Published on Web 02/15/2007

Probing the Electronic Structure and Band Gap Evolution of

Titanium Oxide Clusters (TiO2)n- (n ) 1-10) Using
Photoelectron Spectroscopy
Hua-Jin Zhai and Lai-Sheng Wang*
Contribution from the Department of Physics, Washington State UniVersity, 2710 UniVersity
DriVe, Richland, Washington 99354, and Chemical & Materials Sciences DiVision, Pacific
Northwest National Laboratory, MS K8-88, P.O. Box 999, Richland, Washington 99352
Received November 30, 2006; E-mail: ls.wang@pnl.gov

Abstract: TiO2 is a wide-band-gap semiconductor, and it is an important material for photocatalysis. Here
we report an experimental investigation of the electronic structure of (TiO2)n clusters and how their band
gap evolves as a function of size using anion photoelectron spectroscopy (PES). PES spectra of (TiO2)n-
clusters for n ) 1-10 have been obtained at 193 nm (6.424 eV) and 157 nm (7.866 eV). The high photon
energy at 157 nm allows the band gap of the TiO2 clusters to be clearly revealed up to n ) 10. The band
gap is observed to be strongly size-dependent for n < 7, but it rapidly approaches the bulk limit at n ) 7
and remains constant up to n ) 10. All PES features are observed to be very broad, suggesting large
geometry changes between the anions and the neutral clusters due to the localized nature of the extra
electron in the anions. The measured electron affinities and the energy gaps are compared with available
theoretical calculations. The extra electron in the (TiO2)n- clusters for n > 1 appears to be localized in a
tricoordinated Ti atom, creating a single Ti3+ site and making these clusters ideal molecular models for
mechanistic understanding of TiO2 surface defects and photocatalytic properties.

