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Title: Mode specificity in the OH + CHD{sub 3} reaction: Reduced-dimensional quantum and quasi-classical studies on an ab initio based full-dimensional potential energy surface

Abstract

An initial state selected time-dependent wave packet method is applied to study the dynamics of the OH + CHD{sub 3} reaction with a six-dimensional model on a newly developed full-dimensional ab initio potential energy surface (PES). This quantum dynamical (QD) study is complemented by full-dimensional quasi-classical trajectory (QCT) calculations on the same PES. The QD results indicate that both translational energy and the excitation of the CH stretching mode significantly promote the reaction while the excitation of the umbrella mode has a negligible effect on the reactivity. For this early barrier reaction, interestingly, the CH stretching mode is more effective than translational energy in promoting the reaction except at very low collision energies. These QD observations are supported by QCT results. The higher efficacy of the CH stretching model in promoting this early barrier reaction is inconsistent with the prediction of the naively extended Polanyi’s rules, but can be rationalized by the recently proposed sudden vector projection model.

Authors:
;  [1];  [2];  [3];  [4]
  1. Key Laboratory of Magnetic Resonance in Biological Systems, National Center for Magnetic Resonance in Wuhan, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071 (China)
  2. Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371 (Singapore)
  3. School of Chemistry and Chemical Engineering, Chongqing University, Chongqing 400044 (China)
  4. Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 (United States)
Publication Date:
OSTI Identifier:
22657934
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 144; Journal Issue: 16; Other Information: (c) 2016 Author(s); Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ALIGNED COUPLING SCHEME; POTENTIAL ENERGY; REACTIVITY; SURFACES; TIME DEPENDENCE; WAVE PACKETS

Citation Formats

Song, Hongwei, E-mail: hwsong@wipm.ac.cn, Yang, Minghui, Lu, Yunpeng, Li, Jun, and Guo, Hua. Mode specificity in the OH + CHD{sub 3} reaction: Reduced-dimensional quantum and quasi-classical studies on an ab initio based full-dimensional potential energy surface. United States: N. p., 2016. Web. doi:10.1063/1.4947252.
Song, Hongwei, E-mail: hwsong@wipm.ac.cn, Yang, Minghui, Lu, Yunpeng, Li, Jun, & Guo, Hua. Mode specificity in the OH + CHD{sub 3} reaction: Reduced-dimensional quantum and quasi-classical studies on an ab initio based full-dimensional potential energy surface. United States. doi:10.1063/1.4947252.
Song, Hongwei, E-mail: hwsong@wipm.ac.cn, Yang, Minghui, Lu, Yunpeng, Li, Jun, and Guo, Hua. Thu . "Mode specificity in the OH + CHD{sub 3} reaction: Reduced-dimensional quantum and quasi-classical studies on an ab initio based full-dimensional potential energy surface". United States. doi:10.1063/1.4947252.
@article{osti_22657934,
title = {Mode specificity in the OH + CHD{sub 3} reaction: Reduced-dimensional quantum and quasi-classical studies on an ab initio based full-dimensional potential energy surface},
author = {Song, Hongwei, E-mail: hwsong@wipm.ac.cn and Yang, Minghui and Lu, Yunpeng and Li, Jun and Guo, Hua},
abstractNote = {An initial state selected time-dependent wave packet method is applied to study the dynamics of the OH + CHD{sub 3} reaction with a six-dimensional model on a newly developed full-dimensional ab initio potential energy surface (PES). This quantum dynamical (QD) study is complemented by full-dimensional quasi-classical trajectory (QCT) calculations on the same PES. The QD results indicate that both translational energy and the excitation of the CH stretching mode significantly promote the reaction while the excitation of the umbrella mode has a negligible effect on the reactivity. For this early barrier reaction, interestingly, the CH stretching mode is more effective than translational energy in promoting the reaction except at very low collision energies. These QD observations are supported by QCT results. The higher efficacy of the CH stretching model in promoting this early barrier reaction is inconsistent with the prediction of the naively extended Polanyi’s rules, but can be rationalized by the recently proposed sudden vector projection model.},
doi = {10.1063/1.4947252},
journal = {Journal of Chemical Physics},
number = 16,
volume = 144,
place = {United States},
year = {Thu Apr 28 00:00:00 EDT 2016},
month = {Thu Apr 28 00:00:00 EDT 2016}
}