ARTICLE

pubs.acs.org/JPCC

Structure and Bonding of Tungsten Oxide Clusters on Nanostructured

Cu-O Surfaces
M. Wagner,† S. Surnev,† M. G. Ramsey,† G. Barcaro,‡ L. Sementa,‡ F. R. Negreiros,‡ A. Fortunelli,*,‡
Z. Dohnalek,§ and F. P. Netzer*,†
†
Surface and Interface Physics, Institute of Physics Karl-Franzens University Graz, A-8010 GRAZ, Austria
‡
CNR-IPCF, Istituto per i Processi Chimico-Fisici del CNR, I-56124 Pisa, Italy
§
Chemical and Materials Sciences Division, Fundamental and Computational Sciences Directorate, Pacific Northwest National
Laboratory, Richland, Washington 99352, United States

ABSTRACT: (WO3)3 gas-phase clusters generated via vacuum

sublimation are deposited under UHV and low temperature
(<15 K) conditions on a Cu(110) stripe phase consisting of
alternating Cu-O (2  1) and clean Cu regions. STM imaging
shows that the clusters adsorb as intact units on both substrates,
and the suggested adsorption geometries are confirmed by
density-functional (DF) simulations. On the clean surface, the
overall distortion is minor, and we are able to image the nodal
structure of an individual molecular orbital in the STM at low
bias, whereas on the Cu-O surface both the clusters and the substrate are significantly distorted due to the strong oxygen affinity of W
atoms. On both surfaces, cluster and Cu electronic states are appreciably mixed, and the electron charge is donated by the surface to
the cluster. The experimentally STS-determined DOS signature of the adsorption complex consists of two peaks across the Fermi
energy and is well reproduced by the DF calculations.

1. INTRODUCTION high activity as catalysts for many chemical transformations,4,5

Oxide clusters with well-defined size and stoichiometry on
metal surfaces are interesting nanoscale objects with attractive
features for both fundamental research and technological appli-
cations. The structure and bonding concepts of small oxide
clusters on metal surfaces may be taken in a reductionist
approach to mimic the situation at oxide metal interfaces, with
related interest from the viewpoint of catalysis and diverse fields
of electronic device technologies, where oxide metal interfaces
are of relevance. Oxide clusters supported on metal single crystal
surfaces bear attractive features for studying the fundamental
electronic interactions between molecular systems of oxide
character and metal surfaces, and they may be used to model
catalytic sites with atomic size and composition control. Con-
versely, the immobilization in space of clusters by deposition on a
solid surface allows one to probe cluster properties, which
otherwise are very difficult to reveal.1 For example, the determi-
nation of the structure of clusters in the gas phase is very difficult
and one has to rely on theoretical simulations mainly, whereas on
a metal surface, scanning tunneling microscopy (STM) can be
applied, and the theoretical cluster parameters can be tested
against the experimental results.2 Oxide clusters may be used as
elementary building blocks for the self-assembly of oxide nanos-
tructures on surfaces, and such a procedure has been reported
recently for the formation of two-dimensional W oxide nano-
layers on a platinum surface.3
In this work, we have focused our interest on the interaction of
small tungsten oxide clusters with Cu surfaces. W oxides show
and W clusters supported on a titania substrate have been
presented recently as a very efficient catalyst for the dehydration
of alcohols.6,7 Tungsten oxide clusters can be generated by direct
vacuum sublimation from solid WO3 with the trimeric (WO3)3
cluster as the most abundant species in the gas phase.8 Dohnalek
et al.9,10 have prepared model catalysts by the direct thermal
evaporation of WO3 onto a TiO2 (110) surface and have
analyzed the WOx deposits by STM, finding a nearly mono-
disperse distribution of (WO3)3 clusters. Apart from their
interesting catalytic properties, (WO3)3 clusters are outstanding
molecular-type objects with an unusual bonding type: δ-aromaticity
due to a δ-bonding interaction and a d level delocalization.11 The
electronic interactions of (WO3)3 clusters with metal atoms and
their geometry parameters related to adsorption on a metal
surface as well as their molecular stability are thus fundamental
issues for the description of oxide chemical bonding at metal
surfaces.
We have chosen a nanostructured Cu-O surface as the substrate
for this (WO3)3 cluster study. This so-called Cu(110)-O stripe
phase develops under suitable conditions of oxygen pressure and
of the Cu(110) substrate temperature and consists of a regular
Cu-O stripe pattern in which regions of the Cu-O (2  1) surface
reconstruction self-assemble into nanoscopic Cu-O stripes separated
Received: August 25, 2011
Revised: October 17, 2011
Published: October 24, 2011

