Theoretical Study of the Validity of the Born-Oppenheimer Approximation in the Cl + H 2 → HCl + H Reaction-Reference-Cited by-同舟云学术

Theoretical Study of the Validity of the Born-Oppenheimer Approximation in the Cl + H 2 → HCl + H Reaction

Published:2002-04-26 Issue:5568 Volume:296 Page:715-718
ISSN:0036-8075
Container-title:Science
language:en
Short-container-title:Science

Author:

Alexander Millard H.¹,Capecchi Gabriella²,Werner Hans-Joachim²

Affiliation:

1. Department of Chemistry and Biochemistry and Institute for Physical Sciences and Technology, University of Maryland, College Park, MD 20742–2021, USA.

2. Institüt für Theoretische Chemie, Universität Stuttgart, D-75069 Stuttgart, Germany.

Abstract

Reactivity of the excited spin-orbit state of Cl with H 2 to yield ground-state HCl products is forbidden by the Born-Oppenheimer (BO) approximation. We used new ab initio potential energy surfaces and exact quantum scattering calculations to explore the extent of electronic nonadiabaticity in this reaction. In direct contrast to recent experiments, we predict that the BO-allowed reaction of the ground spin-orbit state will be much more efficient than the BO-forbidden reaction of the excited spin-orbit state. Also, Coriolis coupling opens up an electronically nonadiabatic inelastic channel, which competes substantially with reaction.

Publisher

American Association for the Advancement of Science (AAAS)

Subject

Multidisciplinary

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