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

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	Assessment of mode-mixing and Herzberg-Teller effects on two-photon absorption and resonance hyper-Raman spectra from a time-dependent approach
	Ma, HuiLi ; Zhao, Yi ; Liang, WanZhen ; Zhao Y(赵仪) ; Liang WZ(梁万珍)
刊名	http://dx.doi.org/10.1063/1.4867273
	2014-03-07
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
英文摘要	National Science Foundation of China [21290193, 21373163]; National Basic Research Program of China [2011CB808501]; Ph.D. Programs Foundation of Ministry of Education of China; 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.
语种	英语
出版者	AMER INST PHYSICS
内容类型	期刊论文
源URL	[http://dspace.xmu.edu.cn/handle/2288/89356]
专题	化学化工－已发表论文
推荐引用方式 GB/T 7714	Ma, HuiLi,Zhao, Yi,Liang, WanZhen,et al. Assessment of mode-mixing and Herzberg-Teller effects on two-photon absorption and resonance hyper-Raman spectra from a time-dependent approach[J]. http://dx.doi.org/10.1063/1.4867273,2014.
APA	Ma, HuiLi,Zhao, Yi,Liang, WanZhen,赵仪,&梁万珍.(2014).Assessment of mode-mixing and Herzberg-Teller effects on two-photon absorption and resonance hyper-Raman spectra from a time-dependent approach.http://dx.doi.org/10.1063/1.4867273.
MLA	Ma, HuiLi,et al."Assessment of mode-mixing and Herzberg-Teller effects on two-photon absorption and resonance hyper-Raman spectra from a time-dependent approach".http://dx.doi.org/10.1063/1.4867273 (2014).