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Title: Full-dimensional quantum stereodynamics of the non-adiabatic quenching of OH(A2Σ+) by H2

Journal Article · · Nature Chemistry
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Abstract The Born–Oppenheimer approximation, assuming separable nuclear and electronic motion, is widely adopted for characterizing chemical reactions in a single electronic state. However, the breakdown of the Born–Oppenheimer approximation is omnipresent in chemistry, and a detailed understanding of the non-adiabatic dynamics is still incomplete. Here we investigate the non-adiabatic quenching of electronically excited OH(A 2 Σ + ) molecules by H 2 molecules using full-dimensional quantum dynamics calculations for zero total nuclear angular momentum using a high-quality diabatic-potential-energy matrix. Good agreement with experimental observations is found for the OH(X 2 Π) ro-vibrational distribution, and the non-adiabatic dynamics are shown to be controlled by stereodynamics, namely the relative orientation of the two reactants. The uncovering of a major (in)elastic channel, neglected in a previous analysis but confirmed by a recent experiment, resolves a long-standing experiment–theory disagreement concerning the branching ratio of the two electronic quenching channels.

Research Organization:
Univ. of New Mexico, Albuquerque, NM (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC)
Grant/Contract Number:
SC0015997
OSTI ID:
1812417
Journal Information:
Nature Chemistry, Journal Name: Nature Chemistry Journal Issue: 9 Vol. 13; ISSN 1755-4330
Publisher:
Nature Publishing GroupCopyright Statement
Country of Publication:
United Kingdom
Language:
English

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