Zinc Oxide: A Case Study in Contemporary

Computational Solid State Chemistry

C. RICHARD A. CATLOW,1 SAMUEL A. FRENCH,1 ALEXEY A. SOKOL,1 ABDULLAH A. AL-SUNAIDI,2

SCOTT M. WOODLEY1
1
Department of Chemistry, University College London, 3rd Floor,
Kathleen Lonsdale Building, Gower Street, London WC1E 6BT, United Kingdom
2
Physics Department, King Fahd University of Petroleum and Minerals,
Dhahran 31261, Saudi Arabia

Received 22 February 2008; Accepted 7 May 2008

DOI 10.1002/jcc.21051
Published online 15 July 2008 in Wiley InterScience (www.interscience.wiley.com).

Abstract: Computational techniques have been applied to study a broad range of chemical and physical properties
of zinc oxide. Both interatomic-potential and density functional theory methods are used to investigate structural,
thermodynamic, surface, and defect properties. We survey the structures and energies of nano-particulate zinc oxide.

q 2008 Wiley Periodicals, Inc. J Comput Chem 29: 2234–2249, 2008

Key words: zinc oxide; catalysis; nano chemistry; defects; phase transitions

Introduction ZnO. The computational studies reported in this article provide

The techniques of computational chemistry have had a substan-
tial impact on our understanding of the chemistry and physics of
oxide materials. Over recent years they have developed an
increasingly predictive ability in modeling structures, properties
and defects in both the bulk and surfaces of metal oxides. Simu-
lations of these materials exploit the full range of techniques
available in computational condensed matter science. Earlier
studies demonstrated the viability of minimization methods
employing Born model potentials in modeling accurately the
structures, surfaces, and closed shell defects in oxides.1,2
Interatomic potential (IP) methods are still widely used, but
the rapid expansion of density functional theory (DFT) techni-
ques has had substantial impact on the field, whereas in a num-
ber of applications, Hartree Fock (and post-Hartree Fock)
methods are used; in addition, recent studies3 have demon-
strated the applicability of Quantum Monte-Carlo (QMC) tech-
niques in modeling oxides. Both IP and electronic structure
calculations have employed periodic, cluster, and embedded cluster
approaches, with the latter being used increasingly in recent years.
And, in general, the problems posed by these materials require the
use of a diverse range of techniques and approaches.
In this article, we focus on one particular oxide material,
ZnO, which despite its apparent simplicity has a rich solid-state
chemistry and physics. The material has a wide range of appli-
cations, ranging from electronics to catalysis,4–7 which depend
critically on its defect and surface properties. Moreover, there is
growing interest in the extensive and diverse nano-chemistry of
substantial insight and information on these and other key pro-
perties of the material. They also serve to illustrate the current
capabilities of modeling techniques in oxide chemistry and
physics.
Bulk Properties
As chemical and physical properties of zinc oxide have been
reviewed exhaustively, both from fundamental point of view and
in the context of applications, we focus here on the contributions
of our computational work.
Polymorphism and Physical Properties
In a wide range of temperature and pressure including ambient
conditions, zinc oxide has a wurtzite (B4) crystal structure (min-
eral name zincite) with all atoms having tetrahedral coordination
(see Figs. 1a and 1b).8 This structure can be considered as an
AA0 stack of one atom thick, charge neutral sheets, in which
zinc and oxygen atoms form a honeycomb, hexagonal pattern,
with three equivalent Zn

O bonds for each site (Fig. 1d). The
sheets are corrugated, as clearly seen in Fig. 1c, with all zinc
atoms occupying one side and oxygen atoms the other. As ZnO
is a strongly ionic material, each sheet possesses dipole moment,
Correspondence to: S. M. Woodley; e-mail: scott.woodley@ucl.ac.uk
Contract/grant sponsor: EPSRC; contract/grant number: D504872

q 2008 Wiley Periodicals, Inc.

 Zinc Oxide: A Case Study in Contemporary Computational Solid State Chemistry
which is normal to the surface; and a parallel arrangement of
hexagonal sheets is achieved by bonding between their comple-
mentary Zn and O sides, or surfaces, which is the main cause of
piezoelectric properties of macroscopic samples of ZnO.
A different stacking sequence, AA0 A00 , gives rise to another
well known structure of zinc blende (B3, or sphalerite, as shown
in Figs. 1h and 1i), adopted by many binary semiconductor com-
pounds. The first report on zinc blende structured ZnO, observed
as an oxidized thin film of zinc supported on copper, was made
by Bragg and Darbyshire.9 Surprisingly, their work was not
corroborated until recently—thin films with the zinc blende
structure have now been synthesized on a number of other
supports.10,11
Under pressure, ZnO undergoes a first order phase transition
into a rock salt (B1) structure, with atoms increasing their coor-
dination from four to six (Fig. 1m).12 On theoretical grounds, it
is expected that, at extremely high pressures, ZnO may adopt a
CsCl (B2) structure, with eight-coordinated ions (Fig. 1l), but
this phase has not yet been observed.
More recently, periodic DFT calculations have been used to
predict that, in thin films, hexagonal sheets flatten as ZnO adopts
the hexagonal BN (graphitic) structure while, as Zn

O bonds
disappear between the sheets and the coordination number low-
ers to three (in a trigonal coordination).13 Moreover, under pres-
sure, the hexagonal sheets can bond at each site, increasing the
coordination number of Zn and O atoms to five (in a trigonal
bipiramidal coordination), which has been proposed as an inter-
mediate metastable structure (HX) for nanowires of ZnO under
tensile stress (Figs. 1f and 1g), based on DFT and semiclassical
simulations.14 Based on DFT calculations, a body-centered-tet-
ragonal structure (BCT-4) (Figs. 1j and 1k) has been identified
as another plausible metastable intermediate in ZnO under pres-
sure, which keeps a coordination number of 4, but with the tet-
rahedral coordination strongly distorted.15 Moreover, one can
construct a whole range of microporous structures, which are
isomorphous to both known and hypothetical zeolitic frame-
works. In such structures, zinc and oxygen ions would occupy
alternate cation sites, while anion sites mark mid-bond Zn

