Statistical-diabatic model for state-selected reaction rates. Theory and application of vibrational-mode correlation analysis to OH(nOH) +H2(nHH)→H2O+H

Donald G. Truhlar, Alan D. Isaacson

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Abstract

The state-selected reaction rates OH(nOH = 0,1) + H 2(nHH = 0,1)→H2O + H are calculated by an extension of variational transiton state theory. The reactant vibrational modes are assumed to correlate diabatically with generalized normal modes of a generalized activated complex. Using the Walch-Dunning-Schatz-Elgersma ab initio potential energy surface, the theory predicts that excitation of H2 is 19-68 times more effective than excitation of OH in promoting reaction at 300 K, where the range of values corresponds to different possible assumptions about the quantal effects on reaction-coordinate motion. These values are in much better agreement with the experimental value (about 100) than is a calculation based on the conventional transition state, which yields 2 × 104.

Original languageEnglish (US)
Pages (from-to)3516-3522
Number of pages7
JournalThe Journal of chemical physics
Volume77
Issue number7
DOIs
StatePublished - 1982

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