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Thermal and state‐selected rate constant calculations for O( 3 p ) + H 2 → OH + H and isotopic analogs
Author(s) -
Garrett Bruce C.,
Truhlar Donald G.
Publication year - 1986
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560290538
Subject(s) - reaction rate constant , kinetic isotope effect , semiclassical physics , excited state , chemistry , ab initio , parametrization (atmospheric modeling) , atomic physics , kinetic energy , quantum tunnelling , potential energy , intermolecular force , ab initio quantum chemistry methods , thermodynamics , physics , deuterium , quantum mechanics , molecule , kinetics , quantum , organic chemistry , radiative transfer
We present a new parametrization (based on ab initio calculations) of the bending potentials for the two lowest potential energy surfaces of the reaction O( 3 P ) + H 2 , and we use it for rate constant calculations by variational transition‐state theory with multidimensional semiclassical tunneling corrections. We present results for the temperature range 250–2400 K for both the rate constants and the intermolecular kinetic isotope effects for the reactions of O( 3 P ) with D 2 and HD. In general, the calculated rate constants for the thermal reactions are in excellent agreement with available experiments. We also calculate the enhancement effect for exciting H 2 to the first excited vibrational state. The calculations also provide information on which aspects of the potential energy surfaces are important for determining the predicted rate constants.