M. Salmerón, A.M. Baró, The adsorption and decomposition of water on
Ni (1 1 0) studied by electron energy loss spectroscopy, J. Vac. Sci. Technol., A 3
(1985) 1866–1870.
[3] M.E. Gallagher, S. Haq, A. Omer, A. Hodgson, Water monolayer and multilayer
adsorption on Ni (1 1 1), Surf. Sci. 601 (2007) 268–273.
[4] C. Benndorf, C. Nöbl, M. Rusenberg, F. Thieme, H2O interaction with clean and
oxygen precovered Ni (1 1 0), Surf. Sci. 111 (1981) 87–101.
[5] R.W. Staehle, in: J.C. Scully (Ed.), The Theory of SCC in Alloys, NATO, Brussels,
1971, p. 86
[6] H. Over, A.P. Seitsonen, Oxidation of metal surfaces, Science 297 (2002) 2003–
2005.
[7] G.B. Hoflund, W.S. Epling, Oxidation study of a polycrystalline Ni/Cr alloy II,
Chem. Mater. 10 (1998) 50–58.
[8] S.E. Ziemniak, M. Hanson, Corrosion behavior of NiCrFe alloy 600 in high
temperature, hydrogenated water, Corros. Sci. 48 (2006) 498–521.
[9] F. Huang, J.Q. Wang, E.H. Han, W. Ke, Short-time oxidation of alloy 690 in high-
temperature and high-pressure steam and water, J. Mater. Sci. Technol. 28
(2012) 562–568.
[10] M. Juez-Lorenzo, V. Kolarik, W. Stamm, H. Fietzek, Oxidation of nickel-based
alloys in dry and water vapour containing air, Mater. High Temp. 29 (2012)
229–234.
[11] S.P. Jeng, P.H. Holloway, D.A. Asbury, G.B. Hoflund, Changes induced at Ni/Cr
alloy surfaces by annealing and oxygen exposure, Surf. Sci. 235 (1990) 175–
185.
[12] S.P. Jeng, P.H. Holloway, C.D. Batich, Surface passivation of Ni/Cr alloy at room
temperature, Surf. Sci. 227 (1990) 278–290.
[13] C.W. Bauschlicher Jr., H2O/Ni(1 0 0) and NH3/Ni(1 0 0): a computational
approach, J. Chem. Phys. 83 (1985) 3129–3133.
[14] D. Sebastiani, L.D. Site, Adsorption of water molecules on flat and stepped
nickel surfaces from first principles, J. Chem. Theor. Comput. 1 (2005) 78–82.
[15] M. Nakamura, M. Tanaka, M. Ito, O. Sakata, Water adsorption on a p(2  2)-
Ni(1 1 1)–O surface studied by surface X-ray diffraction and infrared
reflection absorption spectroscopy at 25 and 140 K, J. Chem. Phys. 122
(2005) 224703.
[16] C. Taylor, R.G. Kelly, M. Neurock, First-principles calculations of the
electrochemical reactions of water at an immersed Ni(1 1 1)/H2O interface, J.
Electrochem. Soc. 153 (2006) E207–E214.
[17] G.C. Wang, S.X. Tao, X.H. Bu, A systematic theoretical study of water
dissociation on clean and oxygen-preadsorbed transition metals, J. Catal. 244
(2006) 10–16.
[18] S. Yamagishi, S.J. Jenkins, D.A. King, First principles studies of chemisorbed O
on Ni {1 1 1}, Surf. Sci. 543 (2003) 12–18.
[19] T. Pache, H.-P. Steinrück, W. Huber, D. Menzel, The adsorption of H2O on clean
and oxygen precovered Ni(1 1 1) studied by ARUPS and TPD, Surf. Sci. 224
(1989) 195–214.
[20] S. Garruchet, O. Politano, P. Arnoux, V. Vignal, Diffusion of oxygen in nickel: a
variable charge molecular dynamics study, Solid State Commun. 150 (2010)
439–442.
[21] A.V. Kalinkin, G.K. Boreskov, V.I. Savchenko, K.A. Dadayan, N.N. Bulgakov,
React. Kinet. Catal. Lett. 18 (1981) 55–58.
[22] J. Carrasco, A. Michaelides, M. Scheffler, Insight from first principles into the
nature of the bonding between water molecules and 4d metal surfaces, J.
Chem. Phys. 130 (2009) 184707.
[23] W. An, X.C. Zeng, C.H. Turner, First-principles study of methane
dehydrogenation on a bimetallic Cu/Ni(1 1 1) surface, J. Chem. Phys. 131
(2009) 174702.
