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Quantum reactive scattering via the /ital S/-matrix version of the Kohn variational principle: Differential and integral cross sections for D+H/sub 2/ /r arrow/HD+H

Journal Article · · J. Chem. Phys.; (United States)
OSTI ID:5961397

A comprehensive survey of the quantum scattering methodology that results from applying the /ital S/-matrix version of the Kohn variational principle to the reactive scattering formulation given by Miller (J. Chem. Phys. /bold 50/, 407 (1969)) is presented. Results of calculations using this approach are reported for the reaction D+H/sub 2/ /r arrow/HD+H. The 3-d calculations include total angular momentum values from /ital J/=0 up to 31 in order to obtain converged integral and differential cross sections over a wide range of energy (0.4--1.35 eV total energy). Results are given for reaction probabilities for individual values of /ital J/, integral and differential cross sections for a number of energies, and state-to-state rate constants (i.e., a Boltzmann average over translational energy), and comparisons are made to a variety of different experimental results. A particularly interesting qualitative feature which is observed in the calculations is that the /ital energy//ital dependence/ of the differential cross section in the /ital backward/ /ital direction/ (/theta/=180/degree/) shows a resonance structure (due to a short-lived DH/sub 2/ collision complex) which is very similar to that in the /ital J/=0 reaction probability. This resonance structure does not appear in the energy dependence of the integral cross section, being averaged out by the sum over /ital J/.

Research Organization:
Department of Chemistry, University of California, and Materials and Chemical Sciences Division, Lawrence Berkeley Laboratory, Berkeley, California 94720 (US)
DOE Contract Number:
AC03-76SF00098
OSTI ID:
5961397
Journal Information:
J. Chem. Phys.; (United States), Journal Name: J. Chem. Phys.; (United States) Vol. 91:3; ISSN JCPSA
Country of Publication:
United States
Language:
English