r 2011 American Chemical Society 23480 dx.doi.org/10.1021/jp208207e | J. Phys. Chem. C 2011, 115, 23480–23487
The Journal of Physical Chemistry C ARTICLE

by stripes of the clean Cu(110) surface.12 14 The Cu-O nano-
structured substrate allows us to measure the adsorption behavior
of (WO3)3 clusters under the same experimental conditions on a
surface with two different chemical environments and different
adsorbate substrate coupling strengths. We have recorded STM
images and STS spectra in a low-temperature (∼5 K) scanning
tunneling microscope after depositing the (WO3)3 clusters on to
the Cu-O stripe phase at ∼15 K to determine the adsorption
geometry and the surface interactions of the intact clusters.
First-principles density functional (DF) calculations have been
performed to model the adsorption complex and to address the
structural energetics and bonding concepts of the oxide clusters.
We find that (WO3)3 clusters can adsorb as intact single units
on both bare and oxidized Cu(110) surfaces, and we unambigu-
ously determine their preferred adsorption geometries. The theore-
tical analysis reveals that adsorption is accompanied by a significant
mixing of the electronic states of the interacting fragments and an
appreciable charge flow from the support to the oxide cluster. On
the bare Cu surface, the clusters remain symmetric and we are
able to image the nodal structure of an individual molecular
orbital in the STM at low bias. On the oxidized surface, the
strength of the cluster/support interaction and the oxygen
affinity of W lead to a significant distortion and a structural recon-
struction of both the surface and the cluster.
In section 2, experimental and computational details are
provided. Results are presented and discussed in section 3, while
conclusions are summarized in section 4.

2. EXPERIMENTAL AND COMPUTATIONAL DETAILS

The STM/STS experiments have been carried out in a three-
chamber low-temperature STM system (Createc, Germany) in
Figure 1. Models of (a) Cu(110) and (b) Cu-O (2  1) surfaces used ultrahigh vacuum with a base pressure of ∼5  10 11 mbar,
in the calculations. operated at a measurement temperature of ∼5 6 K in the liquid

Figure 2. (a) STM images of the Cu-O stripe phase with (WO3)3 clusters deposited at 15 K and imaged at 5 K (top, (100  90 Å2), 1 V sample bias,
0.1 nA tunneling current; middle, (100  54 Å2), 1 V, 0.1 nA; bottom, (100  58 Å2), 0.56 V, 0.1 nA). (b) High-resolution STM images of (WO3)3 clusters
on clean Cu(110) (top, (25  25 Å2), 0.8 V, 0.1 nA; bottom, (25  25 Å2), 1 V, 0.8 nA). The line across the cluster in the bottom image indicates the
direction of the line scan displayed in panel c, bottom. (c) Top: schematics of the (WO3)3 cluster geometry in the gas phase. Middle: STM image and
schematic drawing specifying the cluster adsorption sites. Bottom: line scan across the line in panel b, bottom.

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Figure 3. High-resolution STM images of (WO3)3 clusters on the Cu(110)(2  1)-O reconstruction ((25  25 Å2), 1 V, 0.1 nA). The schematic
drawing illustrates the slight rotation of the clusters with respect to the high symmetry directions and three equivalent configurations. The bottom right
panel is a line scan across two maxima of the cluster.