[24] N.K. Das, T. Shoji, A density functional study of atomic oxygen and water
molecule adsorption on Ni(1 1 1) and chromium-substituted Ni(1 1 1) surfaces,
Appl. Surf. Sci. 258 (2011) 442.
[25] N.K. Das, I. Tirtom, T. Shoji, A multi-scale modeling study of a Ni–Cr(1 1 1)
surface oxidation at different stress intensities, Mater. Chem. Phys. 122 (2010)
336–342.
[26] P. Hohenberg, W. Kohn, Inhomogeneous electron gas, Phys. Rev. B 136 (1964)
864–871.
[27] B. Delley, An all-electron numerical method for solving the local density
functional for polyatomic molecules, J. Chem. Phys. 92 (1990) 508–517.
[28] B. Delley, A scattering theoretic approach to scalar relativistic corrections on
bonding, Int. J. Quantum Chem. 69 (1998) 423–433.
[29] B. Delley, From molecules to solid with the DMol3 approach, J. Chem. Phys. 113
(2000) 7756–7764.
[30] J.P. Perdew, Y. Wang, Accurate and simple analytic representation of
the electron-gas correlation energy, Phys. Rev. B 45 (1992) 13244–13249.
[31] J.P. Perdew, K. Burke, M. Ernzerhof, Generalized gradient approximation made
simple, Phys. Rev. Lett. 77 (1996) 3865–3868.
[32] W.J. Hehre, L. Radom, P.V.R. Schleyer, J.A. Pople, Ab initio Molecular Orbital
Theory, Wiley, New York, 1986.
[33] N.K. Das, T. Shoji, An atomic study of hydrogen effect on the early stage
oxidation on transition metal surfaces, Int. J. Hydrogen Energy. 38 (2013)
1644–1656.
[34] H. Yang, J.L. Whitten, The adsorption of water and hydroxyl on Ni(1 1 1), Surf.
Sci. 223 (1989) 131–150.
[35] H. Yang, J.L. Whitten, Adsorption of SH and OH and coadsorption of S, O and H
on Ni(1 1 1), Surf. Sci. 370 (1997) 136–154.
[36] S. Masuda, M. Nishijima, Y. Sakisaka, M. Onchi, Structures of oxygen-covered
Ni (1 1 0) surfaces, Phys. Rev. B 25 (1982) 863–874.
[37] W.-B. Zhang, B.-Y. Tang, First-principles studies of the oxygen adsorption on
unreconstructed and reconstructed Ni(1 1 0) surfaces, Surf. Sci. 603 (2009)
1002–1009.
[38] K.-H. Xiang, R. Pandey, J.M. Recio, E. Francisco, J.M. Newsam, A theoretical
study of the cluster vibrations in Cr2O2, Cr2O3, and Cr2O4, J. Phys. Chem. A 104
(2000) 990–994.
[39] M.L. Peterson, A.F. White, G.E. Brown, G.A. Parks, Surface passivation of
magnetite by reaction with aqueous Cr(VI): XAFS and TEM results, Environ.
Sci. Technol. 31 (1997) 1573–1576.
[40] C.D. Roux, H. Bu, J.W. Rabalais, Structure of the Ni{1 1 0}-p(2  1)–OH
surface from time of flight scattering and recoiling spectrometry, Surf. Sci.
279 (1992) 1.
 N.K. Das, T. Shoji / Corrosion Science 73 (2013) 18–31
[41] C. Nöbl, C. Benndorf, T.E. Madey, H2O adsorption on Ni(1 0 0): evidence for
oriented water dimers, Surf. Sci. 157 (1985) 29–42.
[42] C. Benndorf, C. Nöbl, T.E. Madey, H2O adsorption on oxygen-dosed Ni(1 1 0):
formation and orientation of OH(ad), Surf. Sci. 138 (1984) 292–304.
[43] V.I. Avdeev, I.I. Zakharov, G.M. Zhidomirov, N.M. Neshev, E.I. Proinov, Ab-initio
calculations for adsorbed state of OH group on Ni(1 1 0), React. Kinet. Catal.
Lett. 45 (1) (1991) 61–66.
[44] J.I. Siepmann, M. Sprik, Ordering of fractional monolayers of H2O on Ni(1 1 0),
Surf. Sci. Lett. 279 (1992) L185–L190.
[45] B.W. Callen, K. Griffiths, R.V. Kasza, M.B. Jensen, P.A. Thiel, P.R. Norton,
Structural phenomena related to associative and dissociative adsorption of
water on Ni(1 1 0), J. Chem. Phys. 97 (1992) 3760–3774.
[46] N. Pangher, A. Schmalz, J. Haase, Structure determination of water
chemisorbed on Ni(1 1 0) by use of X-ray absorption fine-structure
measurements, Chem. Phys. Lett. 221 (1994) 189–193.