1. Introduction threshold and thus increasing the utilization of the solar

Titanium dioxide (TiO2) is an important transition-metal oxide spectrum.1,2,4 Quantum confinement in nanocrystals can modify
material and has widespread applications because of its low cost, the optical properties of semiconductors.7 However, TiO2 has
stability, and environmental compatibility.1,2 Of particular recent a relatively small exciton radius (e∼1 nm), and thus, no
interest are its applications as photocatalysts for hydrogen quantum confinement effect has been observed for TiO2
production, in solar cells, and for organic contaminant degrada- nanoparticles down to ∼1 nm radius.6
tion.3,4 Photocatalysis makes use of the semiconducting proper- Atomic clusters have long been considered as models for
ties of TiO2, which has an inherent band gap of 3.0 eV for rutile fundamental mechanistic insight into complex surfaces and
and 3.2 eV for anatase.5,6 However, the wide band gaps imply catalysts. Numerous experimental8-14 and theoretical15-24 studies
that only the portion of the solar spectrum from ultraviolet down
(7) (a) Brus, L. E. J. Chem. Phys. 1984, 80, 4403. (b) Steigerwald, M. L.;
to ∼400 nm can be absorbed by bulk TiO2.1,2 Extensive recent Brus, L. E. Acc. Chem. Res. 1990, 23, 183.
efforts have been focused on tailoring the TiO2 band gap through (8) McIntyre, N. S.; Thompson, K. R.; Weltner, W. J. Chem. Phys. 1971, 75,
3243.
doping with impurities, aimed at lowering the photoexcitation (9) (a) Balducci, G.; Gigli, G.; Guido, M. J. Chem. Phys. 1985, 83, 1909. (b)
Balducci, G.; Gigli, G.; Guido, M. J. Chem. Phys. 1985, 83, 1913.
(1) Diebold, U. Surf. Sci. Rep. 2003, 48, 53. (10) Yu, W.; Freas, R. B. J. Am. Chem. Soc. 1990, 112, 7126.
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2006, 106, 4428. (b) Linsebigler, A. L.; Lu, G.; Yates, J. T. Chem. ReV. Processes 1992, 117, 129.
1995, 95, 735. (c) Hagfeldt, A.; Gratzel, M. Acc. Chem. Res. 2000, 33, (12) Chertihin, G. V.; Andrews, L. J. Phys. Chem. 1995, 99, 6356.
269. (d) Hoffmann, M. R.; Martin, S. T.; Choi, W.; Bahnemann, D. W. (13) Wu, H.; Wang, L. S. J. Chem. Phys. 1997, 107, 8221.
Chem. ReV. 1995, 95, 69. (e) Heller, A. Acc. Chem. Res. 1995, 28, 503. (14) (a) Foltin, M.; Stueber, G. J.; Bernstein, E. R. J. Chem. Phys. 1999, 111,
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M. Nature 1991, 353, 737. (c) Wang, R.; Hashimoto, K.; Fujishima, A.; (15) Ramana, M. V.; Phillips, D. H. J. Chem. Phys. 1988, 88, 2637.
Chikuni, M.; Kojima, E.; Kitamura, A.; Shimohigoshi, M.; Watanabe, T. (16) Bergstrom, R.; Lunell, S.; Eriksson, L. A. Int. J. Quantum Chem. 1996,
Nature 1997, 388, 431. 59, 427.
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293, 269. (b) Khan, S. U. M.; Al-Shahry, M.; Ingler, W. B. Science 2002, 5224.
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Walck, S. D.; Yates, J. T. J. Phys. Chem. B 2004, 108, 6004. (d) Di (19) Albaret, T.; Finocchi, F.; Noguera, C. Faraday Discuss. 1999, 114, 285.
Valentin, C.; Pacchioni, G.; Selloni, A. Phys. ReV. B 2004, 70, 085116. (20) Woodley, S. M.; Hamad, S.; Mejias, J. A.; Catlow, C. R. A. J. Mater.
(e) Lee, J. Y.; Park, J.; Cho, J. H. Appl. Phys. Lett. 2005, 87, 011904. (f) Chem. 2006, 16, 1927.
Batzill, M.; Morales, E. H.; Diebold, U. Phys. ReV. Lett. 2006, 96, 026103. (21) Hamad, S.; Catlow, C. R. A.; Woodley, S. M.; Lago, S.; Mejias, J. A. J.
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Am. Chem. Soc. 1996, 118, 6716. (b) Tang, H.; Berger, H.; Schmid, P. E.; (22) Qu, Z.-W.; Kroes, G.-J. J. Phys. Chem. B 2006, 110, 8998.
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3022 9 J. AM. CHEM. SOC. 2007, 129, 3022-3026 10.1021/ja068601z CCC: $37.00 © 2007 American Chemical Society
(TiO2)n Electronic Structure and Band Gap Evolution ARTICLES

have been reported on titanium oxide clusters. The previous

experimental studies include collision-induced dissociation of
titanium oxide cluster cations,10 chemical reaction of titanium
oxide cluster cations toward oxygen,11 single-photon ionization
mass spectra of TimOn neutral clusters at 118 nm,14 and matrix
vibrational spectroscopy on small titanium oxide molecules.8,12
However, there is a real dearth of experimental electronic
structure information about TiO2 clusters and how it changes
with cluster size, except our previous report on the electronic
structure of TiOx- (x ) 1-3) and (TiO2)n- (n ) 1-4) using
photoelectron spectroscopy (PES) at variable photon energies
up to 6.424 eV.13
PES of size-selected anions is a powerful technique to probe
the electronic structure of atomic clusters and can yield direct
experimental information about the energy gap for neutral
clusters with closed-shell electron configurations.25,26 However,
the (TiO2)n- clusters possess rather high electron binding
energies, and our previous PES study was not able to fully reveal
the energy gap for n > 2.13 Here we report a more compre-
hensive PES study of (TiO2)n- clusters from n ) 1 to n ) 10
at two high photon energies, 6.424 eV (193 nm) and 7.866 eV
(157 nm), and under better controlled experimental conditions.27
The 157 nm data clearly showed the energy gaps in all the
(TiO2)n- clusters up to n ) 10 and allowed a more complete
picture to be revealed about the evolution of the band gap of
TiO2 clusters as a function of size.

