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

Abstract

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{sup −})), 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{sup −} although its one- and two-photon transitions are strongly allowed, and its effect resultsmore » 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{sup −1} agrees well with the experimental measurement.« less

Authors:
 [1];  [2]; ;  [1]
  1. 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)
  2. (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, E-mail: liangwz@xmu.edu.cn. Assessment of mode-mixing and Herzberg-Teller effects on two-photon absorption and resonance hyper-Raman spectra from a time-dependent 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, E-mail: liangwz@xmu.edu.cn. Assessment of mode-mixing and Herzberg-Teller effects on two-photon absorption and resonance hyper-Raman spectra from a time-dependent 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, E-mail: liangwz@xmu.edu.cn. Fri . "Assessment of mode-mixing and Herzberg-Teller effects on two-photon absorption and resonance hyper-Raman spectra from a time-dependent approach". United States. doi:10.1063/1.4867273.
@article{osti_22254999,
title = {Assessment of mode-mixing and Herzberg-Teller effects on two-photon absorption and resonance hyper-Raman spectra from a time-dependent approach},
author = {Ma, HuiLi and Department of Chemical Physics, University of Science and Technology of China, Hefei 230026 and Zhao, Yi and Liang, WanZhen, E-mail: liangwz@xmu.edu.cn},
abstractNote = {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{sup −})), 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{sup −} 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{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 time-dependent theory of Resonance-Raman spectroscopy (TD-RR). Particular attention has been devoted to the generality of the framework and to the possibility of including different effects (Duschinsky mixing, Herzberg-Teller contributions). Furthermore, the effects of different harmonic models for the intermediate electronic state are also investigated. Thanks to the implementation of the TD-RR procedure within a general-purpose quantum-chemistry program, both solvation and leading anharmonicity effects have been included in an effective way. The reliability and stability of our TD-RR implementation are validated against our previously proposed and well-tested time-independent procedure. Practical applications are illustrated withmore » some closed- and open-shell medium-size molecules (anthracene, phenoxyl radical, benzyl radical) and the simulated spectra are compared to the experimental results. More complex and larger systems, not limited to organic compounds, can be also studied, as shown for the case of Tris(bipyridine)ruthenium(II) chloride.« less
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  • We use quantum molecular structure and spectroscopic thoughts of various possible vibronic interactions for the position space of two-electron geminal orbitals with Bloch sums. Our geminals have different degeneracy from one-electron molecular orbitals and are different from the momentum space of BCS free electrons. Based on Herzberg-Teller expansions, our consideration of the aspect of the Renner-Teller effect for cyclic boundary crystals (instead of the usual linear molecules) involves first-order vibronic interaction with isotope effects different from the second-order electron-phonon energy of BCS theory, bipolaron theory, etc. Our consideration of the Jahn-Teller effect with equal-minimum double-well potential leads to the intervalentmore » charge transfer between two degenerate vibrationally affected electronic structures. Our considerations of different style vibrations other than the antisymmetric vibration for the nearest neighbor (e.g., displaced oscillator, etc.) may possibly be related to the case of special chemical structures with special doping and special coherence length. Our simple structural illustrations of such different vibronic Renner-Teller, Jahn-Teller effects and intervalent charge transfer (of La{sub 2{minus}x}Sr{sub x}CuO{sub 4} and YBa{sub 2}Cu{sub 3}O{sub 7{minus}x}) may promote some possible thoughts of quantum chemical structures compared and mixed with the physical treatments of special high-T{sub c} superconductors. {copyright} {ital 1997} {ital The American Physical Society}« less
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