Assessment of mode-mixing and Herzberg-Teller effects on two-photon absorption and resonance hyper-Raman spectra from a time-dependent approach

被引:24
作者
Ma, HuiLi [1 ,2 ,3 ]
Zhao, Yi [1 ,2 ]
Liang, WanZhen [1 ,2 ]
机构
[1] Xiamen Univ, Collaborat Innovat Ctr Chem Energy Mat, State Key Lab Phys Chem Solid Surfaces, Xiamen 361005, Peoples R China
[2] Xiamen Univ, Inst Fujian Prov Theoret & Computat Chem, Coll Chem & Chem Engn, Xiamen 361005, Peoples R China
[3] Univ Sci & Technol China, Dept Chem Phys, Hefei 230026, Peoples R China
基金
美国国家科学基金会;
关键词
DENSITY-FUNCTIONAL THEORY; FRANCK-CONDON PRINCIPLE; FLUORESCENT PROTEINS; POLYATOMIC-MOLECULES; EXCITATION PROFILES; INCLUDING DUSCHINSKY; VIBRONIC TRANSITIONS; DYNAMICAL SYMMETRY; INTENSITY ANALYSIS; RESPONSE FUNCTIONS;
D O I
10.1063/1.4867273
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
A time-dependent approach is presented to simulate the two-photon absorption (TPA) and resonance hyper-Raman scattering (RHRS) spectra including Duschinsky rotation (mode-mixing) and Herzberg-Teller (HT) vibronic coupling effects. The computational obstacles for the excited-state geometries, vibrational frequencies, and nuclear derivatives of transition dipole moments, which enter the expressions of TPA and RHRS cross sections, are further overcome by the recently developed analytical excited-state energy derivative approaches in the framework of time-dependent density functional theory. The excited-state potential curvatures are evaluated at different levels of approximation to inspect the effects of frequency differences, mode-mixing and HT on TPA and RHRS spectra. Two types of molecules, one with high symmetry (formaldehyde, p-difluorobenzene, and benzotrifluoride) and the other with non-centrosymmetry (cis-hydroxybenzylidene-2,3-dimethylimidazolinone in the deprotonated anion state (HDBI-)), are used as test systems. The calculated results reveal that it is crucial to adopt the exact excited-state potential curvatures in the calculations of TPA and RHRS spectra even for the high-symmetric molecules, and that the vertical gradient approximation leads to a large deviation. Furthermore, it is found that the HT contribution is evident in the TPA and RHRS spectra of HDBI- although its one- and two-photon transitions are strongly allowed, and its effect results in an obvious blueshift of the TPA maximum with respect to the one-photon absorption maximum. With the HT and solvent effects getting involved, the simulated blueshift of 1291 cm(-1) agrees well with the experimental measurement. (C) 2014 AIP Publishing LLC.
引用
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页数:17
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