O
positions. Such phases are only likely at reduced (negative) pres-
sures, which could be realized by template molecules within the
pores (at extra framework sites). We provide one such example,
that of the familiar sodalite structure (cf. Fig. 1e and ref. 16),
which has cages that are building blocks for other framework
structures and, as discussed later, one such unit proves to be the
most stable configuration for the particle (ZnO)12.
To investigate the stability and properties of the main observed
and hypothetical polymorphs of ZnO, we have employed the
energy minimization technique, using two-body interatomic poten-
tials. Our model is based on formal charges and polarizable dipo-
lar shells, with parameters of short-range potentials derived by
Whitmore et al.,17,18 using mostly room temperature data, avail-
able at the time. Reparameterisation work is now in progress tak-
ing into account new experimentally measured phonon dispersion
and phase transition data, but even the current set is comparable in
quality to ab initio and alternative semiclassical approaches (see,
for example, refs. 19 and 20). We note that, to account for the
lower stability of the BCT phase, the original set of interatomic
potentials has been amended21 by inclusion of a short-range inter-
Journal of Computational Chemistry
2235
action between Zn ions, which, however, only slightly changed the
calculated physical properties.
In Figure 2, we show the calculated lattice enthalpy as a func-
tion of pressure for the main observed and hypothetical poly-
morphs of ZnO. Below a transition pressure of 8 GPa, the most
stable phase is wurtzite, while above (up to 30 GPa as calculated
here, not shown in the diagram) it is rock salt, assuming entropy
differences between the two phases are small. The wurtzite struc-
ture remains stable, or at least metastable, within the space group
symmetry constraints in the whole pressure range investigated,
while the rock salt structure collapses below 3.7 GPa, as seen
from the appearance of two degenerate imaginary phonon modes
at the G point. With regard to metastable structures (i) the zinc
blende phase remains slightly less favorable than wurtzite; whereas
(ii) the enthalpy of BCT phase, which is closest to that of wurtzite
at zero pressure, diverges from the wurtzite value with pressure;
and, finally, (iii) the CsCl phase is always significantly higher in
enthalpy. The hexagonal structure proved to be unstable in all our
calculations and characteristically we find one imaginary mode,
which corresponds to buckling of the hexagonal sheets.
The overall stability of the wurtzite phase makes it particu-
larly important for numerous applications of ZnO. In Tables 1
and 2, we present a comparison of calculated and experimentally
observed properties of ZnO, at the limit of low temperature and
pressure. The agreement confirms the validity of our semiclassi-
cal model that was employed in the investigation of point
defects, surface morphology and catalysis, and nanoscale struc-
tures of ZnO, all of which are now summarized. Our investiga-
tion of temperature effects on the calculated physical properties
will be reported elsewhere.
Point Defects
Zinc oxide is widely used in catalysis, electrical devices, optoe-
lectronics, and pharmaceuticals, which often crucially depend on
the defect properties of this versatile material. The nature of the
intrinsic defects in ZnO, however, remains elusive, and, so far,
there is no unambiguous assignment of experimental data to par-
ticular defect species (with the possible exception of the positron
annihilation spectroscopic evidence for Zn vacancies—see refs.
4-6 and references therein). Theoretical work is therefore essen-
tial to complement the extensive body of experimental data. The
first periodic calculations using modern electronic structure tech-
niques were performed by Kohan et al.,41 with numerous later
contributions (see, for example, a study of the oxygen vacancy
formation and migration by Carrasco et al.42). A simple electro-
static embedding cluster approach has been employed by Fink,
who studied oxygen vacancies in the bulk and at the surfaces of
ZnO.43,44
Initially, we investigated the intrinsic point defects in ZnO
and then, H, N, P, Li, Fe, Cu, Al, and In impurity centers.45
Atomic and electronic structures, as well as defect formation
energies, were obtained for the main oxidation states of all these
defects using our embedded cluster, hybrid Quantum Mechani-
cal/Molecular Mechanical (QM/MM) approach to the treatment
of localized states in ionic solids.46,47 In contrast to a large num-
ber of recent periodic density functional calculations, for the
QM treatment we chose to employ hybrid exchange-correlation
DOI 10.1002/jcc
2236 Catlow et al. • Vol. 29, No. 13 • Journal of Computational Chemistry
Figure 1. Observed and hypothetical crystal structures of ZnO poly-
morphs. Perspective views along a and c axes for: (a,b) wurtzite,
(c,d) hexagonal ‘‘graphene’’ sheet, (e) sodalite structure, (f,g) hexa-
gonal, (h,i) zinc blende, (j,k) BCT structure, and along a axis for (l)
caesium chloride and (m) rock salt phases. Here and in the follow-
ing figures, red indicates oxygen atoms and grey zinc atoms.
Journal of Computational Chemistry
density functionals, which approach the limit of chemical accu-
racy in the energetics of defect formation. In particular, in this
work we have employed the B97–1 exchange and correlation
functional.48,49 For comparison, we also calculated defect forma-
tion energies using the classical Mott-Littleton approach.
The data in Table 3 summarize predicted energetics, using
the Born-Haber cycle, and show that oxygen Frenkel pairs have
low energies of formation; moreover, we note that O interstitials
have the lowest energies of formation among all intrinsic
defects, which suggests their dominance under oxidizing condi-
tions. However, both Zn interstitials (2.2 eV) and O interstitials
(1.7 eV) have similar, relatively low energies of formation.
Hence, we concluded that the dominant defect species will
depend on the sample history and working conditions.
We have further considered charge compensation in ZnO by
intrinsic mechanisms. A Schottky pair of Zn and O vacancies in
their formal charge states proved to have the lowest energies of
formation, which is still, however, high for the defect concentra-
tions observed in real samples. Therefore we modeled a Zn

O
dimer vacancy, as we expected significant energy gain from the
Coulomb interaction between the two species. The Mott-Little-
ton calculations yielded 4.01 and 3.79 eV for the two possible
orientations, in- and out-of-plane of the hexagonal sheet (see
Figs. 3a and 3d, respectively).
The nearest neighbor ions around the former create a regular
prism (anions and cations both form equilateral triangles), the
length of which (3.17 Å) is constrained by the mean interlayer
separation. In contrast, the anions and cations about the other
vacancy form isosceles triangles, which in Figure 3d are point-
ing upwards (upper unique angles are 59.73 and 56.378, respec-
tively), and are rotated out of phase to each other, approximately
about the axis of the prism, to form an irregular octahedron
shown in Figure 3e. The Zn

O distances are elongated from
3.17 Å to a minimum of 3.94 Å, while an average Zn

Zn sepa-
ration in the first configuration is 3.88 and 4.02 Å in the second,
Figure 2. Pressure phase diagram for ZnO. Inset: magnified section
highlights the phase transition region containing rock salt-zinc
blende and rock salt-wurtzite transition points.
DOI 10.1002/jcc
 Zinc Oxide: A Case Study in Contemporary Computational Solid State Chemistry 2237

Table 1. Physical Properties of ZnO Based on Static Lattice Enthalpy Simulations Calculated Here and
Compared with Experiment, an Alternative Semiclassical Analytical Bond-Order Potential (ABOP) Model
and ab initio Calculations.

