A SIMPLE FACTORIZATION SCHEME TO PREDICT IVR RATES IN MEDIUM-SIZED ORGANIC MOLECULES

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1998

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Ohio State University

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Other factors being equal, it has long been assumed that the IVR rate will decrease as the symmetry of the molecule increases. Recently, Callegari, et al. observed no trend: increasing rates of IVR in a progression from s-triazine to pyrrole to benzene in the first CH stretching overtone bands. The simple factorization method previously $developed^{a}$ has been applied to these systems. Using an anharmonic normal mode basis set for off-diagonal matrix element calculations and the MFD $method^{b}$, good agreement for the linewidths of pyrrole and s-triazine are obtained with only one adjustable parameter.

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$^{a}$xD. Madsen, R. Pearman, M. Gruebele, J. Chem. Phys. 106(14), 5874, (1997). $^{b}$ M. Gruebele, J. Phys. Chem. 100, 12183, (1996).
Author Institution: Department of Chemistry and Beckman Institute for Advanced Science and Technology, University of Illinois

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