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

Abstract

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.

Authors:
 [1]; ORCiD logo [1]
  1. Univ. of New Mexico, Albuquerque, NM (United States)
Publication Date:
Research Org.:
Univ. of New Mexico, Albuquerque, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1511687
Alternate Identifier(s):
OSTI ID: 1417942
Grant/Contract Number:  
SC0015997
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 148; Journal Issue: 4; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Xie, Changjian, and Guo, Hua. Active vs. spectator modes in nonadiabatic photodissociation dynamics of the hydroxymethyl radical via the 22A(3s) Rydberg state. United States: N. p., 2018. Web. https://doi.org/10.1063/1.5017737.
Xie, Changjian, & Guo, Hua. Active vs. spectator modes in nonadiabatic photodissociation dynamics of the hydroxymethyl radical via the 22A(3s) Rydberg state. United States. https://doi.org/10.1063/1.5017737
Xie, Changjian, and Guo, Hua. Wed . "Active vs. spectator modes in nonadiabatic photodissociation dynamics of the hydroxymethyl radical via the 22A(3s) Rydberg state". United States. https://doi.org/10.1063/1.5017737. https://www.osti.gov/servlets/purl/1511687.
@article{osti_1511687,
title = {Active vs. spectator modes in nonadiabatic photodissociation dynamics of the hydroxymethyl radical via the 22A(3s) Rydberg state},
author = {Xie, Changjian and Guo, Hua},
abstractNote = {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.},
doi = {10.1063/1.5017737},
journal = {Journal of Chemical Physics},
number = 4,
volume = 148,
place = {United States},
year = {2018},
month = {1}
}

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Cited by: 2 works
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Figures / Tables:

FIG. 1 FIG. 1: PESs for the ground and first excited states of CH2OH along the R and ϕ coordinates. The three coordinates (R, θ, ϕ) used in the 5D models are shown in the inset.

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