Journal ArticleDOI
Rotational Diffusion Tensor of Liquid Methylene Chloride from Its Infrared Spectrum
TLDR
The rotational motion of the three inertial axes of liquid methylene chloride (CH2Cl2, point group C2υ) has been studied by computing the autocorrelation functions through the Fourier inversion of the observed band contours as discussed by the authors.Abstract:
The rotational motion of the three inertial axes of liquid methylene chloride (CH2Cl2, point group C2υ) has been studied by computing the autocorrelation functions through the Fourier inversion of the observed band contours. Three fundamentals [symmetry species a1 (283 cm−1), b1 (895 cm−1), and b2 (1265.5 cm−1)], as well as three summation bands [symmetry species b1 (2308 cm−1, 2414 cm−1) and b2 (2688 cm−1)], one overtone [symmetry species a1 (2525 cm−1)], and one difference band [symmetry species b2 (452 cm−1)], were investigated. The experimental results indicate that the liquid‐phase molecules do not obey Debye‐type diffusion but, on the contrary, are able to make orientational jumps of 27° – 38° around their inertial axes. The decay of the coherence of the rotational motion takes between 0.6 × 10−12 and 1.1 × 10−12 sec. Further‐more, the anisotropy of the rotational motion in the liquid is observed to be about the same as that of freely rotating CH2Cl2 molecules. The results imply that rotational moti...read more
Citations
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Raman Scattering: Orientational Motions in Liquids
TL;DR: In this paper, a systematic study of reorientational motions by Raman scattering is undertaken for 10 liquids and the theory of orientational broadening of Raman lines is presented with emphasis on the use of symmetry of molecular vibrations to obtain information of reoriented motions about different axes.
Journal ArticleDOI
Depolarized Rayleigh scattering and 13C NMR studies of anisotropic molecular reorientation of aromatic compounds in solution
TL;DR: In this article, the viscosity dependence of reorientation times about the individual molecular axes has been measured for benzene, mesitylene, toluene, and nitrobenzene.
Journal ArticleDOI
Depolarized Rayleigh scattering and orientational relaxation of molecules in solution. I. Benzene, toluene, and para‐xylene
TL;DR: In this article, a plot of reorientational relaxation time of each solute versus solution viscosity was found to fit a straight line with nonzero intercept, and the slopes of the lines were compared with those predicted by the Stokes-Einstein relation.
Journal ArticleDOI
Temperature dependent Raman study of molecular motions and interactions of CH3 I in the liquid phase
TL;DR: In this article, the polarized and depolarized components of the 524 cm−1 Raman band in liquid methyl iodide were measured between 196 and 300°K and the temperature dependence of the isotropic correlation times was opposite to that predicted by current theories of vibrational relaxation and collisional broadening.
Journal ArticleDOI
Intermolecular vibrational relaxation in liquids
TL;DR: In this paper, the influence of intermolecular vibrational relaxation on dipole moment correlation functions, as obtained from IR band shapes, is discussed, and the implications for various procedures used to “correct” Raman and IR band shape for vibrational relaxations are discussed.
References
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Journal ArticleDOI
Intensities and Shapes of Infrared Absorption Bands of Substances in the Liquid Phase
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Molecular Motion in Infrared and Raman Spectra
TL;DR: In this article, the Fourier transformation of infrared and Raman band shapes reveals the meaning of the spectrum in terms of molecular rotation much more clearly than does the usual frequency shape.
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Infrared Study of Liquids. I. The Theory of the ir Spectra of Diatomic Molecules in Inert Solutions
S. Bratŏz,J. Rios,Y. Guissani +2 more
TL;DR: In this article, a stochastic-type theory related to similar theories of the NMR spectra is proposed to explain the ir spectra of inert solutions of diatomic molecules, which predicts the existence of a continuous sequence of band forms comprising, among others, the profile with P and R type wings, the Lorentzian profile, the Gaussian profile, Voigt profile and several sorts of asymmetric profiles.
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Molecular Motion and the Moment Analysis of Molecular Spectra. III. Infrared Spectra
TL;DR: In this paper, the shape of infrared rotation-vibration bands is analyzed theoretically in terms of their moments, and explicit expressions are given for the third and fourth moments of interacting almost classical rigid asymmetric rotors, with respect to functions of intermolecular torques, the temperature, the principal moments of inertia and the polarization direction of the transition.