Ab initio calculations14,15,22–29
Shell model ABOP
this work Experiment (ref. 19) LDA GGA Hybrid HF

Wurtzite, Space group No. 186, P63mc (B4)

U (eV/pair) 239.900
a (Å) 3.2498 3.2417(8) 3.219 3.199 3.292 3.253 3.233 7 3.290
c (Å) 5.2029 5.1876(8) 5.2566 5.207 5.200 7 5.241
u 0.38025 0.3819(1) 0.3750 0.377 7 0.379 0.380 7 0.381 0.385 0.385 7 0.383
B (GPa) 160.2 135.37183 144 138 7 162 125 7 134 157.8 130.6 7 154
c11 (GPa) 210.8 222.6 212 246
c12 (GPa) 136.7 132.1 116 127
c13 (GPa) 129.5 122.0 109 105
c33 (GPa) 228.9 236.8 219 246
c44 (GPa) 52.6 47.5 43 56
c66 (GPa) 37.1 44.3 48 60
e31 (C/m2) 20.30 20.62 20.51 20.59 20.56 20.55 7 20.54
e33 (C/m2) 1.36 0.96 0.8971.21 1.20 1.06 1.19 7 1.21
e15 (C/m2) 0.16 20.37 20.16 20.46
e011 9.35 7.7778.33
e033 10.60 8.8178.91
e111 3.89 3.70
e133 3.99 3.75
Rock salt, Space group No. 225, Fm-3m (B1)
DU (eV/pair) 0.179 0.237 0.158;0.197 0.237 0.242
a0 4.309 4.275 4.229 7 5.316 4.345 4.225 7 4.294
B0 (GPa) 210.4 177.4 200 205 7 210.5 173 132 7 203
PTr (GPa) 8.0 7.5 7 9.1 10 8.22 7 8.4 8.0
Zinc blende, Space group No. 216, F-43m (B3)
DU (eV/pair) 0.021 0.0 0.015 0.013 0.057
a0 4.554 4.47 7 4.62 4.552 4.509 4.633 4.614 7 4.619
B0 (GPa) 161.0 144 162 135 157
Caesium chloride, Space group No. 221, Pm-3m (B2)
DU (eV/pair) 2.306 0.976 1.307 1.358 1.555
a0 2.707 2.642 2.624 2.705 2.605
B0 (GPa) 256.6 218 194 157 216
BCT-4, Space group No. 136, P42/mnm
DU (eV/pair) 0.007 0.3
a0 3.216 3.17
c0 5.585 5.48
B0 (GPa) 192.8
Sodalite, Space group No.223, Pm3n (SOD)
DU (eV/pair) 0.214
a0 5.610
B0 (GPa) 129.9

Experimental data are taken from the literature for the lowest available temperature: wurtzite structure from neutron
diffractometry at 20 K30; rock salt structure and bulk modulus, B, are from room temperature measurements and
equation of state fits31; B4 ? B1 transition onset pressure from room temperature measurements of elastic constants32
and X-Ray diffraction data,33,34 zinc blende lattice constant from refs. 9 (on copper substrate), 10 (on GaAs), and 11
(on Zn2TiO4); wurtzite elastic and piezoelectric constants, c and e, at 4 K35; static dielectric constants, e0, from room
temperature infrared spectroscopic ellipsometry36 and from ref. 35, high-frequency dielectric constants, e1, calcu-
lated in ref. 36 from room temperature infrared and Raman spectroscopic data using Lyddane-Sachs-Teller relation.37
The enthalpy difference, DU, is reported with respect to the most stable phase of wurtzite.

the O

O separation in turn is 3.42 and 3.44 Å. Thus it appears These calculations have shown that the observed defect con-
that the vacancy is larger for the more stable configuration. The centrations cannot be fully explained by assuming only intrinsic
value of 3.79 eV is the lowest formation energy we have calcu- mechanisms. We will show that the existence of a surface plays
lated for intrinsic defect pairs in ZnO. a crucial role in introducing the defects into the material.

Journal of Computational Chemistry DOI 10.1002/jcc

2238 Catlow et al. • Vol. 29, No. 13 • Journal of Computational Chemistry

21
Table 2. Phonon frequencies (in cm ) at the G Point for Our calculated donor and acceptor properties of impurities
Wurtzite Structure. are generally in good agreement with experiment, where avail-
able. Curiously, our calculations suggest that a number of such
Mode Shell model (this work) Experiment (i) and (ii) ABOP LDA extrinsic defects, for example, Li and N, can also contribute to
the green luminescence band, the origins of which have caused
E2low 93.85 100 114 91 much controversy in the literature.
B1low 282.38 268;275 279 261 Future studies will report on other extrinsic defects and
A1TO 356.01 378;380 659 391
defect complexes.
E1TO 378.52 410;410 659 409
E2high 407.18 438;438 635 440
B1high 528.89 552;580 589 552
A1LO 579.98 581.4;584 659 560 Surfaces and Catalysis
E1LO 586.59 593;595 659 556
Surface Structure and Properties of Zincite
Experimental literature data are from the Raman measurements on zin-
cite (i) at 7 K,38 except for silent Raman B1 modes, which were assigned For the wurtzite phase, single crystals of zinc oxide usually have
tentatively by Manjón et al.39 based on the anomalous Raman data from a prismatic shape with hexagonal bases exposing two opposite
defected samples; (ii) in the range of 80–300 K and longitudinal modes polar, Zn-(0001) and O-(000
1) terminated surfaces, while the
extrapolated to 0 K40; silent Raman B1 modes are extracted from room side faces show nonpolar, (10
10) and (11
20) surfaces (see Fig.
temperature combination (2B1low at 536 cm21) and difference (B1high – 5).50–52 The nonpolar surfaces terminate with Zn