2. Experimental Method
The experiments were carried out using a magnetic-bottle PES
apparatus equipped with a laser vaporization cluster source, details of
which have been described previously.28 Briefly, TimOn- clusters were
produced by laser vaporization of a pure Ti disk target in the presence
of a He carrier gas seeded with 0.5% O2 and analyzed using a time-
of-flight mass spectrometer. The TimOn- cluster distributions depended
on the O2 content in the carrier gas.13 Under the current experimental
conditions, the TimOn- clusters were dominated by the (TiO2)n- and
oxygen-rich (TiO2)nO- clusters, with very weak contributions from more
O-rich species, such as (TiO2)nO2- or (TiO2)nO3-.13 This characteristic
mass pattern allowed for clean mass selection for the (TiO2)n- species,
despite the potential mass degeneracy between (TiO2)n- and (TiO2)n-1O5-.
The (TiO2)n- (n ) 1-10) species of current interest were each mass-
selected and decelerated before being photodetached at two photon
energies, 193 nm (6.424 eV) and 157 nm (7.866 eV). Effort was made
to control cluster temperatures and to choose colder clusters for
photodetachment, which has proved essential for obtaining high-quality
PES data.27 Photoelectrons were collected at nearly 100% efficiency
by the magnetic bottle and analyzed in a 3.5 m long electron flight
tube. PES spectra were calibrated using the known spectrum of Au-,
and the energy resolution of the PES apparatus was ∆Ek/Ek ≈ 2.5%, Figure 1. Photoelectron spectra of (TiO2)n- (n ) 1-10) at 193 nm (6.424
that is, ∼25 meV for 1 eV electrons. eV) and 157 nm (7.866 eV). The 193 nm spectra are shown as insets. Only
the X band is shown for the 193 nm spectra, and the higher binding energy
3. Experimental Results side is cut off for clarity.

Figure 1 displays the PES spectra of (TiO2)n- (n ) 1-10) binding energy features are observed for n < 4 at 193 nm and
taken at 193 and 157 nm, where the 193 nm spectra are shown are cut off in Figure 1 for clarity. Each (TiO2)n- cluster exhibits
as insets for the lowest binding energy feature only. Higher a weak low-binding-energy PES band (X), followed by an
energy gap and more intense and congested PES features at
(25) Busani, R.; Folkers, M.; Cheshnovsky, O. Phys. ReV. Lett. 1998, 81, 3836. higher binding energies. A second band (A) can be clearly
(26) Thomas, O. C.; Zheng, W.; Xu, S.; Bowen, K. H. Phys. ReV. Lett. 2002,
89, 213403. resolved for n ) 1 and 2, but it appears to broaden and becomes
(27) (a) Wang, L. S.; Li, X. In Clusters and Nanostructure Interfaces; Jena, P.,
Khanna, S. N., Rao, B. K., Eds.; World Scientific: River Edge, NJ, 2000;
pp 293-300. (b) Akola, J.; Manninen, M.; Hakkinen, H.; Landman, U.; (28) (a) Wang, L. S.; Cheng, H. S.; Fan, J. J. Chem. Phys. 1995, 102, 9480. (b)
Li, X.; Wang, L. S. Phys. ReV. B 1999, 60, R11297. (c) Wang, L. S.; Li, Wang, L. S.; Wu, H. In AdVances in Metal and Semiconductor Clusters,
X.; Zhang, H. F. Chem. Phys. 2000, 262, 53. (d) Zhai, H. J.; Wang, L. S.; Vol. 4, Cluster Materials; Duncan, M. A., Ed.; JAI Press: Greenwich, CT,
Alexandrova, A. N.; Boldyrev, A. I. J. Chem. Phys. 2002, 117, 7917. 1998; pp 299-343.