He STM cryostat stage.15 Sample surface cleaning and prepara-

tion and in situ STM tip treatments are performed in the
preparation chamber, which is equipped with a liquid He cool-
able manipulator (reaching sample temperatures of ∼15 K),
LEED optics, a mass spectrometer, and the usual provisions for
surface cleaning and thin film evaporation. The samples can be
transferred cold into the STM stage directly from the cooled
manipulator. Electrochemically etched W tips and PtIr tips have
been treated in situ by electron bombardment heating and by
field emission via voltage pulses. STS spectroscopy (differential
conductance dI/dV versus V) was performed by a lock-in
technique with a 1.35 kHz modulation frequency and typical
100 mV modulation amplitude. The voltages quoted are sample
potentials with respect to the tip.
The Cu(110) surface was cleaned by standard techniques, i.e.,
Ar+ ion sputtering (700 eV) and annealing (825 K) cycles in
UHV. The Cu(110)(2  1)-O stripe phase was prepared by
dosing 0.5 1.5 L (1 Langmuir (L) = 1  10 6 Torr 3 s) of O2 at a Figure 4. STM images of (WO3)3 clusters as a function of sample bias:
sample temperature of 600 K followed by annealing (600 K) in (a) Cu(110) surface; and (b) Cu(110)(2  1)-O surface ((25  25 Å2),
UHV for 1 min. The (WO3)3 clusters were deposited via direct 0.1 nA). (c) Comparison between the experimental STM image at +0.23
sublimation from WO3 powder on to the cooled Cu surface eV bias (extreme left) and that simulated using a single virtual MO
(∼15 K) using a high-temperature alumina effusion cell located 0.35 eV above the Fermi level (middle left); isosurface (value of
(Createc) operated at ∼1200 1300 K. 0.0001 au) of the same MO for the (WO3)3 cluster, both Cu(110)-
supported (middle right) and in the gas-phase (extreme right).
DF calculations were performed using the QuantumEspresso
package16 employing a basis set of plane waves, ultrasoft
pseudopotentials,17 and the Perdew Burke Ernzerhof (PBE) The metal support was modeled by 4 Cu slabs in (110) stacking,
exchange-correlation (xc) functional.18 To describe adsorption where the bottom 3 layers were kept frozen in their bulk lattice
over the Cu(110) clean surface, we employed a (3  4) positions. In the case of adsorption over a Cu-O (2  1) surface,
rectangular unit cell, extending 10.99 Å along the x axis and the unit cell is shown in Figure 1b, and is similar to that used for
10.36 Å along the y axis, as shown in Figure 1a. The first-neighbor the bare surface except that we added a fifth metal layer
distance in the metal was set to 2.59 Å, corresponding to the composed of rows of alternating Cu and O atoms according to
equilibrium lattice parameter of bulk Cu according to our DF the (2  1) pattern. Local relaxations were performed until the
approach, to be compared with an experimental value of 2.56 Å. total forces resulted smaller than 0.01 eV/Å. Along the z axis, a
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The Journal of Physical Chemistry C
Figure 5. (a) STS spectra taken from the clean Cu(110) surface and from the top of a (WO3)3 cluster. Note that the sharp feature near 0 V bias is due to
the STM tip. PDOS (in arbitrary units) of the (WO3)3 cluster in the gas-phase (b) and Cu(110)-supported (c). The one-electron levels are broadened
using a Gaussian smearing with σ = 0.2 eV.
minimum empty space of 10 Å was chosen to avoid interactions
between replicated cells. A dipole correction19 was applied to
cancel spurious Coulombic interactions among replicated
images. Values of 40 and 240 Ry were chosen as the energy
cutoff for the selection of the plane waves for the description of
the wave function and the electronic density, respectively. The
first Brillouin zone was k-sampled at the Gamma point only,
having verified that the results are at convergence with respect to
a finer (2,2,1) grid; the electronic levels were broadened with a
Gaussian smearing of about 0.03 eV. All the calculations per-
formed were spin-polarized. STM images were simulated apply-
ing the Tersoff Hamann approach20 at a constant height of
about 2 Å above the surface.
3. RESULTS AND DISCUSSION
Figure 2a shows a set of STM images of the Cu-O stripe phase
with a small number of individual (WO3)3 clusters, deposited at
∼15 K and imaged at ∼5 K. The Cu-O stripes are readily
recognized by the atomic corrugation, while the bare Cu areas
cannot be atomically resolved at the respective tunneling condi-
tions. The clusters are distinguished in the STM images forming
triangular trimers of bright maxima, consistent in shape and size
with their expected structure in the gas phase1 (see Figure 2c, top
panel). Concentrating first on the clean Cu(110) areas, the
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clusters are adsorbed in two orientations, as detailed in the high-
resolution STM images in Figure 2b. The atomic corrugation of
the well-known structure of the Cu-O (2  1) reconstruction
serves as a calibration mesh to determine the accurate adsorption
sites of the (WO3)3 clusters. Interestingly, two different adsorp-
tion sites can be distinguished by the analysis. As shown in the
STM image and the schematic drawing of Figure 2c, two of the
bright STM blobs forming the basis of the (WO3)3 triangle are
centered on top of one Cu row along the [110] direction, while
the third blob at the apex of the triangle is located in a short-
bridge site on top of the adjacent Cu row (this is depicted in the
upper cluster of the schematic); this yields a symmetric site with
two equivalent configurations with the triangle up or down (as
shown in Figure 2b). However, clusters have also been detected,
where the basis and the apex of the triangle are centered above
the Cu troughs along (110), as illustrated with the lower cluster
in the schematic drawing; again, two equivalent configurations
with the triangles up or down have been observed. The two
different adsorption sites of clusters are thus on-top of the ridges
or in the troughs of the (110) surface. The line scan (bottom
panel of Figure 2c) taken along the line in Figure 2b (bottom)
reveals a distance of ∼5 Å between the maxima and an apparent
height of ∼1.4 Å. Further details concerning the adsorption sites are
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discussed below in conjunction with the results of DF