O dimers,
B1low at 284 cm21) modes. ABOP data have been extracted from Figure
3a in ref. 19. LDA DFT are from ref. 38; we note that the ABOP model, Table 3. Calculated Energies for the Defect Formation in ZnO.
fundamentally, cannot model the splitting of transverse and longitudinal
modes, and the appearance of the phononic gap at the G point in their QM/MM MM
dispersion diagram is fortuitous. energy energy
Defect reactionsa (eV) (eV)
Defect levels in the band gap of the ZnO are illustrated in
Figure 4. The values were determined from our calculations of Oxygen vacancy
the vertical ionization potential and electron affinity, and thus O3O ? V3O 1 ½ O2(g) 5.296
present many-electron calculations as opposed to schemes using O3O ? VO 1 e0 1 ½ O2(g) 5.275
Kohn-Sham orbital energies. Using these diagrams we can O3O ? VO 1 2 e0 1 ½ O2(g) 5.403
explain a large number of diverse experimentally observed phe- Oxygen interstitial
nomena as follows: V3i 1 ½ O2 (g) ? O3i 1.652
V3i 1 ½ O2 (g) ? O0 i 1 h 6.129
V3i 1 ½ O2 (g) ? O@i 1 2 h 10.345
 We proposed that the neutral and positively charged, Zn3i and
Zinc vacancy
Zni, defects are responsible for E1 and E3 (majority) donor Zn3Zn ? VZn 1 2 e0 1 Zn(s) 10.895
bands from electric measurements. Zn3Zn ? VZn 1 e0 1 Zn(s) 8.776
 Zn vacancies are proposed as the majority acceptor, in agree- Zn3Zn ? V3Zn 1 Zn(s) 7.280
ment with experimental assignment based on positron annihi- Zn3Zn ? V0 Zn 1 h 1 Zn(s) 9.514
lation spectroscopic and other studies. This defect is found to Zn3Zn ? V@Zn 1 2 h 1 Zn(s) 12.077
be stable in five charge states. Importantly, exciton recombina- Zinc interstitial
tion at this defect species in these states was proposed as a V3i 1 Zn(s) ? Zn3i 4.722
source of the main photoluminescence bands: ultraviolet (an V3i 1 Zn(s) ? ZnI 1 e0 3.563
acceptor level at 3.2 eV in a Donor to Acceptor Photolumines- V3i 1 Zn(s) ? ZnI 1 2 e0 2.183
Frenkel pair in O sublattice
cence, DAP, transition); green (a triplet level at 2.5 eV), and
O3O 1 V3i ? V3O 1 O3i 6.948
red (at 1.9–2.0 eV). O3O 1 V3i ? VO 1 O0 i 7.964
 The neutral O interstitial in a split-interstitial peroxy configu- O3O 1 V3i ? VO 1 O@i 8.868 8.797
ration (at 2.8 eV) should also contribute to blue and green lu- Frenkel pair in Zn sublattice
minescence by an exciton recombination and DAP transition Zn3Zn 1 V3i ? V3Zn 1 Zn3i 12.002
from donor Zn interstitials. Zn3Zn 1 V3i ? V0 Zn 1 Zni 9.637
 O vacancies could not be a source of green luminescence, but Zn3Zn 1 V3i ? V@Zn 1 Zni 7.380 7.501
could contribute to near-gap (UV) and red–orange lumines- Zn3Zn 1 V3i ? V3Zn 1 Zni 1 2 e0 9.463
cence bands (at 2.1 eV and below) via the exciton recombina- Schottky pair
tion mechanism. Zn3Zn 1 O3O ? V3Zn 1 V3O 1 ZnO(s) 8.872
Zn3Zn 1 O3O ? V0 Zn 1 VO 1 ZnO(s) 7.645
 Our calculations confirm that Cu, which is stable in ZnO in
Zn3Zn 1 O3O ? V@Zn 1 VO 1 ZnO(s) 6.896 6.749
two charge states, is an efficient electron scavenger. The nega-
tively charged Cu0 Zn impurity is proposed as an E4 donor. The Kröger-Vink defect notation is used throughout. Letters g and s in
Calculated defect levels (at 2.7 and 0.55 eV) are in good parentheses indicate the gas phase and solid standard reference states.
agreement with experiment, which established Cu as a distinct a
Pure MM energies, obtained using Mott-Littleton approach and inter-
source of green luminescence from ZnO. atomic potentials, are shown for comparison for relevant charged defects.

Journal of Computational Chemistry DOI 10.1002/jcc

 Zinc Oxide: A Case Study in Contemporary Computational Solid State Chemistry 2239

Figure 3. Using the Mott-Littleton approach: the structure about a vacancy site within (c) region 1,
which is created by the removal of a Zn

O unit (semi-transparent dumbbell) that aligned (a,b) parallel to
and (d,e) perpendicular to the c axis, respectively. Spheres indicate three-coordinated ions, sticks (in a,d)
indicate bonds between ions nearest to the vacancy (i.e. spheres and ions within 2.2 Å from spheres), and
additional sticks (in d) are used to emphasise bonds that are parallel to the dumbbell. Distances are in Å.

arranged in parallel and zigzag patterns, while the polar surfaces
are stabilized by a reconstruction that creates discrete surface
vacancies.53–58 These surface vacancies are surrounded by
undercoordinated surface ions and can provide anchor sites for
metal ‘‘seeds’’ in nucleation, where strong interactions between
the support and a cluster can be expected. There have been
extensive computational studies concerning the structure and
properties of both polar and nonpolar surfaces of ZnO, using
semi-classical and electronic structure techniques (e.g. see refs.
13,27,59-64), but as the approaches adopted by different authors
resulted in very different conclusions, the subject remains open.
We have modeled the structure of the four surfaces using lat-
tice energy minimization techniques based on interatomic poten-
tials as outlined in ref. 17.
In our study of nonpolar surfaces, we rationalized the main
observed structural features and reconciled contradictory experi-
mental and theoretical evidence. In particular, for the (10
10)
surface, we have constructed models that proved to have a

Journal of Computational Chemistry DOI 10.1002/jcc

2240 Catlow et al. • Vol. 29, No. 13 • Journal of Computational Chemistry

Figure 4. Calculated energy levels of intrinsic and extrinsic defects in ZnO (in eV). [Color figure can
be viewed in the online issue, which is available at www.interscience.wiley.com.]

relatively low Zn

O dimer vacancy formation energy, which is the stepped surface (see Fig. 6) were found to be remarkably en-
in line with experimental reports of the fractional occupation of ergetically inexpensive, and our calculations suggest that steps
surface layers. The defects that occur due to the formation of would be widespread. As each type of surface defect studied is

Journal of Computational Chemistry DOI 10.1002/jcc

 Zinc Oxide: A Case Study in Contemporary Computational Solid State Chemistry 2241

Figure 5. Stable observed surfaces of zincite: a–(0001)-Zn and b–(000
1)-O terminated polar surfaces;
and c–(10
10) and d–(11
20) nonpolar surfaces. Features highlighted on the polar surfaces are bulk like
island and vacant interstitial sites. [Color figure can be viewed in the online issue, which is available
at www.interscience.wiley.com.]