J. AM. CHEM. SOC. 9 VOL. 129, NO. 10, 2007 3023

ARTICLES Zhai and Wang

Table 1. Observed Adiabatic and Vertical Detachment Energies of

the Ti 3d-Derived Band (X) and O 2p-Derived Band (A) and the
Energy Gaps (Excitation Energies) from the Photoelectron Spectra
of (TiO2)n- (n ) 1-10)
Ti 3d band (X) O 2p band (A)
ADEa,b VDEa ADEa energy gapa
TiO2- 1.59(3)c 1.59(3)c 3.81(10) 2.22(10)
(TiO2)2- 2.06(5)d 2.27(5) 4.65(10) 2.59(10)
(TiO2)3- 2.78(10)d 3.15(5) 5.04(10) 2.26(10)
(TiO2)4- 3.00(15) 3.65(5) 5.60(15) 2.60(15)
(TiO2)5- 3.15(20) 4.13(10) 6.00(20) 2.85(20)
(TiO2)6- 3.20(20) 4.00(10) 6.20(20) 3.00(20)
(TiO2)7- 3.30(25) 4.20(15) 6.40(25) 3.10(25)
(TiO2)8- 3.5(3) 4.70(15) 6.6(3) 3.1(3)
(TiO2)9- 3.6(3) 4.75(15) 6.7(3) 3.1(3)
(TiO2)10- 3.6(3) 4.80(15) 6.7(3) 3.1(3)

a Energies are in electronvolts. Numbers in parentheses represent

estimated experimental uncertainties in the last digits. b The ADE of the
anions also represents the adiabatic electron affinity of the neutrals. c From
ref 13. d From reanalyses of the 355 and 266 nm PES data in ref 13.

a shoulder in the spectra for n > 2. The electron binding energies Figure 2. Observed adiabatic detachment energies (solid dots) for the Ti
increase rapidly with n, and the higher binding energy features 3d band and the O 2p band of (TiO2)n- (n ) 1-10). Previous theoretical
results are also shown for comparison. Key: (0) LUMO energies from ref
can no longer be reached at 193 nm for n > 4. Our previous
20; (O) adiabatic electron affinities from ref 22.
PES study at 193 nm was only able to show the onset of the A
band for n ) 3 and 4.13 The X band becomes broad, and its
relative intensity decreases with increasing cluster size. The
overall PES patterns for (TiO2)n- are characteristic of stable
closed-shell neutral species with a large gap between the highest
occupied (HOMO) and lowest unoccupied (LUMO) molecular
orbital.29-31 The extra electron in the (TiO2)n- anion occupies
the LUMO of the neutral cluster and yields the X band in the
PES spectra, whereas the A band corresponds to ionization of
the HOMO.
The adiabatic detachment energy (ADE) of the X band defines
the electron affinity (EA) of the neutral (TiO2)n clusters. The
EA of the TiO2 monomer was determined in our previous study
to be 1.59 ( 0.03 eV from vibrationally resolved PES spectra
at lower photon energies.13 However, for n > 1 no vibrational
structure could be resolved, and the ADEs were estimated by
drawing a straight line along the leading edge of the X band
and then adding the instrumental resolution to the intersections
with the binding energy axis. Although this was an approximate
procedure, we were able to obtain a consistent set of ADEs for
Figure 3. Observed energy gaps (b) of (TiO2)n- (n ) 1-10), as measured
band X of each species from the spectra taken at different photon from the ADE difference between bands X and A (Figures 1 and 2). The
energies, as given in Table 1. The ADEs for n ) 2-4 were TiO2 bulk limits (rutile, 3.0 eV; anatase, 3.2 eV) are shown as horizontal
also reported in our previous study.13 However, we reanalyzed dashed lines. Available theoretical results (4) from ref 22 are also shown
for comparison.
the previous data at lower photon energies in combination with
the current high-photon-energy data and obtained a set of more given in Table 1, were obtained from the maximum of the X
accurate ADEs (Table 1) for these species compared to those band. The measured ADEs and energy gaps are also plotted in
of the previous report. Because of the broad nature of the X Figures 2 and 3, respectively, in comparison with previous
band, relatively large uncertainties were associated with the calculations.
ADEs for the larger clusters.
The ADE for band A was obtained from the 157 nm data 4. Discussion
following the same procedure (Table 1). The ADE difference 4.1. General Spectral Assignments: Ti 3d- vs O 2p-
between the X and A bands defines the singlet to triplet Derived Features. Titanium has an electron configuration of
excitation energy in neutral (TiO2)n clusters, and it provides an 3d24s2. In TiO2, Ti has transferred its four valence electrons to
experimental measure for the HOMO-LUMO energy gaps O, and they each assume their favorite Ti4+ and O2- formal
(Table 1). The vertical detachment energies (VDEs), as also oxidation states. The chemical bonding between Ti and O in
(29) (a) Wang, X. B.; Ding, C. F.; Wang, L. S. J. Chem. Phys. 1999, 110, 8217.
the TiO2 bulk materials, and in the stoichiometric (TiO2)n
(b) Wang, X. B.; Woo, H. K.; Wang, L. S. J. Chem. Phys. 2005, 123, clusters as well,19 is strong with both ionic and covalent
051106. characters. In bulk TiO2, the O 2p orbitals form the valence
(30) Li, J.; Li, X.; Zhai, H. J.; Wang, L. S. Science 2003, 299, 864.
(31) Zhai, H. J.; Kiran, B.; Li, J.; Wang, L. S. Nat. Mater. 2003, 2, 827. band and the empty Ti sd orbitals from the conduction band
3024 J. AM. CHEM. SOC. 9 VOL. 129, NO. 10, 2007
(TiO2)n Electronic Structure and Band Gap Evolution ARTICLES

