Assessment of modemixing and HerzbergTeller effects on twophoton absorption and resonance hyperRaman spectra from a timedependent approach
Abstract
A timedependent approach is presented to simulate the twophoton absorption (TPA) and resonance hyperRaman scattering (RHRS) spectra including Duschinsky rotation (modemixing) and HerzbergTeller (HT) vibronic coupling effects. The computational obstacles for the excitedstate 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 excitedstate energy derivative approaches in the framework of timedependent density functional theory. The excitedstate potential curvatures are evaluated at different levels of approximation to inspect the effects of frequency differences, modemixing and HT on TPA and RHRS spectra. Two types of molecules, one with high symmetry (formaldehyde, pdifluorobenzene, and benzotrifluoride) and the other with noncentrosymmetry (cishydroxybenzylidene2,3dimethylimidazolinone in the deprotonated anion state (HDBI{sup −})), are used as test systems. The calculated results reveal that it is crucial to adopt the exact excitedstate potential curvatures in the calculations of TPA and RHRS spectra even for the highsymmetric 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{sup −} although its one and twophoton transitions are strongly allowed, and its effect resultsmore »
 Authors:
 State Key Laboratory of Physical Chemistry of Solid Surfaces, Collaborative Innovation Center of Chemistry for Energy Materials, and Institute of Fujian Provincial Theoretical and Computational Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005 (China)
 (China)
 Publication Date:
 OSTI Identifier:
 22254999
 Resource Type:
 Journal Article
 Resource Relation:
 Journal Name: Journal of Chemical Physics; Journal Volume: 140; Journal Issue: 9; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
 Country of Publication:
 United States
 Language:
 English
 Subject:
 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION; COUPLING; CROSS SECTIONS; DENSITY FUNCTIONAL METHOD; DIPOLE MOMENTS; EXCITED STATES; PHOTONS; RAMAN EFFECT; RAMAN SPECTRA; SIMULATION; SOLVENTS; TIME DEPENDENCE
Citation Formats
Ma, HuiLi, Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, Zhao, Yi, and Liang, WanZhen, Email: liangwz@xmu.edu.cn. Assessment of modemixing and HerzbergTeller effects on twophoton absorption and resonance hyperRaman spectra from a timedependent approach. United States: N. p., 2014.
Web. doi:10.1063/1.4867273.
Ma, HuiLi, Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, Zhao, Yi, & Liang, WanZhen, Email: liangwz@xmu.edu.cn. Assessment of modemixing and HerzbergTeller effects on twophoton absorption and resonance hyperRaman spectra from a timedependent approach. United States. doi:10.1063/1.4867273.
Ma, HuiLi, Department of Chemical Physics, University of Science and Technology of China, Hefei 230026, Zhao, Yi, and Liang, WanZhen, Email: liangwz@xmu.edu.cn. Fri .
"Assessment of modemixing and HerzbergTeller effects on twophoton absorption and resonance hyperRaman spectra from a timedependent approach". United States.
doi:10.1063/1.4867273.
@article{osti_22254999,
title = {Assessment of modemixing and HerzbergTeller effects on twophoton absorption and resonance hyperRaman spectra from a timedependent approach},
author = {Ma, HuiLi and Department of Chemical Physics, University of Science and Technology of China, Hefei 230026 and Zhao, Yi and Liang, WanZhen, Email: liangwz@xmu.edu.cn},
abstractNote = {A timedependent approach is presented to simulate the twophoton absorption (TPA) and resonance hyperRaman scattering (RHRS) spectra including Duschinsky rotation (modemixing) and HerzbergTeller (HT) vibronic coupling effects. The computational obstacles for the excitedstate 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 excitedstate energy derivative approaches in the framework of timedependent density functional theory. The excitedstate potential curvatures are evaluated at different levels of approximation to inspect the effects of frequency differences, modemixing and HT on TPA and RHRS spectra. Two types of molecules, one with high symmetry (formaldehyde, pdifluorobenzene, and benzotrifluoride) and the other with noncentrosymmetry (cishydroxybenzylidene2,3dimethylimidazolinone in the deprotonated anion state (HDBI{sup −})), are used as test systems. The calculated results reveal that it is crucial to adopt the exact excitedstate potential curvatures in the calculations of TPA and RHRS spectra even for the highsymmetric 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{sup −} although its one and twophoton transitions are strongly allowed, and its effect results in an obvious blueshift of the TPA maximum with respect to the onephoton absorption maximum. With the HT and solvent effects getting involved, the simulated blueshift of 1291 cm{sup −1} agrees well with the experimental measurement.},
doi = {10.1063/1.4867273},
journal = {Journal of Chemical Physics},
number = 9,
volume = 140,
place = {United States},
year = {Fri Mar 07 00:00:00 EST 2014},
month = {Fri Mar 07 00:00:00 EST 2014}
}

We present a new formulation of the timedependent theory of ResonanceRaman spectroscopy (TDRR). Particular attention has been devoted to the generality of the framework and to the possibility of including different effects (Duschinsky mixing, HerzbergTeller contributions). Furthermore, the effects of different harmonic models for the intermediate electronic state are also investigated. Thanks to the implementation of the TDRR procedure within a generalpurpose quantumchemistry program, both solvation and leading anharmonicity effects have been included in an effective way. The reliability and stability of our TDRR implementation are validated against our previously proposed and welltested timeindependent procedure. Practical applications are illustrated withmore »

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