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Line merging in the OH and SH stretching vibrational Raman profiles of ethanol and ethanethiol in the liquid state due to conformational dynamics

Line merging in the OH and SH stretching vibrational Raman profiles of ethanol and ethanethiol in the liquid state due to conformational dynamics,10.1

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Line merging in the OH and SH stretching vibrational Raman profiles of ethanol and ethanethiol in the liquid state due to conformational dynamics  
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The isotropic OH and SH stretching vibrational Raman scattering profiles of ethanol and ethanethiol have been measured in n-alkane solution at different temperatures. The merging of the two lines with increasing temperature (particularly in the case of ethanol), corresponding to the different molecular conformations, is attributed essentially to an increase in the interconversion rate. By means of a statistical treatment of the conformational dynamics on the basis of a Markov process taking into account further possible line broadening mechanisms, the characteristic time constants of the isomerization reactions are approximately determined as (in 10-12 s) 4·4 at 293 K and 2·0 at 423 K in the case of ethanol, and 16 183 K and 5 at 333 K in the case of ethanethiol.
Journal: Molecular Physics - MOL PHYS , vol. 60, no. 3, pp. 691-699, 1987
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