achievable at a moderate energy cost, the method of sample vacancies in layers close to the surface to occur as dimers rather
preparation should play an important role in the observed sur- than to be separated. We find that one-layer isolated dimer
face structure. Surface annealing and polishing techniques can vacancies (up to 0.25 equivalent monolayer) have formation
easily provide enough thermal energy to form either step or energies of less than 0.8 eV per dimer and certain two-layer
dimer vacancy defects. We consider that even small differences clustered vacancies have formation energies of 1.45 eV per
in the treatment of samples during preparation may thus be a dimer. The formation energies for these latter defect types may
large factor in the type and concentration of defects. Similar appear relatively large. However, they should be attainable dur-
conclusions could be made for the other nonpolar surface.
Considering each of the major experimental observations, of
Jedrecy et al.65 and Parker et al.,66 we came to the following
conclusions: First, our model was consistent with the two-layer
step across the [010] direction (see Figure 6), which has an edge
parallel to the surface dimers; we found a low energy per dimer
for step creation. The work of Parker et al. also identified a sec-
ond two-layer step, running perpendicular to the dimers, across
the [001] direction. Our calculations suggested that a step in this
direction is energetically much less favorable either as a one-
layer or a two-layer step due to the polar character of the
exposed step edges. We suggested that a step in this direction
must be stabilized by a step edge reconstruction.
Next, regarding the occupancy factors of the first and second Figure 6. Most stable step feature on the (10
10) surface with the
layers, our model suggested that all types of vacancies caused step running parallel to the Zn

O surface dimers. [Color figure can
by incomplete occupation are energetically unfavorable to differ- be viewed in the online issue, which is available at www.interscience.
ent extents compared to a perfect surface. In general, we expect wiley.com.]

Journal of Computational Chemistry DOI 10.1002/jcc

2242 Catlow et al. • Vol. 29, No. 13 • Journal of Computational Chemistry
ing mechanical polishing and at the elevated temperatures used
in sample preparation as reported by both Jedrecy55 and
Parker.66 Remarkably, these energetics show a strong stabiliza-
tion effect on a single dimer subsurface formation, for which we
calculated the energy of 5.02 eV, which is in fact appreciably
higher than our bulk lowest value of 3.79 eV.
Our calculations found that groove formation in the direction
parallel to the dimers had a formation energy (0.128 eV), which
would be achievable under ambient conditions. Grooves have not
been reported as a surface feature, but a fuller investigation of
defect migration and agglomeration would be needed to determine
whether the groove defect would coexist with the step defect.
We describe next our work on the (0001)-Zn and (000
1)-O ter-
minated polar surfaces. In our model, the quenching of the
dipole across the slab is achieved by the simultaneous abstrac-
tion of 6 out of 25 surface ions from the two opposing surfaces,
which required the modeling of reconstruction and relaxation
processes in a 5 3 5 surface supercell model. In fact, surface
relaxation upon reconstruction resulted in a significant rumpling,
which is associated with the surface dipole. Such a dipole is spe-
cific to surface regions of any polar material, but usually is
assumed to be rather small and therefore unimportant. This
assumption, however, does not hold true for ZnO, for which we
calculated the resultant voltage to be 2.7 V due to the surface
dipoles in both Zn and O terminated surfaces. This voltage in a
real material is cancelled by further charge transfer, which we
propose as the main mechanism for defect formation in ZnO.
We are currently investigating the surface to bulk defect migra-
tion with the focus on surface morphology, results of which will
be reported elsewhere.
In the described reconstructed polar surfaces of ZnO, we iden-
tified two typical local environments, viz. terrace termination and
vacant interstitial surface sites. The vacant sites have been pro-
posed as the active site for the majority of processes we consid-
ered. The low coordinated sites are intrinsically highly reactive
and are exposed to guest adsorbate species as they are situated on
the surfaces (see Figs. 5a and 5b). All our subsequent work on
surfaces and catalysis, which we now discuss, employed the hybrid
QM/MM embedded cluster technique (already referred to above).
The vacant oxygen interstitial surfaces sites (VOISS shown in Fig.
5b) have been used throughout our investigations of methanol syn-
thesis over ZnO. Complementary investigations in surface hydro-
genation and anchoring of metal clusters were performed on the
vacant zinc interstitial surface sites (VZISS shown in Fig. 5a).
The hydrogenation of ZnO is a crucial step in many catalytic
processes, the leading example being the production of methanol
from the feed gas, as discussed in the next section. There has
been a rapid increase in experimental and theoretical studies
concerned with elucidating the complex atomistic processes
involved in sorption, reaction and then desorption of hydrogen
from ZnO. However, no fully validated mechanism or active site
has been proposed. To this end we have explored the potential
sites for the physisorption and chemisorption of hydrogen, which
have been considered on the catalytically important polar zinc
(0001) and oxygen (000
1) terminated surfaces of ZnO, while the
nonpolar (10
10) surface has been used for comparison.
Two major modes for the adsorption of hydrogen have been
identified.67 Type I adsorption is the reversible dissociative
Journal of Computational Chemistry
adsorption of H2 on Zn

O dimers to give Zn

H and O

H
species. Type II is also the dissociative adsorption of H2, but is
irreversible and has been suggested to comprise bridging
Zn

H

Zn and O

H.. . .O species. Thus, the different binding
sites are related to the chemical environments of the surface
atoms arising from the differences in the coordination number
and the proximity to defect sites. Our work sheds light on two
particular bands 1475 and 1710 cm21, characterizing the Type I
and II zinc hydride stretches.
The two key structures of chemisorbed hydrogen are shown
in Figure 7. When a single H2 molecule is dissociatively
adsorbed at the O vacant site, a trigonal zinc hydride and a
hydroxyl are formed, with a binding energy of 195 kJ/mol (2.02
eV). The strong chemisorption and the associated stretching fre-
quency of the hydrides are consistent with hydrogen being irre-
versibly adsorbed (at and below room temperature) and assigned
to Type II. Upon adsorption of a second molecule of hydrogen
there is a large drop in binding energy to 79 kJ/mol (0.82 eV)
per H2 molecule.
We have demonstrated that the appearance of the higher fre-
quency peak, 1745 cm21 necessitates the filling of the vacancy
with a Type II hydride (AZn), followed by Type I adsorption at
one of the stabilized Zn sites. The IR signal of the Type II
hydride depends on coverage, as has been shown experimentally
by the IR studies of Ghiotti et al.,67 which finds that the signal
at 1475 cm21 evolves with time. At low coverage, the (AZn)
band is weak due to the high symmetry, hydrogen being in a tri-
gonal configuration (see Fig. 7a). Upon further adsorption
(resulting in a Type I hydride) the (AZn) hydride, in the vacancy,
moves from a trigonal to a bridging configuration of lower sym-
metry. This change in configuration introduces a substantial
dipole moment, which in turn leads to a larger dipole derivative
associated with Zn