calculations.
The (WO3)3 clusters on the Cu-O stripes also appear mostly
as triangular trimer features in the STM, but the finer details of
the adsorbate configuration are different from clean Cu. Figure 3
displays high-resolution STM images of (WO3)3 clusters on Cu-
O in three different orientations. As illustrated by the super-
imposed (2  1) mesh and the schematic drawing, the clusters
are slightly rotated with respect to the high-symmetry [110] and
[001] azimuth directions. In principle, four equivalent orienta-
tions should be possible, although we have observed only three of
them (shown in Figure 3). The line scan in Figure 3 shows that
the apparent cluster sizes are similar on clean Cu(110) and
Cu(110)-O, with ∼5 Å maxima distances and ∼1.2 Å height in
the latter case.
The cluster shapes in STM as shown in Figures 2 and 3 are
robust with bias conditions down to approximately (0.3 V. This
is illustrated in Figure 4, where STM images of clusters as a
function of the (positive) sample bias for the clean Cu and the
Cu-O surface are displayed. The clusters show their typical
triangular shape down to a bias of about 0.3 V, but the symmetry
becomes somewhat lost at lower bias and a segmentation of the
pattern with dark lines, reminiscent of nodal planes, appears
especially on the bare Cu(110) surface. Figure 5a compares plots
of the differential conductance dI/dV versus V taken from the
clean Cu surface and from the top of a (WO3)3 cluster (on clean
Cu). The STS spectrum of the cluster shows two pronounced
peaks at 1.85 V and +1.5 V (arrows in Figure 5a), which are
associated most naturally with peaks in the density of states of the
adsorption complex. The sharp peak just above 0 V bias is
observed both on the clean Cu surface and on the cluster and is
therefore ascribed to a tip induced feature.
Figure 6. Adsorption geometry and structure of the (WO3)3 cluster on
DF simulations confirm the intuitive interpretation of the bare Cu(110): (a) top and two side views of the global minimum
experimental STM images on the clean Cu(110) surface: the structure; (b) simulated STM at a positive bias of 1.00 V plus a different
preferred adsorption configuration of a (WO3)3 cluster is shown top view with a superimposed grid. (c) Top and side views of the
in Figure 6a, together with the simulated STM image calculated configuration shifted by a half period along a direction perpendicular to
at positive bias (Figure 6b). In this geometry, the (WO3)3 cluster the surface ridges; (d) simulated STM at a positive bias of 1.00 V plus a
is pinned via the three oxygen atoms lying below the W plane of different top view with a superimposed grid.
the cluster to two parallel ridges of the Cu(110) surface occupy-
ing bridge sites between two vicinal Cu atoms. An energy perpendicular to the surface ridges. This configuration is shown
decomposition analysis shows that the (WO3)3 cluster interacts in Figure 6c and is at 0.62 eV higher in energy with respect to the
strongly with the metal surface: the adhesion energy, i.e., the global minimum. In this geometry, the adhesion energy is
difference between the total energy of the system and that of the 5.51 eV, and the distortion energy is 2.90 eV. The corresponding
two isolated fragments taken in the interacting configuration, simulated STM image shown in Figure 6d demonstrates that in
amounts to 6.47 eV, while the distortion energy of the oxide this configuration, the three oxygen atoms fall atop the troughs
cluster (i.e., the energy difference between the DF-optimized gas- between the surface ridges, in full agreement with the alternative
phase geometry and the energy of the cluster in the interacting adsorption site observed in the experiment.
configuration) is 3.32 eV, and the distortion energy of the metal A plot of the Projected Density of States (PDOS) is reported
surface is negligible. The significant distortion of the oxide cluster in Figure 5b,c for a (WO3)3 cluster in the gas-phase and adsorbed
is thus largely compensated by the formation of strong copper/ in its global minimum configuration on the Cu(110) surface,
oxygen chemical bonds. The STM simulated image of Figure 6b respectively. A comparison of Figure 5b,c immediately shows a
indicates that the oxygen atoms lying above the W plane of the substantial mixing of the electronic states of the cluster and the
cluster are imaged as bright spots, forming a quasi-equilateral metal surface in the adsorption complex, thus confirming the
triangle (side length of 4.5 4.6 Å). The three spots have similar strong interaction between the Cu(110) surface and the (WO3)3