[47] M. Pozzo, G. Carlini, R. Rosei, D. Alfe, Comparative study of water dissociation
on Rh(1 1 1) and Ni(1 1 1) studied with first principles calculations, J. Chem.
Phys. 126 (2007) 164706.
[48] M. Nakamura, M. Ito, Monomer structures of water adsorbed p(2  2)-
Ni(1 1 1)–O surface at 25 and 140 K studied by surface X-ray diffraction,
Phys. Rev. Lett. 94 (2005) 035501.
[49] M.L. Xu, S.Y. Tong, Multilayer relaxation for the clean Ni(1 1 0) surface, Phys.
Rev. B 31 (1985) 6332–6336.
[50] D.L. Adams, L.E. Petersen, C.S. Sörensen, Oscillatory relaxation of the Ni(1 1 0)
surface: a LEED study, J. Phys. C 18 (1985) 1753.
[51] F. Mittendorfer, A. Eichler, J. Hafner, Structural, electronic and magnetic
properties of nickel surfaces, Surf. Sci. 423 (1999) 1–11.
[52] D.S.D. Gunn, S.J. Jenkins, Adsorbate modification of the structural, electronic,
and magnetic properties of ferromagnetic fcc 1 1 0 surfaces, Phys. Rev. B 83
(2011) 115403.
[53] D. Brennan, D.O. Hayward, B.M.W. Trapnell, The calorimetric determination of
the heats of adsorption of oxygen on evaporated metal films, Proc. Roy. Soc.
Lond. A 256 (1960) 81.
[54] H. Conrad, G. Ertl, J. Kuppers, E.E. Latta, Interaction of NiO with a Ni(1 1 1)
surface, Surf. Sci. 50 (1975) 296.
[55] W.F. Egelhoff Jr., Core-level binding – energy-shift analysis of adsorption and
dissociation, Phys. Rev. B 29 (1984) 3681–3683.
[56] A. Goursot, F. Mele, N. Russo, D.R. Salahub, M. Toscano, Geometrical
spectroscopic and magnetic properties of an oxygen atom adsorbed on the
Ni(1 0 0) surface, Int. J. Quantum Chem. 48 (1993) 277–286.
[57] J.E. Demuth, D.W. Jepsen, P.M. Marcus, Chemisorption bonding of c(2  2)
chalcogen overlayers on Ni(0 0 1), Phys. Rev. Lett. 31 (1973) 540–542.
[58] L. Wenzel, D. Arvanitis, W. Daum, H.H. Rotermund, J. Stöhr, K. Baberschke, H.
Ibach, Structural determination of an adsorbed-induced surface
reconstruction: p4g(2  2) versus c(2  2)O on Ni(1 0 0), Phys. Rev. B 36
(1987) 7689–7692.
[59] W. Oed, H. Lindner, U. Starke, K. Heinz, K. Müller, Adsorbate-induced
relaxation and reconstruction of c(2  2)O/Ni(1 0 0): a reinvestigation by leed
structure analysis, Surf. Sci. 224 (1989) 179–194.
[60] A.B. Hayden, P. Pervan, D.P. Woodruff, K-resolved inverse photoemission study
of half-monolayer structure of O, C and N on Ni(1 0 0): a fingerprint of
adsorbate-induced restructuring?, Surf Sci. 306 (1994) 99–113.
[61] J. Stohr, R. Jaeger, T. Kendelewicz, Structure of p(2  2) and c(2  2) oxygen on
Ni(1 0 0): a surface extended-X-ray absorption fine-structure study, Phys. Rev.
Lett. 49 (1982) 142–146.
[62] S.Y. Tong, W.M. Kang, D.H. Rosenblatt, J.G. Tobin, D.A. Shirley, Photoelectron-
diffraction analysis of the structure of c(2  2)O on Ni(0 0 1), Phys. Rev. B 27
(1983) 4632–4636.
[63] C.R. Brundle, J.Q. Broughton, in: D.A. King, D.P. Woodruff (Eds.), The Chemical
Physics of Solid Surfaces and Heterogeneous Catalysis, vol. 3A, Elsevier,
Amsterdam, 1990 (Chapter 3).
31
[64] T.S. Rahman, D.L. Mills, J.E. Black, J.M. Szeftel, S. Lehwald, H. Ibach, Surface
phonons and the c(2  2) oxygen overlayer on Ni(1 0 0): theory and
experiment, Phys. Rev. B 30 (1984) 589–603.
[65] R.L. Strong, J.L. Erskine, Adsorbate structure determination using surface
vibrational spectroscopy, Phys. Rev. Lett. 54 (1985) 346–348.
