TY - JOUR

T1 - Variational transition state theory with least-action tunneling calculations for the kinetic isotope effects in the Cl+H2 reaction

T2 - Tests of extended-LEPS, information-theoretic, and diatomics-in-molecules potential energy surfaces

AU - Tucker, Susan C.

AU - Truhlar, Donald G.

AU - Garrett, Bruce C.

AU - Isaacson, Alan D.

PY - 1985

Y1 - 1985

N2 - We apply conventional and variational transition state theory with least-action-ground-state and other transmission coefficients to calculate the rate constants and kinetic isotope effects for the reaction Cl+H 2→HCl+H. First we consider collinear reactions and compare the calculated results to accurate quantal results for a given potential energy surface. This tests the dynamical methods and shows that they are reliable enough for testing potential energy surfaces. We then make calculations for the three-dimensional reactions employing 11 potential energy surfaces that have been proposed in previous work. Seven of the surfaces are extended LEPS surfaces, as proposed by Persky, Klein, and Stern; Truhlar, Magnuson, and Garrett; and Valencich and co-workers; one is an information-theoretic-bond- order-plus-anti-Morse-bend surface (called AL/AB) proposed by Agmon, Levine, Truhlar, Magnuson, and Garrett; and the final three surfaces are a diatomics-in-molecules-plus-three-center-terms surface proposed by Baer and Last and two diatomics-in-molecules surfaces proposed by Isaacson and Muckerman. Three of the surfaces (the final surface of Persky, Klein, and Stern; the first surface of Truhlar, Magnuson, and Garrett; and the AL/AB surface-all of which have relatively symmetric saddle points) are shown to be more reasonable than the others for predicting the rate constants and the H2/D2 and the HD/DH kinetic isotope effects. The calculations also indicate that the room temperature rate constants are dominated by quantum mechanical tunneling.

AB - We apply conventional and variational transition state theory with least-action-ground-state and other transmission coefficients to calculate the rate constants and kinetic isotope effects for the reaction Cl+H 2→HCl+H. First we consider collinear reactions and compare the calculated results to accurate quantal results for a given potential energy surface. This tests the dynamical methods and shows that they are reliable enough for testing potential energy surfaces. We then make calculations for the three-dimensional reactions employing 11 potential energy surfaces that have been proposed in previous work. Seven of the surfaces are extended LEPS surfaces, as proposed by Persky, Klein, and Stern; Truhlar, Magnuson, and Garrett; and Valencich and co-workers; one is an information-theoretic-bond- order-plus-anti-Morse-bend surface (called AL/AB) proposed by Agmon, Levine, Truhlar, Magnuson, and Garrett; and the final three surfaces are a diatomics-in-molecules-plus-three-center-terms surface proposed by Baer and Last and two diatomics-in-molecules surfaces proposed by Isaacson and Muckerman. Three of the surfaces (the final surface of Persky, Klein, and Stern; the first surface of Truhlar, Magnuson, and Garrett; and the AL/AB surface-all of which have relatively symmetric saddle points) are shown to be more reasonable than the others for predicting the rate constants and the H2/D2 and the HD/DH kinetic isotope effects. The calculations also indicate that the room temperature rate constants are dominated by quantum mechanical tunneling.

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U2 - 10.1063/1.448851

DO - 10.1063/1.448851

M3 - Article

AN - SCOPUS:0001247117

VL - 82

SP - 4102

EP - 4119

JO - Journal of Chemical Physics

JF - Journal of Chemical Physics

SN - 0021-9606

IS - 9

ER -