TiO2基态和激发态的几何结构、激发能和偶极矩

doi:10.3866/PKU.WHXB201304221

摘要/Abstract

摘要：

采用二阶微扰理论MP2、密度泛函B3LYP方法和含时密度泛函TD-B3LYP方法分别优化了TiO₂分子的基态¹A₁和六个激发态¹B₂、³B₂、¹B₁、³B₁、¹A₂和³A₂的几何结构. ¹A₁、¹B₂、³B₂、¹B₁和³B₁具有弯曲几何结构, ¹A₂和³A₂具有线性对称结构. 我们发现激发态¹B₂、³B₂、¹B₁和³B₁键偶极矩的数值大小顺序和相应的键角大小顺序完全一致. 另外, 采用完全活化空间自洽场(CASSCF)CASSCF(6,6)、CASSCF(8,8)、多参考组态相互作用(MRCI)和含时密度泛函TD-B3LYP 计算了TiO₂ 分子各激发态的垂直激发能和绝热激发能. 对¹B₂、³B₂和¹B₁三个态, MRCI/CASSCF(6,6) 计算的垂直激发能和绝热激发能与已有的实验值最接近. 对其他三个激发态³B₁、¹A₂和³A₂, 计算的激发能和文献报道的激发能计算值基本一致. 最后, 还计算了TiO₂分子的基态和激发态的偶极矩. 对¹A₁和¹B₂态, 偶极矩的计算值与已有的实验值相吻合. 采用原子偶极矩校正的Hirshfeld 布居方法计算了TiO₂分子在¹A₁、¹B₂、³B₂、¹B₁和³B₁态时各原子的电荷, 发现从基态到激发态偶极矩的变化与电荷从氧原子向钛原子的转移有关. 整个计算中还考察了基函数cc-pVDZ、cc-pVTZ和cc-pVQZ对计算结果的影响.

关键词: 二氧化钛, 几何结构, 垂直激发能, 绝热激发能, 偶极矩

Abstract:

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.

Key words: TiO₂, Geometrical structure, Vertical excitation energy, Adiabatic excitation energy, Dipole moment

MSC2000:

O641

韦美菊, 贾德强, 陈飞武. TiO₂基态和激发态的几何结构、激发能和偶极矩[J]. 物理化学学报, 2013, 29(07): 1441-1452.

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 Phys. -Chim. Sin., 2013, 29(07): 1441-1452.

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TiO₂基态和激发态的几何结构、激发能和偶极矩

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

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