Table 2. Comparison of the Experimental Spectroscopic Data of

(TiO2)n- (n ) 1-3) with Theoretical Calculations from
Reference 18
ADEb VDEb energy gapb
symmetrya-c exptl theora exptl theora exptl theora
TiO2- C2V (0.00) 1.59 ( 0.03 1.58 1.59 ( 0.03 2.22 ( 0.10 2.35 Figure 4. Schematic lowest energy structures of (TiO2)n- (n ) 1-3) from
(TiO2)2- C3V (0.00) 2.06 ( 0.05 1.74 2.27 ( 0.05 1.92 2.59 ( 0.10 2.71 previous theoretical calculations (refs 10 and 15-24). Structure b is the
C2h (0.02) 1.28 1.33 3.48 global minimum for n ) 2.
(TiO2)3- Cs (0.00) 2.78 ( 0.10 2.31 3.15 ( 0.05 2.63 2.26 ( 0.10 2.52
C2 (1.15) 1.68 1.76 3.20 produces the 1A1 ground state of TiO2 (band X), whose ADE
C2V (1.25) 1.71 1.98 2.63 was calculated to be 1.58 eV at the DFT/LDA level (Table 2)18
a Reference 18. b All energies in electronvolts. c Numbers in parentheses
and 1.68, 1.62, and 1.60 eV at the B3LYP, BP86, and CCSD-
are relative energies with respect to the ground state. (T)//B3LYP levels,17 respectively. All these computational
results are in excellent agreement with the experimental data
with a band gap of 3.0 eV for rutile and 3.2 eV for anatase.1,5,6 (1.59 ( 0.03 eV, Table 2),13 thus confirming the identified anion
In the (TiO2)n- anion, the extra electron enters the predominantly and neutral ground states. The predicted energy gap (2.35 eV)18
Ti 3d-based LUMO of neutral (TiO2)n, which should evolve is also in good agreement with the experimental observation
into the conduction band of the bulk. The HOMO of the neutral (2.22 eV, Table 2).
(TiO2)n clusters derives primarily from O 2p orbitals and should 4.2.2. (TiO2)2-. Two main isomers, a C2h and a C3V structure
evolve into the bulk valence band. Photodetachment of the extra (Figure 4) have been located for the (TiO2)2 neutral. The C2h
electron from (TiO2)n- gives the weak lowest binding energy (1Ag) structure is the ground state, being 0.44 eV (DFT/LDA)18
feature (X), whereas all the features beyond the energy gap on or 0.85 eV (B3LYP)22 lower in energy than the C3V (1A1) isomer.
the higher binding energy side correspond to detachment from However, upon attachment of the extra electron in (TiO2)2-,
O 2p-derived MOs. Thus, regardless of the cluster size, the X the C3V anion (Figure 4b) becomes the global minimum with
band always comes from detachment of a lone 3d electron, the C2h anion (Figure 4c) slightly higher in energy by 0.02 eV
yielding the singlet ground electronic state of the corresponding at the DFT/LDA level (Table 2).18 As shown in Table 2, the
neutral (TiO2)n cluster. This is the main reason why the relative computed ADE, VDE, and energy gap for the C3V isomer are
intensity of the X band decreases with increasing cluster size. in good agreement with the experimental values, whereas those
The broad X band suggests that the addition of an electron into computed for the C2h isomer are all off in comparison to the
the LUMO of (TiO2)n induces a large geometry change. experiment. Thus, the current experimental data verify un-
Since all O 2p-derived MOs are occupied, both singlet and equivocally the C3V global minimum for (TiO2)2-.
triplet final excited states can be reached from one-electron It is interesting to speculate the reason for the energetic
detachment transitions. Thus, the A band in the PES spectra of differences between the C3V and C2h structures in the (TiO2)2
