標題: Solute-solvent intermolecular vibronic coupling as manifested by the molecular near-field effect in resonance hyper-Raman scattering
作者: Shimada, Rintaro
Hamaguchi, Hiro-o
應用化學系
應用化學系分子科學碩博班
Department of Applied Chemistry
Institute of Molecular science
公開日期: 21-一月-2011
摘要: Vibronic coupling within the excited electronic manifold of the solute all-trans-beta-carotene through the vibrational motions of the solvent cyclohexane is shown to manifest as the "molecular near-field effect," in which the solvent hyper-Raman bands are subject to marked intensity enhancements under the presence of all-trans-beta-carotene. The resonance hyper-Raman excitation profiles of the enhanced solvent bands exhibit similar peaks to those of the solute bands in the wavenumber region of 21 700-25 000 cm(-1) (10 850-12 500 cm(-1) in the hyper-Raman exciting wavenumber), where the solute all-trans-beta-carotene shows a strong absorption assigned to the 1A(g) -> 1B(u) transition. This fact indicates that the solvent hyper-Raman bands gain their intensities through resonances with the electronic states of the solute. The observed excitation profiles are quantitatively analyzed and are successfully accounted for by an extended vibronic theory of resonance hyper-Raman scattering that incorporates the vibronic coupling within the excited electronic manifold of all-trans-beta-carotene through the vibrational motions of cyclohexane. It is shown that the major resonance arises from the B-term (vibronic) coupling between the first excited vibrational level (v = 1) of the 1B(u) state and the ground vibrational level (v = 0) of a nearby A(g) state through ungerade vibrational modes of both the solute and the solvent molecules. The inversion symmetry of the solute all-trans-beta-carotene is preserved, suggesting the weak perturbative nature of the solute-solvent interaction in the molecular near-field effect. The present study introduces a new concept, " intermolecular vibronic coupling," which may provide an experimentally accessible/theoretically tractable model for understanding weak solute-solvent interactions in liquid. (C) 2011 American Institute of Physics. [doi:10.1063/1.3512923]
URI: http://dx.doi.org/10.1063/1.3512923
http://hdl.handle.net/11536/25871
ISSN: 0021-9606
DOI: 10.1063/1.3512923
期刊: JOURNAL OF CHEMICAL PHYSICS
Volume: 134
Issue: 3
結束頁: 
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  1. 000286472200057.pdf