Dynamic Kerr effect study on six-membered-ring molecular liquids: benzene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, cyclohexene, and cyclohexane

The Journal of Physical Chemistry. B
Shohei Kakinuma, Hideaki Shirota

Abstract

The intermolecular dynamics of five six-membered-ring molecular liquids having different aromaticities-benzene, 1,3-cyclohexadiene, 1,4-cyclohexadiene, cyclohexene, and cyclohexane-measured by femtosecond Raman-induced Kerr effect spectroscopy have been compared in this study. The line shapes of the Fourier transform low-frequency spectra, which arise from the intermolecular vibrational dynamics, are trapezoidal for benzene and 1,3-cyclohexadiene, triangular for 1,4-cyclohexadiene and cyclohexene, and monomodal for cyclohexane. The trapezoidal shapes of the low-frequency spectra of benzene and 1,3-cyclohexadiene are due to the librational motions of their aromatic planar structures, which cause damped nuclear response features. The time integrals of the nuclear responses of the five liquids correlate to the squares of the polarizability anisotropies of the molecules calculated on the basis of density functional theory. The first moments of the low-frequency spectra roughly linearly correlate to the bulk parameters of the square roots of the surface tensions divided by the densities and the square roots of the surface tensions divided by the molecular weights, but the plots for cyclohexene deviate slightly from the correlations....Continue Reading

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Citations

Jan 3, 2016·The Journal of Chemical Physics·Christopher M MacDermaidGiacomo Fiorin
Oct 24, 2020·Physical Chemistry Chemical Physics : PCCP·Kamil PolokAbdenacer Idrissi
Sep 21, 2018·The Journal of Physical Chemistry Letters·Masanari NagasakaNobuhiro Kosugi
Jul 12, 2018·The Journal of Physical Chemistry. B·Judith Reichenbach, Klaas Wynne

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