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Title: Mode specificity in the OH + CHD3 reaction: Reduced-dimensional quantum and quasi-classical studies on an ab initio based full-dimensional potential energy surface

Abstract

Here, an initial state selected time-dependent wave packet method is applied to study the dynamics of the OH + CHD3 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 fulldimensional 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]; ORCiD logo [2];  [3];  [1];  [4]
  1. Chinese Academy of Sciences (CAS), Wuhan (China). Key Lab. of Magnetic Resonance in Biological Systems, National Center for Magnetic Resonance in Wuhan, State Key Lab. of Magnetic Resonance and Atomic and Molecular Physics and Wuhan Inst. of Physics and Mathematics
  2. Nanyang Technological Univ. (Singapore). Division of Chemistry and Biological Chemistry and School of Physical and Mathematical Sciences
  3. Chongqing Univ. (China). School of Chemistry and Chemical Engineering
  4. Univ. of New Mexico, Albuquerque, NM (United States). Dept. of Chemistry and Chemical Biology
Publication Date:
Research Org.:
Univ. of New Mexico, Albuquerque, NM (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Natural Science Foundation of China (NNSFC)
Contributing Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
OSTI Identifier:
1470767
Alternate Identifier(s):
OSTI ID: 1249620
Grant/Contract Number:  
FG02-05ER15694; 21373226
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 144; Journal Issue: 16; 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; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; bimolecular reactions; vibrational states; chemical elements; chemical kinetics and dynamics; zero point energy; transition state; potential energy surfaces; vibrational spectroscopy; collision energies; reaction probability

Citation Formats

Song, Hongwei, Lu, Yunpeng, Li, Jun, Yang, Minghui, and Guo, Hua. Mode specificity in the OH + CHD3 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, Lu, Yunpeng, Li, Jun, Yang, Minghui, & Guo, Hua. Mode specificity in the OH + CHD3 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, Lu, Yunpeng, Li, Jun, Yang, Minghui, and Guo, Hua. Wed . "Mode specificity in the OH + CHD3 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. https://www.osti.gov/servlets/purl/1470767.
@article{osti_1470767,
title = {Mode specificity in the OH + CHD3 reaction: Reduced-dimensional quantum and quasi-classical studies on an ab initio based full-dimensional potential energy surface},
author = {Song, Hongwei and Lu, Yunpeng and Li, Jun and Yang, Minghui and Guo, Hua},
abstractNote = {Here, an initial state selected time-dependent wave packet method is applied to study the dynamics of the OH + CHD3 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 fulldimensional 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 = {2016},
month = {4}
}

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