title: Anisotropic dissymmetry factor, g: theoretical investigation on single molecule chiroptical spectroscopy.
abstract: 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°.
authors.affiliation: Department of Biomolecular Engineering, Tokyo Institute of Technology , 4259 Nagatsuta-cho, Midori-ku, Yokohama, Kanagawa 226-8501, Japan.
authors.forename: Masamitsu
authors.initials: M
authors.lastname: Wakabayashi
authors.forename: Satoshi
authors.initials: S
authors.lastname: Yokojima
authors.forename: Tuyoshi
authors.initials: T
authors.lastname: Fukaminato
authors.forename: Ken-ichi
authors.initials: K
authors.lastname: Shiino
authors.forename: Masahiro
authors.initials: M
authors.lastname: Irie
authors.forename: Shinichiro
authors.initials: S
authors.lastname: Nakamura
mesh_terms: D002942:Circular Dichroism; D008962:Models, Theoretical; D013057:Spectrum Analysis / Q000379:methods*