intensity, as the oxygen atoms lie at almost the same height above cluster. This is also due to a charge transfer from the surface to
the surface. By looking at Figure 6b, we can see that the two spots the cluster: an analysis of Lowdin atomic charges shows that each
aligned along the [110] direction of the metal substrate corre- W and O atom in direct contact with the surface receives about
sponds to oxygen atoms on-top of a ridge of the Cu(110) surface, 0.3 electrons in the adsorption process. In addition, below and
confirming the interpretation of the experimental STM images. above the Fermi energy (0 V), two peaks are found in the DOS
In addition to this global minimum, a local minimum has also (arrows in Figure 5c), one at around 1.9 V and one at around
been found from the DF calculations, corresponding to an +1.2 V (composed of states centered on both W atoms and O
adsorption geometry shifted by a half period along a direction atoms above the W plane). These compare fairly well with the
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Figure 7. Same as that of Figure 6 for (WO3)3 clusters on Cu-O (2  1): (a) global minimum top and side views together with a simulated STM image
at a positive bias of 1.00 V plus an isosurface contour of 0.0001; (b) same for the first excited state geometry located 0.18 eV above the GS; (c) same for
the second excited state geometry located 0.43 eV above the GS.
peaks at 1.85 V and +1.5 V from the experimental STS plot in
Figure 5a; note that the energies of the empty states are often
underestimated using a semilocal exchange-correlation func-
tional as that employed in the present study.
The fragmentation in the STM images observed at low bias in
Figure 4a lends itself to a more detailed analysis. In Figure 4c, the
simulated STM image of an individual molecular orbital (MO) of
a (WO3)3 cluster adsorbed in its global minimum configuration
on the Cu(110) surface is shown; it corresponds to an unoccu-
pied orbital located at 0.35 eV above the Fermi energy. One can
observe a fair correspondence between the experimental and
theoretical STM images suggesting that at low bias (and thus at a
very small tip-cluster distance) the nodal structure of an indivi-
dual molecular orbital can actually be imaged. This orbital is
mainly of antibonding character derived from the antiphase
combination of atomic d-functions of W atoms, as shown in
Figure 4c. In the same figure, the molecular orbital of the free
cluster most closely resembling the state of the supported system
is also shown: in the gas-phase, this orbital lies at 0.48 eV above
the LUMO, is nondegenerate (A1 point group symmetry), and
corresponds to an unoccupied shell of the δ-aromatic electronic
system.11 Once supported, it mixes in with low-energy states
from the surface as shown in Figure 4c. Imaging of individual
molecular orbitals has been previously realized for quantum well
states observed in Au clusters supported on an ultrathin MgO
film21 or organic molecules on ultrathin NaCl films.2 Here, this
possibility is realized thanks to the electronic shell structure
associated with δ-aromaticity.11
In the case of adsorption on the Cu-O stripes, DF calculations
present a more complicated energy landscape. The main reason
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is that the W atoms in the (WO3)3 units are very reactive toward
oxygen. This makes it so that the adsorption process is accom-
panied by a substantial structural rearrangement, in which both
the oxide cluster and surface geometries are appreciably dis-
torted. Starting from configurations derived from an analysis of
the experimental STM images, several local relaxations were
performed at the DF level to single out the lowest-energy
structures. The putative global minimum according to our
calculations and its simulated STM image at positive bias are
shown in Figure 7a. The strong interaction between the oxide
cluster and the oxidized surface makes it so that the W atoms of
the (WO3)3 unit tend to extract oxygen atoms from the surface.
In the STM image, the oxygen atoms lying above the W plane of
the cluster are still imaged, but their different heights make it so
that the brightness of the corresponding spots is quite diverse. By
comparing the orientation of the oxide cluster with respect to the
surface and the brightness of the spots, we find a reasonable
agreement with the experiment. In general, the clusters appear
more symmetric in the experimental STM images, but it should
be considered that in the simulation, we plot STM images at
constant height, whereas in the experiment, STM images at
constant current are registered. Indeed, the contour of a STM
