INTERACTION OF TORSION AND OVERALL ROTATION IN P-CRESOL
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Date
1993
Journal Title
Journal ISSN
Volume Title
Publisher
Ohio State University
Abstract
The 1e-2e torsional band of the near prolate asymmetric rotor p-cresol shows a significantly broadened structure in comparison to the electronic origin 0a1-0a1. This broadening is due to an interaction between the torsional vibration of the methylgroup and the overall rotation of the molecule, which is absent in the case of the electronic $origin^{1}$. This interaction is strong, because the axis of internal rotation (z) and overall rotation (a) nearly coincide in the case of p-cresol. A simulation of the rotational band contour of the le-2e band, including this interaction leads to the following rotational constants [$cm^{-1}$]: $\begin{array}{lll}A^{\prime \prime}= 0.183603& B^{\prime \prime}= 0.048573& C^{\prime \prime}= 0.038685\\ A^{\prime} = 0.172803& B^{\prime} = 0.049173& C^{\prime} = 0.038525\end{array}$ Within the error these are the same rotational constants as obtained by simulation of the electronic origin Oai-Oai of p-cresol. A simulation of the le-2e band without consideration of the perturbation is only succesfull under the assumption of a very large change of the rotational constant A, which has no physical meaning.
Description
$^{1}$ M. Gerhards, B. Kimpfel, M. Pohl, M. Schmitt, K. Kleinermanns J. Mol. Struct. 270. 301 (1992)
Author Institution: Institut f\""{u}r physikalische Chemie, Heinriche Heine Universit\""{a}t
Author Institution: Institut f\""{u}r physikalische Chemie, Heinriche Heine Universit\""{a}t