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Title: Full-dimensional quantum dynamics study of the H{sub 2} + C{sub 2}H → H + C{sub 2}H{sub 2} reaction on an ab initio potential energy surface

Abstract

This work performs a time-dependent wavepacket study of the H{sub 2} + C{sub 2}H → H + C{sub 2}H{sub 2} reaction on a new ab initio potential energy surface (PES). The PES is constructed using neural network method based on 68 478 geometries with energies calculated at UCCSD(T)-F12a/aug-cc-pVTZ level and covers H{sub 2} + C{sub 2}H↔H + C{sub 2}H{sub 2}, H + C{sub 2}H{sub 2} → HCCH{sub 2}, and HCCH{sub 2} radial isomerization reaction regions. The reaction dynamics of H{sub 2} + C{sub 2}H → H + C{sub 2}H{sub 2} are investigated using full-dimensional quantum dynamics method. The initial-state selected reaction probabilities are calculated for reactants in eight vibrational states. The calculated results showed that the H{sub 2} vibrational excitation predominantly enhances the reactivity while the excitation of bending mode of C{sub 2}H slightly inhibits the reaction. The excitations of two stretching modes of C{sub 2}H molecule have negligible effect on the reactivity. The integral cross section is calculated with J-shift approximation and the mode selectivity in this reaction is discussed. The rate constants over 200-2000 K are calculated and agree well with the experimental measured values.

Authors:
 [1];  [2]; ;  [3];  [2];  [1];  [4]
  1. Key Laboratory of Magnetic Resonance in Biological Systems, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, National for Magnetic Resonance in Wuhan, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071 (China)
  2. (China)
  3. University of Chinese Academy of Sciences, Beijing 100049 (China)
  4. State Key Laboratory of Molecular Reaction Dynamics and Center for Theoretical Computational Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China)
Publication Date:
OSTI Identifier:
22658015
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 144; Journal Issue: 19; 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; COMPUTER CALCULATIONS; EXCITATION; EXPERIMENTAL DATA; HYDROGEN; INTEGRAL CROSS SECTIONS; NEURAL NETWORKS; POTENTIAL ENERGY; REACTION KINETICS; REACTIVITY; SURFACES; TIME DEPENDENCE; VIBRATIONAL STATES

Citation Formats

Chen, Liuyang, University of Chinese Academy of Sciences, Beijing 100049, Shao, Kejie, Chen, Jun, State Key Laboratory of Molecular Reaction Dynamics and Center for Theoretical Computational Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Yang, Minghui, E-mail: yangmh@wipm.ac.cn, and Zhang, Dong H.. Full-dimensional quantum dynamics study of the H{sub 2} + C{sub 2}H → H + C{sub 2}H{sub 2} reaction on an ab initio potential energy surface. United States: N. p., 2016. Web. doi:10.1063/1.4948996.
Chen, Liuyang, University of Chinese Academy of Sciences, Beijing 100049, Shao, Kejie, Chen, Jun, State Key Laboratory of Molecular Reaction Dynamics and Center for Theoretical Computational Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Yang, Minghui, E-mail: yangmh@wipm.ac.cn, & Zhang, Dong H.. Full-dimensional quantum dynamics study of the H{sub 2} + C{sub 2}H → H + C{sub 2}H{sub 2} reaction on an ab initio potential energy surface. United States. doi:10.1063/1.4948996.
Chen, Liuyang, University of Chinese Academy of Sciences, Beijing 100049, Shao, Kejie, Chen, Jun, State Key Laboratory of Molecular Reaction Dynamics and Center for Theoretical Computational Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Yang, Minghui, E-mail: yangmh@wipm.ac.cn, and Zhang, Dong H.. Sat . "Full-dimensional quantum dynamics study of the H{sub 2} + C{sub 2}H → H + C{sub 2}H{sub 2} reaction on an ab initio potential energy surface". United States. doi:10.1063/1.4948996.
@article{osti_22658015,
title = {Full-dimensional quantum dynamics study of the H{sub 2} + C{sub 2}H → H + C{sub 2}H{sub 2} reaction on an ab initio potential energy surface},
author = {Chen, Liuyang and University of Chinese Academy of Sciences, Beijing 100049 and Shao, Kejie and Chen, Jun and State Key Laboratory of Molecular Reaction Dynamics and Center for Theoretical Computational Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 and Yang, Minghui, E-mail: yangmh@wipm.ac.cn and Zhang, Dong H.},
abstractNote = {This work performs a time-dependent wavepacket study of the H{sub 2} + C{sub 2}H → H + C{sub 2}H{sub 2} reaction on a new ab initio potential energy surface (PES). The PES is constructed using neural network method based on 68 478 geometries with energies calculated at UCCSD(T)-F12a/aug-cc-pVTZ level and covers H{sub 2} + C{sub 2}H↔H + C{sub 2}H{sub 2}, H + C{sub 2}H{sub 2} → HCCH{sub 2}, and HCCH{sub 2} radial isomerization reaction regions. The reaction dynamics of H{sub 2} + C{sub 2}H → H + C{sub 2}H{sub 2} are investigated using full-dimensional quantum dynamics method. The initial-state selected reaction probabilities are calculated for reactants in eight vibrational states. The calculated results showed that the H{sub 2} vibrational excitation predominantly enhances the reactivity while the excitation of bending mode of C{sub 2}H slightly inhibits the reaction. The excitations of two stretching modes of C{sub 2}H molecule have negligible effect on the reactivity. The integral cross section is calculated with J-shift approximation and the mode selectivity in this reaction is discussed. The rate constants over 200-2000 K are calculated and agree well with the experimental measured values.},
doi = {10.1063/1.4948996},
journal = {Journal of Chemical Physics},
number = 19,
volume = 144,
place = {United States},
year = {Sat May 21 00:00:00 EDT 2016},
month = {Sat May 21 00:00:00 EDT 2016}
}