H

Zn asymmetric stretching vibrations.
These vibrations are characterized by a stronger IR signal, which
we calculated to be 1507 cm21 (cf. the experimental peak at
1475 cm21).67,68 The calculated stretching frequency of 1745
cm21 agrees well with the observed band at 1708–1710
cm21,67,68 and is characteristic of the oxygen surface and in par-
ticular the vacant oxygen interstitial surface sites. This is the
only theoretically proposed structural configuration able to
assign the mode at 1708–1710 cm21.
Hydrogenation of ZnO might also contribute to the formation
of space charge in accumulation layers, which are localized pre-
dominantly at polar surfaces.69–75 In turn, charge trapping is inti-
mately related to defect formation and more generally to the sur-
face morphology and properties of ZnO, which is demonstrated in
our proposed catalytic cycle introduced in the next section.
As mentioned, the primary candidate for the active site for
methanol synthesis on ZnO has been identified as surface oxy-
gen vacancies. Extensive experimental evidence can be found in
the literature, giving support for the presence of such sites at
ZnO surfaces in high concentrations.69,76–83 Several physical
phenomena including electron paramagnetic resonance, lumines-
cence, electrical conduction by hopping, find their natural expla-
nation in these centers, even though, a comprehensive theoretical
model should be developed. Such centers, however, could be
associated both with surface point defects and interstitial surface
sites.
DOI 10.1002/jcc
 Zinc Oxide: A Case Study in Contemporary Computational Solid State Chemistry 2243

Figure 7. Computational structural models for type I and II hydrogen adsorbed on a VOISS, which
dominate the morphology of the oxygen terminated surface of ZnO. White color indicates hydrogen
atoms. [Color figure can be viewed in the online issue, which is available at www.interscience.wiley.
com.]

We considered the formation of a neutral surface oxygen va-
cancy, VO, or F-center, an important point defect, which is also
present as a color center in the bulk of other oxide materials.
Whereas, in the bulk, there is only one unique oxygen site, a num-
ber of candidate sites can be considered for the removal of oxygen
from the surface and the topmost subsurface layers. Here we con-
centrated on an island oxygen surface site (Fig. 5b). It is important
to remember that a neutral VO defect localizes two electrons, in
contrast to neutral vacant oxygen interstitial sites.
Formation of oxygen vacancies at the oxygen terminated sur-
face of ZnO is envisaged as a result of pretreatments including
annealing, evacuation of samples in vacuo as well as surface
reduction under typical catalytic conditions where samples are
exposed to hydrogen:
ZnOðsÞ þ H2 ðgÞ ! VO þ H2 OðgÞ
We calculate an energy of only 0.27 eV for this reaction,
which suggests that these defects would be formed relatively
easily under catalytic conditions. A further significant gain in
energy can be obtained by introduction of a more powerful
reducing agent, CO, which is used in catalysis.

Figure 8. The vacant oxygen active site on oxygen terminated surface of ZnO, viewed along the sur-
face normal and in plane of the surface. The trapped electron is shown by its spin density distribution.
(Spin density isosurfaces are shown in cyan). [Color figure can be viewed in the online issue, which is
available at www.interscience.wiley.com.]

Journal of Computational Chemistry DOI 10.1002/jcc

2244 Catlow et al. • Vol. 29, No. 13 • Journal of Computational Chemistry
As we showed in our description of bulk defects, free carriers
are present in ZnO, even prior to hydrogenation, and usually
attributed to nonstoichiometry of ZnO with an excess of zinc.
Aluminum and other impurities also contribute to the n-type
conduction in ZnO. The energy balance between electron trap-
ping at VOISS and the interband transition leads to potential sta-
bilization of surface states. Trapping of an electron at a VOISS
would lead to a defect that is isoelectronic with a singly charged
oxygen vacancy, Vo (or surface F1 centre). For electron trap-
ping on VOISS, we obtain the energy of 24.64, and 6.21 eV for
the vacancy ionization.
The (VOISS)0 is the site of primary interest when considering
localized electrons that can potentially be seen in EPR and opti-
cal experiments. As the electron is trapped, its spin density
localizes nearly entirely within the vacant site, as shown in Fig-
ure 8. Integration of the spin density around the vacant site
shows that about 0.75 e2 is localized within the sphere that
touches the undercoordinated zinc ions. The remaining quarter
of an electron is localized on the six oxygen ions in the second
coordination shell of the VOISS.
Thus, the oxygen interstitial site can facilitate the formation
of anionic adsorbates. The site is able to trap an electron, and
adsorption can occur kinetically in two different ways: (i) neu-
tral adsorbates would approach the active site, at which an elec-
tron was already trapped, to form a surface anionic species; (ii)
transfer of an electron to the neutral active site would occur
simultaneously with the adsorption of neutral adsorbates.
Methanol Production From Syngas over ZnO Catalysts
Based on our surface studies and analysis of experimental litera-
ture, oxygen vacant sites on the oxygen terminated surface of
ZnO were predicted to be the active sites for the full catalytic
cycle: from surface hydrogenation to CO2 chemisorption, forma-
tion of formate, methoxy, and other key intermediates. Methanol
is released via C

