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

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(A2Σ+) molecules by H2 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(X2Π) 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.

SUBMITTER: Zhao B 

PROVIDER: S-EPMC8440216 | biostudies-literature | 2021 Sep

REPOSITORIES: biostudies-literature

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Full-dimensional quantum stereodynamics of the non-adiabatic quenching of OH(A<sup>2</sup>Σ<sup>+</sup>) by H<sub>2</sub>.

Zhao Bin B   Han Shanyu S   Malbon Christopher L CL   Manthe Uwe U   Yarkony David R DR   Guo Hua H  

Nature chemistry 20210809 9

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<sup>2</sup>Σ<sup>+</sup>) molecules by H<sub>2</sub> molecules using full-dimen  ...[more]

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