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Semiclassical variational transition state calculations for the reactions of H and D with thermal and vibrationally excited H 2
Author(s) -
Garrett Bruce C.,
Truhlar Donald G.,
Varandas A. J. C.,
Blais Normand C.
Publication year - 1986
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550180913
Subject(s) - chemistry , excited state , semiclassical physics , reaction rate constant , quantum tunnelling , transition state theory , potential energy surface , atomic physics , range (aeronautics) , thermal , atmospheric temperature range , rectangular potential barrier , thermodynamics , molecule , kinetics , condensed matter physics , quantum mechanics , physics , materials science , organic chemistry , composite material , quantum
We present calculations of the rate constants for the title reactions on a new accurate potential energy surface with a 9.65 kcal mol −1 barrier and a carefully fitted long‐range attraction. The low‐temperature thermal rate constant decreases from the previously calculated value, corresponding to a surface with a barrier of 9.80 kcal mol −1 , which is opposite to the direction of change expectedbecause of the change in barrier height. This demonstrates the sensitivity of tunneling contributions to more global characteristics of the surface. The excited‐state ( n = 1) rate constants alsochange slightly, but not nearly enough to settle the controversial disagreement of theory with experiment for these rate constants.