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Torsion-vibration coupling in methanol: The adiabatic approximation and intramolecular vibrational redistribution scaling

J. Chem. Phys. 125, 104313 (2006); doi:10.1063/1.2336431

Published 14 September 2006

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Trocia N. Clasp and David S. Perry
Department of Chemistry, The University of Akron, Akron, Ohio 44325-3601
The four-dimensional model Hamiltonian of Wang and Perry [J. Chem. Phys. 109, 10795 (1998)] is used to compare the approximate adiabatic separation of the torsion and CH stretches in methanol to an exact solution of the same Hamiltonian. The adiabatic approximation accounts for the pattern of the energy levels in the lowest torsional states, including the inverted tunneling splittings, but does not account for the pattern of systematic two- and four-fold near degeneracies at high torsional excitation. In the adiabatic basis, the nonadiabatic couplings mix the torsional and vibrational degrees of freedom and hence are a source for intramolecular vibrational redistribution (IVR). These IVR matrix elements are found to decrease by only a factor of 2 or 3 with each higher coupling order, in agreement with the results of Pearman and Gruebele [Z. Phys. Chem. Munich 214, 1439 (2000)]. This gentle scaling behavior, which contrasts with a steeper falloff with coupling order in more rigid molecules, points to a more important role for direct high-order couplings in torsional molecules. In this model, the scaling behavior derives from a single coupling term that is low order in the torsional angular momentum in combination with one-dimensional torsional functions that include contributions from many torsional angular momenta. ©2006 American Institute of Physics
History: Received 30 May 2006; accepted 19 July 2006; published 14 September 2006
Permalink: http://link.aip.org/link/?JCPSA6/125/104313/1
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KEYWORDS and PACS

Keywords
PACS
  • 34.50.Ez
    Rotational and vibrational energy transfer (atoms and molecules)
  • 34.10.+x
    General theories and models of atomic and molecular collisions and interactions including statistical theories, transition state, stochastic and trajectory models, etc
  • YEAR: 2006

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0021-9606 (print)   1089-7690 (online)
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