Figure 1 should represent the lowest triplet excited state of neutral and anion. In the C3V isomer, one Ti atom is tetracoor-
neutral (TiO2)n clusters. The ADE difference between the Ti dinated and the other Ti atom is tricoordinated (Figure 4b). The
3d-derived band X and the O 2p-derived band A represents extra electron should be localized on the tricoordinated Ti atom
strictly the lowest triplet excitation energy of the (TiO2)n clusters, in the C3V (TiO2)2-. On the other hand, the two Ti atoms are
which is also an experimental measure of the HOMO-LUMO equivalent in the C2h isomer, and the extra electron has to be
energy gap (Table 1).29-31 Note that the lowest triplet excitation shared or delocalized over the two Ti atoms. The stability for
energy of the (TiO2)n clusters is the molecular analogue of the the C3V isomer in the (TiO2)2- anion suggests that the extra
band gap of bulk TiO2. electron prefers to be localized on one Ti atom. In fact, the C3V
4.2. Comparison with Available Theoretical Calcula- (TiO2)2- can be considered to contain a Ti4+ and a Ti3+, the
tions: (TiO2)n- (n ) 1-3). There have been numerous latter being the most common and important defect site in bulk
theoretical calculations on the smaller (TiO2)n- (n ) 1-3) TiO2 surfaces. Thus, the C3V (TiO2)2- may be viewed as the
clusters, making it possible to compare with the current simplest cluster to model a Ti3+ defect site.
experimental data to verify their structures.10,15-24 In particular, 4.2.3. (TiO2)3-. Both (TiO2)3 and (TiO2)3- have been
Albarret et al.18 have carried out detailed density functional predicted to adopt Cs symmetry as the ground states (Figure
theory (DFT) calculations and computed the ADEs, VDEs, and 4d).18 Alternative C2 and C2V structures are substantially higher
energy gaps for n ) 1-3, which are compared with the in energy (Table 2). Indeed, the computed ADE, VDE, and
experimental data in Table 2. energy gap for the Cs (TiO2)3- are in good agreement with the
4.2.1. TiO2-. The TiO2- monomer has been discussed in current experiment, whereas those predicted for the C2 and C2V
detail in our previous study.13 It is discussed here again in light isomers differ significantly from the experimental measurements.
of the new experimental and theoretical results, as well as It is interesting to note that the Cs (TiO2)3- also contains a
providing a reference for the larger clusters. Both TiO2 and tricoordinated Ti site (Figure 4d), where the extra electron is
TiO2- have been studied extensively.8,10,12,13,15-24 TiO2 has a supposedly localized, similar to the C3V (TiO2)2- (Figure 4b).
C2V (1A1) ground state with a bond angle of 113 ( 5°.12 Its 4.3. Band Gap Evolution. Figure 2 shows the ADE trends
HOMO (6b2) is primarily O-centered with slight O-O anti- for both bands X and A as a function of cluster size, whereas
bonding character, whereas its LUMO (10a1) is basically a Figure 3 displays the evolution of the observed energy gaps.
nonbonding orbital of Ti 3d character. In the TiO2- anion, the Available computational data from the literature20,22 are also
extra electron enters the 10a1 LUMO of the neutral, resulting plotted in the figures for comparison. The ADE of the X band
in a doublet C2V (2A1) anion ground state with an increased bond displays a rapid increase from n ) 1 to n ) 3 and appears to
angle (128 ( 5°).12 The removal of the extra electron in TiO2- level off for n > 3. The calculated EAs of (TiO2)n (n ) 2-9)

