Abstract
Very detailed experimental studies of the isomerization of trans-stilbene in the S 1 excited electronic state show features which are not readily explained by current theory, e.g., of RRKM type. In this work the deuteration shifts seen in the series C 14H 12, C 14H 10D 2, C 14D 10H 2, C 14D 12, where in the middle two species the ethylenic bridge positions are listed last, are investi RRKM theory modified so as to allow for a finite energy transfer rate between a critical oscillator and the remaining modes of the molecule. Vibrational frequencies are estimated on the basis of experimental results for the ground state molecule with the help of a product rule for deuteration shifts.
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