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

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...

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Bibliographic Details
Published in:The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 2014-07, Vol.118 (27), p.5046-5057
Main Authors: Wakabayashi, Masamitsu, Yokojima, Satoshi, Fukaminato, Tuyoshi, Shiino, Ken-ichi, Irie, Masahiro, Nakamura, Shinichiro
Format: Article
Language:English
Subjects:
Anisotropy
Circular Dichroism
Density functional theory
Electric dipoles
Mathematical analysis
Models, Theoretical
Simulation
Spectroscopy
Spectrum Analysis - methods
Vectors (mathematics)
Wave functions
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Summary: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°.
ISSN:1089-5639
1520-5215
DOI:10.1021/jp409559t