Theoretical studies of intersystem crossing effects in the O+H2 reaction

Mark R. Hoffmann, George C Schatz

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Abstract

A theory of intersystem crossing effects is developed that is applicable to atom-diatom and related chemical reactions where global potential energy surfaces can be developed. The theory is applied to singlet-triplet interactions in the reaction O(3P, 1D) + H2 → OH(2Π) + H. This theory uses quasiclassical trajectory surface-hopping methods to determine dynamical information based on a diabatic representation in which the usual nonrelativistic potential surfaces define the diagonal potentials, and matrix elements of the Breit-Pauli spin-orbit operator determine the couplings. A key result is that the spin-orbit matrix elements may be determined adequately using relatively low level theory such as complete active space self-consistent field methods, and with significant truncation of the electronic state basis set. In addition, the spin-orbit matrix elements is found to have a relatively simple dependence on internuclear geometry, such that determining global spin-orbit coupling surfaces is much easier than determining the Born-Oppenheimer surfaces.

Original languageEnglish
Pages (from-to)9456-9465
Number of pages10
JournalJournal of Chemical Physics
Volume113
Issue number21
DOIs
Publication statusPublished - Dec 2000

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ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

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