Active vs. spectator modes in nonadiabatic photodissociation dynamics of the hydroxymethyl radical via the 22A(3s) Rydberg state

Xie, Changjian; Guo, Hua

doi:10.1063/1.5017737

Title: Active vs. spectator modes in nonadiabatic photodissociation dynamics of the hydroxymethyl radical via the 2²A(3s) Rydberg state

Journal Article · 24 January 2018 · Journal of Chemical Physics

DOI: https://doi.org/10.1063/1.5017737 · OSTI ID:1511687

Xie, Changjian ^[1];

^[1]

Univ. of New Mexico, Albuquerque, NM (United States)

The choice of the active degrees of freedom (DOFs) is a pivotal issue in a reduced-dimensional model of quantum dynamics when a full-dimensional one is not feasible. Here, several five-dimensional (5D) models are used to investigate the nonadiabatic photodissociation dynamics of the hydroxymethyl (CH₂OH) radical, which possesses nine internal DOFs, in its lowest absorption band. A normal-mode based scheme is used to identify the active and spectator modes, and its predictions are confirmed by 5D quantum dynamical calculations. Furthermore our results underscore the important role of the CO stretching mode in the photodissociation dynamics of CH₂OH, originating from the photo-induced promotion of an electron from the half-occupied π*_CO antibonding orbital to a carbon Rydberg orbital.

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Research Organization:: Univ. of New Mexico, Albuquerque, NM (United States)

Sponsoring Organization:: USDOE Office of Science (SC); USDOE

Grant/Contract Number:: SC0015997

OSTI ID:: 1511687

Alternate ID(s):: OSTI ID: 1417942

Journal Information:: Journal of Chemical Physics, Vol. 148, Issue 4; ISSN 0021-9606

Publisher:: American Institute of Physics (AIP)Copyright Statement

Country of Publication:: United States

Language:: English

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