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Title: Nonadiabatic Dynamics in Photodissociation of Hydroxymethyl in the 3 2 A(3p x ) Rydberg State: A Nine-Dimensional Quantum Study

Abstract

The nonadiabatic predissociation dynamics of the hydroxymethyl radical (CH2OH) in its 32A(3px) state is investigated using a nine-dimensional quantum mechanical model based on an ab initio three coupled diabatic state potential energy matrix. The calculated absorption spectrum, which is dominated by predissociative resonances, is in excellent agreement with experiment. The predissociation is facilitated by two conical intersection seams formed between the 32A(3px) and 22A(3s) states near the Franck–Condon region. The h and g vectors of energy minimized points on these seams are analyzed using the normal modes of the 32A equilibrium structure. The low-lying predissociative resonances have been assigned and their lifetimes are less than 100 fs and moderately mode specific. The absorption spectrum is dominated by a CO vibrational progression, due apparently to the promotion of an electron from the ground state antibonding πCO* orbital to the carbon Rydberg orbital, which effectively increases the C–O bond order.

Authors:
 [1];  [2]; ORCiD logo [3]; ORCiD logo [2]; ORCiD logo [1]
  1. Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131, United States
  2. Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, United States
  3. Institute of Theoretical and Computational Chemistry, Key Laboratory of Mesoscopic Chemistry, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center (NERSC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1530408
DOE Contract Number:  
SC0015997
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 123; Journal Issue: 10; Journal ID: ISSN 1089-5639
Country of Publication:
United States
Language:
English

Citation Formats

Xie, Changjian, Malbon, Christopher L., Xie, Daiqian, Yarkony, David R., and Guo, Hua. Nonadiabatic Dynamics in Photodissociation of Hydroxymethyl in the 3 2 A(3p x ) Rydberg State: A Nine-Dimensional Quantum Study. United States: N. p., 2019. Web. doi:10.1021/acs.jpca.8b12184.
Xie, Changjian, Malbon, Christopher L., Xie, Daiqian, Yarkony, David R., & Guo, Hua. Nonadiabatic Dynamics in Photodissociation of Hydroxymethyl in the 3 2 A(3p x ) Rydberg State: A Nine-Dimensional Quantum Study. United States. doi:10.1021/acs.jpca.8b12184.
Xie, Changjian, Malbon, Christopher L., Xie, Daiqian, Yarkony, David R., and Guo, Hua. Thu . "Nonadiabatic Dynamics in Photodissociation of Hydroxymethyl in the 3 2 A(3p x ) Rydberg State: A Nine-Dimensional Quantum Study". United States. doi:10.1021/acs.jpca.8b12184.
@article{osti_1530408,
title = {Nonadiabatic Dynamics in Photodissociation of Hydroxymethyl in the 3 2 A(3p x ) Rydberg State: A Nine-Dimensional Quantum Study},
author = {Xie, Changjian and Malbon, Christopher L. and Xie, Daiqian and Yarkony, David R. and Guo, Hua},
abstractNote = {The nonadiabatic predissociation dynamics of the hydroxymethyl radical (CH2OH) in its 32A(3px) state is investigated using a nine-dimensional quantum mechanical model based on an ab initio three coupled diabatic state potential energy matrix. The calculated absorption spectrum, which is dominated by predissociative resonances, is in excellent agreement with experiment. The predissociation is facilitated by two conical intersection seams formed between the 32A(3px) and 22A(3s) states near the Franck–Condon region. The h and g vectors of energy minimized points on these seams are analyzed using the normal modes of the 32A equilibrium structure. The low-lying predissociative resonances have been assigned and their lifetimes are less than 100 fs and moderately mode specific. The absorption spectrum is dominated by a CO vibrational progression, due apparently to the promotion of an electron from the ground state antibonding πCO* orbital to the carbon Rydberg orbital, which effectively increases the C–O bond order.},
doi = {10.1021/acs.jpca.8b12184},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
issn = {1089-5639},
number = 10,
volume = 123,
place = {United States},
year = {2019},
month = {2}
}