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Title: State-to-state mode selectivity in the HD + OH reaction: Perspectives from two product channels

Abstract

The state-to-state quantum dynamics (Jtot = 0) of the HD + OH(υ2 = 0,1) reaction is studied using a reactant coordinate based method, which allows the analysis of both the H + DOH and D + HOH channels with a single propagation. The stretching vibration of the newly formed bond, namely, the OD bond in DOH and one OH bond in HOH, is excited, thanks to its strong coupling with the reaction coordinate at the transition state. On the other hand, the vibrational energy deposited into the OH reactant (υ2 = 1) is sequestered during the reaction in the spectator OH mode. The combined effect leads to the excitation of both the OD and OH stretching modes in the DOH product, and the dominance of the (002) normal-mode state population in the HOH product, which in the local-mode picture corresponds to the excitation of both OH bonds with one quantum each. Lastly, the energy flow in this prototypical tetratomic reaction can be understood in terms of the sudden vector projection model.

Authors:
 [1]; ORCiD logo [2];  [1]
  1. Univ. of New Mexico, Albuquerque, NM (United States). Dept. of Chemistry and Chemical Biology
  2. Chinese Academy of Sciences (CAS), Dalian (China). Center for Theoretical and Computational Chemistry and State Key Lab. of Molecular Reaction Dynamics, Dalian Inst. of Chemical Physics
Publication Date:
Research Org.:
Univ. of New Mexico, Albuquerque, NM (United States)
Sponsoring Org.:
USDOE; National Natural Science Foundation of China (NNSFC)
OSTI Identifier:
1471509
Alternate Identifier(s):
OSTI ID: 1255312
Grant/Contract Number:  
FG02-05ER15694; 21222308; 21133006; 21433009
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 144; Journal Issue: 21; 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

Zhao, Bin, Sun, Zhigang, and Guo, Hua. State-to-state mode selectivity in the HD + OH reaction: Perspectives from two product channels. United States: N. p., 2016. Web. doi:10.1063/1.4952764.
Zhao, Bin, Sun, Zhigang, & Guo, Hua. State-to-state mode selectivity in the HD + OH reaction: Perspectives from two product channels. United States. doi:10.1063/1.4952764.
Zhao, Bin, Sun, Zhigang, and Guo, Hua. Tue . "State-to-state mode selectivity in the HD + OH reaction: Perspectives from two product channels". United States. doi:10.1063/1.4952764. https://www.osti.gov/servlets/purl/1471509.
@article{osti_1471509,
title = {State-to-state mode selectivity in the HD + OH reaction: Perspectives from two product channels},
author = {Zhao, Bin and Sun, Zhigang and Guo, Hua},
abstractNote = {The state-to-state quantum dynamics (Jtot = 0) of the HD + OH(υ2 = 0,1) reaction is studied using a reactant coordinate based method, which allows the analysis of both the H + DOH and D + HOH channels with a single propagation. The stretching vibration of the newly formed bond, namely, the OD bond in DOH and one OH bond in HOH, is excited, thanks to its strong coupling with the reaction coordinate at the transition state. On the other hand, the vibrational energy deposited into the OH reactant (υ2 = 1) is sequestered during the reaction in the spectator OH mode. The combined effect leads to the excitation of both the OD and OH stretching modes in the DOH product, and the dominance of the (002) normal-mode state population in the HOH product, which in the local-mode picture corresponds to the excitation of both OH bonds with one quantum each. Lastly, the energy flow in this prototypical tetratomic reaction can be understood in terms of the sudden vector projection model.},
doi = {10.1063/1.4952764},
journal = {Journal of Chemical Physics},
number = 21,
volume = 144,
place = {United States},
year = {2016},
month = {6}
}

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