[66] H. Yang, J.L. Whitten, Energetics of hydroxyl and influence of coadsorbed
oxygen on metal surfaces, J. Phys. Chem. B 101 (1997) 4090–4096.
[67] T.E. Madey, F.P. Netzer, The adsorption of H2O on Ni(1 1 1); influence of
preadsorbed oxygen on azimuthal ordering, Surf. Sci. 117 (1982) 549–560.
[68] W. Oed, U. Starke, K. Heinz, K. Müller, Adsorbate-induced reconstruction of
O and S on Ni(1 0 0): a local model, J. Phys.: Condens. Matter 3 (1991) S223–
S230.
[69] N.K. Das, T. Shoji, Geometry, orbital interaction, and oxygen chemisorption
properties of chromium-doped nickel clusters, J. Phys. Chem. C 116 (2012)
13353–13367.
[70] C.S. Wang, A.J. Freeman, Self-consistent electronic structure of chemisorption
bonding: c(2  2) O on Ni(0 0 1), Phys. Rev. B 19 (1979) 4930.
[71] H. Tillborg, A. Nilsson, T. Wiell, N. Wassdahl, N. Mårtensson, J. Nordgren,
Electronic structure of atomic oxygen adsorbed on Ni(1 0 0) and Cu(1 0 0)
studied by soft-X-ray emission and photoelectron spectroscopies, Phys. Rev. B
47 (1993) 16464–16470.
[72] V.I. Avdeev, I.I. Zakharov, G.M. Zhidomirov, N.M. Neshev, E.I. Proinov,
Electronic structure of OH adsorbed on nickel, J. Struct. Chem. 33 (2) (1992)
179–185.
[73] J. Li, S. Zhu, Y. Li, E.E. Oguzie, F. Wang, Electronic structure of monomeric water
adsorption on Ni{1 1 1}: beyond the general model, J. Phys. Chem. C 112 (2008)
8301–8303.
[74] Q.L. Tang, Z.X. Chen, Density functional slab model studies of water adsorption
on flat and stepped Cu surfaces, Surf. Sci. 601 (2007) 954.
[75] I. Panas, P. Siegbahn, U. Wahlgren, Model studies of the chemisorption of
hydrogen and oxygen on nickel surfaces, Theor. Chim. Acta 74 (1988) 167–
184.
[76] N.K. Das, K. Suzuki, Y. Takeda, K. Ogawa, T. Shoji, Quantum chemical molecular
dynamics study of stress corrosion cracking behaviour for fcc Fe and Fe–Cr
surfaces, Corros. Sci. 50 (2008) 1701–1706.
[77] L.H. Germer, A.U. MacRae, Surface reconstruction caused by adsorption, PNAS
48 (1962) 997–1000.
[78] P.R. Norton, R.L. Tapping, J.W. Goodale, A photoemission study of the
interaction of Ni(1 0 0), Ni(1 1 0) and Ni(1 1 1) surfaces with oxygen, Surf. Sci.
65 (1977) 13–36.
[79] T.D. Tribbeck, J.W. Linnett, P.G. Dickens, Oxidation of metals and alloys. Part 1.
– Oxidation of nickel containing small amounts of chromium, Trans. Faraday
Soc. 65 (1969) 890–895.
[80] P. Combrade, in: T.R. Allen, P.J. King, and L. Nelson (Eds.), Proceedings of the
12th International Conference on Environmental Degradation of Materials in
Nuclear Power System – Water Reactors, TMS, 2005.
[81] T. Terachi, N. Totsuka, T. Yamada, T. Nakagawa, H. Deguchi, M. Horiuchi, M.
Oshitani, J. Nucl. Sci. Technol. 40 (2003) 509–516.
[82] F. Carrette, F.L. Guinard, B. Pieraggi, in: Proceedings of the 9th International
Conference on Water Chemistry of Nuclear Reactor Systems, Avignon, France,
SFEN, 2002.
[83] M. Seo, N. Sato, Int. Congress Metal. Corros. 2 (1984) 362.
[84] P.A. Thiel, T.E. Madey, The interaction of water with solid surfaces:
fundamental aspects, Surf. Sci. Rept. 7 (1987) 211–385.
[85] R.F.W. Bade, Atoms in Molecules: A Quantum Theory, Clarendon Press, Oxford,
1990.
[86] J.E. Kirsch, S. Harris, Electronic structure studies of Ni(1 0 0) surface
reconstructions resulting from carbon, nitrogen, or oxygen atom adsorption,
Surf. Sci. 522 (2003) 125–142.
[87] G. Kresse, J. Hafner, First-principles study of the adsorption of atomic hydrogen
on Ni(1 1 1), Ni(1 0 0) and Ni(1 1 0), Surf. Sci. 459 (2000) 287–302.