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:
-
- 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. doi: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}
}
Web of Science
Figures / Tables:

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