iso-surface, showing at the same time the orientation of the oxide
cluster and that of the oxygen atoms of the surface, also plotted
in Figure 7a, suggests that a constant current simulation (not
available in our software) would produce a more triangular shape
and a closer match with experimental STM images. The adhesion
energy of the putative global minimum amounts to 7.65 eV, while
the distortion energies of the cluster and the oxidized metal
surface are 3.24 and 2.59 eV, respectively. The adhesion energy is
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Figure 8. Large scale STM images of the Cu(110)(2  1)-O surface
after the deposition of (WO3)3 clusters at 15 K. (a) (200  200 Å2),
0.9 V, 0.13 nA; (b) (100  100 Å2), 1.3 V, 0.12 nA. Besides the triangular
clusters in their ground state configuration (square frames), other
features and geometries of excited clusters can also be discerned (see,
e.g., circles).
higher than on the bare surface, but at the price of a significant
surface reconstruction. The fluxional character of the oxidized
surface and the strength of W O bonds thus make it so that the
(WO3)3 clusters are structurally different from the gas-phase
configuration. Additionally, an analysis of Lowdin charges shows
that also in this case a substantial charge flow takes place from the
oxidized metal surface to the oxide cluster.
Apart from this global minimum, and at variance with the case
of the clean Cu(110) surface, on the oxidized surface, several
configurations quite close in energy but structurally very different
are found. As an example, in Figure 7b,c, we show two such
structures that are only 0.18 and 0.43 eV, respectively, higher
than the global minimum (ground state, GS). It can be noted in
this connection that also in the experiment, an STM pattern
exhibiting three spots of comparable size and brightness is not
the rule for clusters on the oxidized surface. As an example, in
Figure 8, larger scale STM images of clusters on the oxidized
surface are displayed, where, besides clusters in their ground state
geometries, the frequent presence of irregular cluster patterns is
apparent, suggesting a variety of adsorption geometries that can
be put in fair correspondence with the simulated STM images of
Figure 7b,c. These distorted geometries are probably due to
excited cluster configurations frozen-in at the low deposition
temperature of 15 K.
4. CONCLUSIONS
The interaction of (WO3)3 clusters with bare Cu(110) and
oxygen-reconstructed Cu(110)(2  1) surfaces has been inves-
tigated experimentally in a low-temperature (5 K) STM and
analyzed theoretically by DF calculations: adsorption site geo-
metries and bonding modes were the major topics of interest.
The (WO3)3 clusters remain intact after deposition at low tem-
perature (<15 K) from the gas phase on both surfaces, but the
cluster surface interactions are strong, and significant differences in
the adsorption complex geometries are apparent between the
bare Cu and the Cu-O surfaces. The DF energy decomposition
analysis allows us to separate adhesive bonding and distortion
strain contributions to the global adsorption energy. On Cu(110),
the (WO3)3 clusters are bonded via the three oxygen atoms
below the W plane to the Cu surface atoms, yielding a symmetric
adsorbate configuration. On Cu-O, the energy landscape is more
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complex and the W atoms of the cluster also interact with the
substrate with a significant distortion of both the W-O cluster
and Cu-O surface. Substantial mixing of the cluster and surface
electronic states with charge transfer from the surface to the
cluster is indicated on both Cu and Cu-O surfaces. The experi-
mentally STS-determined DOS signature of the adsorption
complex consists of two peaks across the Fermi energy reminis-
cent of the HOMO and LUMO states of the isolated cluster and
is well reproduced by the DF calculations. At low bias, the STM
cluster images show a fragmentation, which is interpreted in
terms of imaging individual MOs, connected with the orbital
structure of the aromatic δ-bonding in the (WO3)3 cluster.
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: alessandro.fortunelli@cnr.it (A.F.); falko.netzer@
uni-graz.at (F.P.N.).
’ ACKNOWLEDGMENT
This work has been supported by the ERC Advanced Grant
SEPON. CPU time at the CINECA supercomputing center via
the ISCRA UT-Ox project is gratefully acknowledged. A part of
this work was supported by the U.S. Department of Energy
Office of Basic Energy Sciences, Division of Chemical Sciences,
Biosciences, and Geosciences.
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