Citation: WEI Mei-Ju, JIA De-Qiang, CHEN Fei-Wu. Geometric Structures, Excitation Energies and Dipole Moments of the Ground and Excited States of TiO₂[J]. Acta Physico-Chimica Sinica, ;2013, 29(07): 1441-1452. doi: 10.3866/PKU.WHXB201304221 shu

Geometric Structures, Excitation Energies and Dipole Moments of the Ground and Excited States of TiO₂

1.
School of Chemistry and Biological Engineering, University of Science and Technology Beijing, Beijing 100083, P. R. China

Received Date: 21 January 2013
Available Online: 22 April 2013
Fund Project: 国家自然科学基金(21173020) (21173020)中央高校基本科研业务费专项资金(FRF-TP-12-114A, FRF-BR-11-026B)资助项目 (FRF-TP-12-114A, FRF-BR-11-026B)

The geometries of the ground and excited states of titanium dioxide, ¹A₁, ¹B₂, ³B₂, ¹B₁, ³B₁, ¹A₂ and ³A₂, have been optimized using Møller-Plesset second-order perturbation theory, density functional theory B3LYP, and time-dependent density functional theory TD-B3LYP methods. ¹A₁, ¹B₂, ³B₂, ¹B₁ and ³B₁ have bent structures, while ¹A₂and ³A₂ have symmetrical linear structures. The bond angles of ¹B₂, ³B₂, ¹B₁ and ³B₁ correlate directly with the magnitudes of the corresponding bond dipole moments. Vertical and adiabatic excitation energies have been computed with complete active space self-consistent field (CASSCF) CASSCF(6,6), CASSCF(8,8), multi-reference configuration interaction (MRCI), and TD-B3LYP. For ¹B₂、³B₂and ¹B₁, the excitation energies calculated with MRCI/CASSCF(6,6) are much closer to the experimental values than the results calculated using other methods. For excited states ³B₁, ¹A₂ and ³A₂, excitation energies calculated with CASSCF(6,6), CASSCF(8,8), MRCI, and TD-B3LYP are almost consistent with theoretical results available in the literature. Dipole moments of the ground and excited states have been computed with B3LYP and TD-B3LYP. The calculated dipole moments of ¹A₁ and ¹B₂ agree well with experimental data. The atomic charges of TiO₂ in ground and excited states have been calculated with the atomic dipole moment corrected Hirshfeld population method. This calculation revealed that changes of dipole moments from the ground state to the excited states are related to electron transfer from the oxygen atom to the titanium atom. During the above calculations, the influences of the basis sets cc-pVDZ, cc-pVTZ, and cc-pVQZ were also investigated.
- TiO₂,
- Geometrical structure,
- Vertical excitation energy,
- Adiabatic excitation energy,
- Dipole moment
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通讯作者: 陈斌, bchen63@163.com

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沈阳化工大学材料科学与工程学院沈阳 110142

Geometric Structures, Excitation Energies and Dipole Moments of the Ground and Excited States of TiO2

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通讯作者: 陈斌, bchen63@163.com

Geometric Structures, Excitation Energies and Dipole Moments of the Ground and Excited States of TiO₂