O bond cleavage that leaves the active site
with an oxygen atom contained in the vacancy. The active site
is recycled by interaction with CO and H2. Research on the cata-
lytic cycle has involved modeling relevant spectroscopic signa-
tures and reaction energetics. We continued our work by consid-
ering the Cu/ZnO system, where we identified zinc vacancies on
the zinc terminated surface of ZnO as the preferential anchor
sites for copper adsorption. Further work includes the growth of
copper and other coinage metal clusters, before considering
methanol synthesis intermediates adsorbed on these clusters. A
review of this work and the consideration of the vital informa-
tion confirming our model of the active site on ZnO will be pre-
sented in the following section.
There has been confusion in the literature (see, for example,
the work of Kurtz et al.84), both experimental and computa-
tional, as to the nature of the key species in methanol synthesis
over both the industrial catalyst, Cu/ZnO/Al2O3 and the pure
ZnO support, which, with dopants such as Cr, was the initial
catalyst used by BASF. The foundation of this disparity is the
understanding of the correct active site. With the knowledge that
the vital process is the creation of oxygen vacancies in the sur-
face layer, the role of the three feed gases becomes clear and,
Journal of Computational Chemistry
importantly, CO2 is the key species that goes on to form
methanol.
The use of co-feed gases, H2 and CO, under high temperature
conditions, provides the adsorption sites, for CO2, that remain
stable enough for this species to be hydrogenated to form metha-
nol. Significant experiments, temperature programmed reduction/
desorption techniques (TPR/D) and frontal chromatography from
the group of Waugh (see ref. 85 and references therein), have
clearly shown that on ZnO it is CO2 that is the vital intermedi-
ate. Moreover, the same conclusion was made for the more
active Cu clusters that constitute the active sites in the industrial
catalyst.
TPD showed that, when CO and H2 were fed over the cata-
lyst, the product formed was CO2. In contrast, CO2 and H2 feeds
yielded formate, the signature of methanol formation. The role
of H2 is to pre-reduce ZnO, and thus provide binding sites for
CO2. After several hydrogenation steps, C

O scissions and O is
left in the vacant surface site, which is in turn cleared during the
H2 prereduction step, healing the surface. Along with further H2,
CO also scavenges for this O to release H2O and CO2, respec-
tively. CO is a more powerful reductant than H2 and therefore
more likely to create active adsorption sites in the surface lattice
for CO2. While H2 is able to re-reduce sites that were previously
healed, H2 is not strong enough to create further binding sites
by removing a lattice oxygen; CO, however, can do this. (See
ref. 86 for further details of the TPD studies.)
Studies of the reverse reaction, i.e. methanol decomposi-
tion, provided further vital insight into the mechanism of
methanol synthesis. By adsorbing methanol on ZnO at 473 K,
the formate species is formed. Furthermore, these experiments
unambiguously showed that this formate species was formed
by the interaction of CO2/H2 rather than CO/H2 at 473 K.
Deuterated reactants were also used to characterize this pro-
cess more reliably, helping to show that CO2 is not split to
form CO on ZnO.87,88
The most active ZnO surface (from those shown in Fig. 5)
has not been uniquely identified, and different authors have
presented contradictory evidence. However, from single crys-
tal studies, it has been shown with certainty that the adsorp-
tion and reaction processes are confined to the polar surfaces.
For the purposes of our investigations, we therefore concen-
trated on the oxygen-terminated polar surface. This surface
presents low coordinated oxygen in a structural motif where
the generation of vacancies should naturally be expected by
either prereduction steps, using H2, or CO reduction during
catalysis.*
A hydroxylated surface can be used as a model for the catalyst;
however, under reaction conditions, a fully hydroxylated surface
is not realistic. As described above, our early work on the hydro-
genation of the surface, where we correlated IR vibrational modes
from experiment and calculations, has clearly shown that the
mechanism of hydrogen dissociation is heterolytic, in which
hydroxyl and hydride species are formed simultaneously.89 The
*Of course, one can readily envisage formation of oxygen vacancies on
the zinc terminated surface at steps and other morphological features,
but such sites would still be isostructural with our model.
DOI 10.1002/jcc
 Zinc Oxide: A Case Study in Contemporary Computational Solid State Chemistry 2245

Figure 9. Methanol production from syngas (CO/CO2/H2) over (a) ZnO/Al2O3 and (b) Cu/ZnO cata-
lysts. Green color indicates carbon and orange indicates copper. [Color figure can be viewed in the
online issue, which is available at www.interscience.wiley.com.]

surface with a full coverage of hydroxyl groups would be a
more realistic representation of the initial, or as-delivered mate-
rial (exposed to water in air), i.e. prior to the initial reduction
step that is required to produce the active catalyst.
We have already discussed the formation of the active site,
shown in Figure 6. It is clear that CO2 can bind in the hole cre-
ated by removal of surface oxygen during the reconstruction
process. We calculated binding energies of CO2 and CO to this
polar surface site. Upon adsorption of CO2, an electron is trans-
ferred to the adsorbate. Electrons are available in pure ZnO as
the Fermi level lies 0.01–0.02 eV below the bottom of the con-
duction band. The native donors, the concentration of which can
reach 1018 cm23, are thought to be Zn interstitals and O vacan-
cies.45 In the context of catalysis however, and most impor-
tantly, the original catalyst includes 10% mixture of Al2O3 and
Cr2O3. Al and Cr substitute into the Zn sublattice where Al and
Cr work as electron donors. The O terminated surface, having a
higher electrostatic potential than the bulk, traps conduction
electrons, which become localized at vacant sites. In particular,
our calculations showed the reaction:
Al3 þ ðVOISSÞ3 ! Al þ ðVOISSÞ0 ;
ates in the reaction mechanism of CO2 to methanol (see Fig.
9b).95 Further characterization of the ZnO catalysts, with a par-
ticular emphasis on reaction mechanisms and novel systems e.g.
supported gold clusters, is in progress.96
Structure and Stability at Subnano-
and Nanoscale
The properties of subnano- and nanoscale zinc oxide structures
depend on their size and, importantly, structural motif, i.e., ring,
rod, tubular, bubble, onion, and bulk. Before we can predict the
properties of low-dimensional structures of a certain size, we
first need to determine their atomic structure.
There are a number of ways of finding the plausible struc-
tures of zinc oxide particles of a specific size. Usually, as a first
approximation, it is assumed that the minimum energy structure
is adopted or favored, although, of course, under real preparation
conditions kinetic factors may dominate. To obtain our cluster
models, using this first approximation, we have employed three
complementary approaches:21,97,98 (i) construction from smaller
known stable building units, (ii) dissection of bulk phases of

to be highly exothermic with a reaction energy of 2.30 eV.

We have modeled the whole reaction cycle, from CO2 to
methanol, see Figure 9a and refs. 90 and 91, with key stable
species, formate and methoxy like species, which are known to
be long lived intermediates in methanol synthesis.
We have extended our study of methanol synthesis to con-
sider the adsorption of copper on the ZnO polar surfaces.92–94
The mechanism of cluster growth, from the initial anchoring of
the first adatom to the surface, to subsequent stepwise addition
of copper, has been modeled. Here, we have considered different Figure 10. Examples of periodic, one dimensional structures for
charge states of the cluster at each step and the impact on the ZnO nanotubes. Each of the three tetragonal mesh structures can be
cluster morphology. We then took a representative model of a strained (periodic length changed) to create the hexagonal and tet-
copper cluster, planar Cu7 on the zinc terminated surface, and ragonal/octagonal mesh. [Color figure can be viewed in the online
performed calculations of the adsorption modes of all intermedi- issue, which is available at www.interscience.wiley.com.]