J. AM. CHEM. SOC. 9 VOL. 129, NO. 10, 2007 3025

ARTICLES Zhai and Wang

from ref 22 and the LUMO orbital energies of (TiO2)n (n ) around this atom. Similar broad PES features were observed in
1-8) from ref 20 exhibit the same overall trend as the current our previous work on (SiO2)n- clusters,32 in which the extra
PES data. As discussed above, for n ) 2 and 3 the extra electron electron in the anions is well-characterized to be localized on a
in the (TiO2)n- anion seems to prefer to be localized on a single single Si site. Furthermore, our recent preliminary PES study
tricoordinated Ti site (Figure 4). The leveling off of the binding on (V2O5)n- (n ) 2-4) clusters has shown that there is a
energies of the extra electron in the large clusters suggests that significant spectral broadening from (V2O5)2- to (V2O5)3- and
a similar tricoordinated site may exist to accommodate the extra (V2O5)4-, which is perfectly in line with a previous theoretical
electron. This conjecture is supported by the calculated struc- prediction of a delocalized-to-localized electron transition in the
tures.22 same cluster sizes.33
ADEs for band A appear to increase faster than those for The highly localized nature of the extra electron in (TiO2)n-
band X, thus opening up the energy gap with increasing size, or the LUMO in (TiO2)n should have important implications
as shown in Figure 3. The energy gap displays an even-odd for TiO2 bulk materials and surfaces. First of all, in each
alternation from n ) 1 to n ) 4 and then a rapid increase from (TiO2)n- anion the localization of the extra electron means that
n ) 3 to n ) 6. Surprisingly, the energy gap already reaches it contains a Ti3+ site, which is equivalent to the F-center defect
the bulk limit at n ) 6 and stays nearly constant up to n ) 10 in bulk TiO2. The TiO2 surface chemistry is also dominated
within our experimental uncertainties. Singlet-triplet excitation
by the presence of Ti3+ sites.1,2 Thus, the (TiO2)n- clusters
energies, which correspond exactly to the measured energy gaps
may be considered as good molecular models for the Ti3+
plotted in Figure 3, have been calculated in ref 22 and are also
centers on the TiO2 surfaces. Furthermore, the bulk exciton
plotted in Figure 3. Except for the trend from n ) 2 to n ) 3,
in TiO2 involves an electron-hole pair due to the excitation
the theoretical results seem to differ significantly from the
of an electron from the valence band to the conduction
experiment. The discrepancy may be partly due to the fact that
band. The localization of the conduction electron on a single
the calculations were done for the global minimum of the neutral
Ti site is probably the reason why TiO2 has a very small exciton
(TiO2)n clusters, which may be different from those of the
radius.
anions, as is the case for n ) 2. However, the even-odd
alternation in the band gaps for n ) 1-4 (Figure 3) has actually
5. Conclusions
been predicted by several previous theoretical calculations.18,20,22
In particular, Albaret et al.18 predicted the correct trend in their In conclusion, we have investigated the electronic properties
calculated excitation energies for n ) 1-3 within ∼0.1-0.3
of a series of titanium dioxide clusters, (TiO2)n- (n ) 1-10),
eV of the experimental values (Table 2).
using photoelectron spectroscopy. A clear energy gap is
