Anisotropic Dissymmetry Factor, g: Theoretical Investigation on Single Molecule Chiroptical Spectroscopy

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• 作者：Masamitsu Wakabayashi ; Satoshi Yokojima ; Tuyoshi Fukaminato ; Ken-ichi Shiino ; Masahiro Irie ; Shinichiro Nakamura
• 刊名：Journal of Physical Chemistry A
• 出版年：2014
• 出版时间：July 10, 2014
• 年：2014
• 卷：118
• 期：27
• 页码：5046-5057
• 全文大小：441K
• ISSN：1520-5215

文摘

A formula for an anisotropic dissymmetry factor g evaluating the chiroptical response of orientationally fixed molecules is derived. Incorporating zeroth- and first-order multipole expansion terms, it is applied to bridged triarylamine helicene molecules to examine the experimental results of single-molecule chiroptical spectroscopy. The ground- and excited-state wave functions and a series of transition moments required for the evaluation of the anisotropic g value are calculated using time-dependent density functional theory (TDDFT). The probability histograms obtained for simulated g values, uniformly sampled in regard to the direction of light propagation toward the fixed molecule, show that even for a given diastereomer, the dissymmetry factors have positive and negative values and can deviate from their averages to a considerable extent when the angle between the electric dipole transition moment and the propagation vector of the incident light is near 0 or 180掳.