Journal of Computational Chemistry DOI 10.1002/jcc

2246 Catlow et al. • Vol. 29, No. 13 • Journal of Computational Chemistry

Figure 11. Examples of global minimum structures: (ZnO)n for (clockwise) n 5 1 to 6, 12, 15, 16,
18, 20, 21 and 28. [Color figure can be viewed in the online issue, which is available at www.inter-
science.wiley.com.]

Figure 12. Energies of formation for differing nanoscale morphologies of ZnO, together with the
global minima (GM, as found by an evolutionary algorithm). Lines connect structures with constant L,
length of tube, rather than diameter, D, or circumference, R. The GM structural motif changes from
stick to rings, cages, double cages, and then bulk cuts (BC), where GM line would cut BC curve.
[Color figure can be viewed in the online issue, which is available at www.interscience.wiley.com.]

ZnO, and (iii) evolution of a population of initially random
candidate structures.
Rings and double rings are known to form the most stable
configurations for the smallest particles. Using rings as building
blocks, it is easy to construct low-energy one-dimensional peri-
odic structures—tubes (see Fig. 10)—and by applying tensile
stress more stable rod morphologies can be obtained. By termi-
nating these tubes at specific length and relaxing, a multitude of
zero-dimensional configurations (nanoparticles) can be obtained.
Another approach to construction is to bend hexagonal sheets.
One set of bubble clusters can be built from eight sheets, where
the sheets are bowed to create octahedron-based cages. The
smallest octahedral bubble is a sodalite cage. The strain induced
by the curvature of the cages is reduced by the inclusion of just
six four-membered rings. We note that our constructed cages
have, by Euler’s law, the minimum number of four-membered
rings and no eight-membered rings.
The rock salt structure is, perhaps, the easiest phase to dis-
sect as perfect cuboid cuts produce low energy clusters, the size
of which corresponds to magic numbers of rock salt materials.y
We can also cut from other binary bulk phases, and, importantly,
the stable polymorph of ZnO under ambient conditions. Care
must be taken to reduce the macroscopic dipole formed in hex-
agonal prismatic cuts of wurtzite between the opposite basal
planes. For larger clusters, this dipole reduction could be
achieved following the same recipe as for the atomically recon-
structed polar surfaces of ZnO, outlined above. For smaller clus-
ters, however, the cost of reconstruction might change its struc-
tural motif.
An evolutionary algorithm (EA) mimics nature to evolve can-
didate structures that best fit the imposed constraints (fixed size,
stoichiometry and definition of energy of formation). Performing
several searches for each cluster size, we found many structures
y
Cluster sizes, which form more abundantly as seen in mass spectra dur-
ing laser ablation of rock salt structured materials. For II-VI compound
examples, see reference 99.

Journal of Computational Chemistry DOI 10.1002/jcc

 Zinc Oxide: A Case Study in Contemporary Computational Solid State Chemistry
already found in the two other approaches, although, impor-
tantly, some lower energy configurations were discovered.
Examples of lowest energy configurations for (ZnO)n for sev-
eral values of n are shown in Figure 11. Ring structures are
found to be most stable for the smallest clusters. The structure
for n 5 6 can be constructed from two three-member rings, cut
from zinc blende, and readily found by EA. Many of the smaller
bubble structures can also be found by relaxing cuts from two
parallel hexagonal sheets, upon which the structures pop open
breaking all the internal interconnecting bonds. Some external
bonds should also break, as, for example, breaking every other
external bond creates hexagonal faces from two edge-sharing tet-
ragonal faces, which is energetically favorable.
Typically above n 5 6, we find bubble structures, but we
know that the structural motif must eventually change to that of
bulk phase. Between these two regimes there is the possibility
of other structural motifs, for example, onions and bulk cuts
from other phases.15,99
In Figure 12, we plot the energies of formation as a function
of size for differing structural motifs, as well as the global minima
structures so far found by EA. To estimate the size, at which the
nanoparticles would adopt the bulk structural motif, we can extrap-
olate the GM curve to where it intercepts the bulk cuts. Interest-
ingly, this intersection does not show dramatic dependence of the
chosen phase and occurs at ca. n 5 120. Thus, the bulk-like struc-
ture is predicted to be adopted by nanoparticles with greater than
120 formula units. We note that this transition is not necessarily
accompanied by a dramatic change in cluster volume (or diameter)
as onion structures would probably dominate in the intermediate
size range between bulk and single layer bubbles. Fine tuning of
properties can be achieved by changing the cluster size within the
size range for each structural motif.
Future Work
The work summarized in this article has clearly shown the power
of contemporary computational techniques in modeling bulk and
surface properties of oxide materials. As a sign of rapid develop-
ment in the field, after submission of this paper, there have
appeared new studies in the literature101–103 that will be of interest
to the reader. There remain however, many challenges: tempera-
ture effects should be included using quasiharmonic or molecular
dynamics approaches. In the modeling of reactivity activation bar-
riers need to be calculated. Structure prediction and structure–
property relationship in larger pure and doped nanoscale ZnO
including excited electronic and vibrational states will be of direct
interest in the rapidly developing nanotechnologies. Fundamental
properties of ZnO including polymorphism will need to be investi-
gated with a focus on the effects of temperature and size. Finally
the future application in optoelectronics vitally depend on our
understanding of defect complexation, while one- and two-dimen-
sional defects in the form of dislocations and grain boundaries play
crucial roles in several applications of the material.
Acknowledgments
The authors thank the previous collaborators in different parts of
this work: S. Bromley, L. Whitmore, N. Phala, P. Sherwood, H.
Journal of Computational Chemistry
2247
van Dam, J. Kendrick, S. Roger, F. King. We are grateful for
useful discussions and advice to B. Slater, G. Dutta, M. Nygren,
J. Gale, K. Waugh, J. Gavartin, L. Kantorovich, F.-X. Coudert,
B. Kerkeni, S. Shevlin, S. Shluger, P. Sushko. Accelrys is kindly
thanked for the provision of the Materials Studio visualiser. The
work has been supported by an EPSRC Portfolio Partnership,
and HPC computer resources supplied via our membership of
the UK’s Materials Chemistry Consortium.
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DOI 10.1002/jcc
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Journal of Computational Chemistry DOI 10.1002/jcc