The rapid approach to the bulk band gap in the TiO2 clusters observed in the PES spectra of each cluster species, which
at n ) 6 is a surprise. The small clusters are molecular-like, feature a weak leading Ti 3d-based band at low binding energies
but the cluster at n ) 10 has a dimension of ∼1 nm, which is followed by an energy gap and more intense O 2p-based bands
expected to exhibit a quantum confinement effect,7 i.e., an at high binding energies. Major size dependence of the binding
enlarged band gap relative to that of the bulk. The current energies of the Ti 3d- and O 2p-derived bands is observed only
observation is consistent with previous optical experiments on for the small clusters in the size range from n ) 1 to n ) 6.
TiO2 nanoparticles,6 which showed no quantum confinement
The energy gap is observed to approach the bulk limit at n )
effect down to nanoparticles with ∼1 nm radius. This observa-
6 and remains nearly constant for n ) 6-10 within the
tion was understood on the basis of the small exciton radius of
experimental uncertainties. The broad ground-state PES features
TiO2 (∼1 nm or less).6 Quantum confinement is expected only
observed are attributed to the localized nature of the extra
when the nanoparticle size is smaller than the exciton radius.7
electron in the (TiO2)n- clusters. Considering the importance
The small exciton radius of bulk TiO2 leaves little room to
of TiO2 and the dearth of experimental data on titanium oxide
explore the quantum confinement effects in TiO2 nanocrystals.
clusters, the current spectroscopic data may be valuable to verify
Hence, quite possibly (TiO2)n and (TiO2)n- clusters reported in
future high-level theoretical calculations.
the present work represent the only size region where size-
dependent electronic and optical properties may be expected
Acknowledgment. This work was supported by the Chemical
for TiO2 clusters and nanocrystals.
Sciences, Geosciences and Biosciences Division, Office of Basic
4.4. Electron Localization in (TiO2)n- Clusters. As dis- Energy Sciences, U.S. Department of Energy (DOE), under
cussed in section 4.2, the extra electron in the (TiO2)2- and Grant No. DE-FG02-03ER15481 (catalysis center program) and
(TiO2)3- clusters is localized on a single tricoordinated Ti site. was performed at the W. R. Wiley Environmental Molecular
The EA trend shown in Figure 2 also suggests that the extra
Sciences Laboratory, a national scientific user facility sponsored
electron may be localized on a similar Ti site in the larger
by DOE’s Office of Biological and Environmental Research
clusters. Further evidence for the localization of the extra
and located at Pacific Northwest National Laboratory, operated
electron in the (TiO2)n- clusters is hinted by the X band shape
for DOE by Battelle.
in the PES spectra (Figure 1). The width of the X band increases
with size and become very broad in the larger clusters, JA068601Z
suggesting a large geometry change from the anion to the neutral
ground states. This large geometry change is related to the (32) Wang, L. S.; Nicholas, J. B.; Dupuis, M.; Wu, H.; Colson, S. D. Phys.
localized nature of the extra 3d electron on a single Ti site, ReV. Lett. 1997, 78, 4450.
(33) Asmis, K. R.; Santambrogio, G.; Brummer, M.; Sauer, J. Angew. Chem.,
which is expected to significantly alter the bonding environment Int. Ed. 2005, 44, 3122.

3026 J. AM. CHEM. SOC. 9 VOL. 129, NO. 10, 2007