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Title: Communication: Mode specific quantum dynamics of the F + CHD3 → HF + CD3 reaction

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4948547· OSTI ID:1471067
ORCiD logo [1];  [2];  [2]; ORCiD logo [3];  [4];  [5]
  1. Chinese Academy of Sciences (CAS), Wuhan (China). Key Lab. of Magnetic Resonance in Biological Systems, State Key Lab. of Magnetic Resonance and Atomic and Molecular Physics, National Center for Magnetic Resonance in Wuhan, Wuhan Inst. of Physics and Mathematics
  2. Chinese Academy of Sciences (CAS), Wuhan (China). Key Lab. of Magnetic Resonance in Biological Systems, State Key Lab. of Magnetic Resonance and Atomic and Molecular Physics, National Center for Magnetic Resonance in Wuhan, Wuhan Inst. of Physics and Mathematics
  3. Univ. Nacional de Quilmes, Bernal (Argentina). National Scientific and Technical Research Council (CONICET), Dept. de Ciencia y Tecnologia
  4. Univ. Bielefeld, Bielefeld (Germany). Theoretische Chemie
  5. Univ. of New Mexico, Albuquerque, NM (United States). Dept. of Chemistry and Chemical Biology
+ Show Author Affiliations

The mode specific reactivity of the F + CHD3 → HF + CD3 reaction is investigated using an eightdimensional quantum dynamical model on a recently developed ab initio based full-dimensional potential energy surface. Here, our results indicate prominent resonance structures at low collision energies and absence of an energy threshold in reaction probabilities. It was also found that excitation of the C–D stretching or CD3 umbrella mode has a relatively small impact on reactivity. On the other hand, the excitation of the C–H vibration (v1) in CHD3 is shown to significantly increase the reactivity, which, like several recent quasi-classical trajectory studies, is at odds with the available experimental data. Possible sources of the disagreement are discussed.

Research Organization:
Univ. of New Mexico, Albuquerque, NM (United States)
Sponsoring Organization:
USDOE; National Natural Science Foundation of China (NSFC)
Grant/Contract Number:
FG02-05ER15694
OSTI ID:
1471067
Alternate ID(s):
OSTI ID: 1250390
Journal Information:
Journal of Chemical Physics, Vol. 144, Issue 17; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 42 works
Citation information provided by
Web of Science

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Cited By (9)

A neural network potential energy surface for the F + CH 4 reaction including multiple channels based on coupled cluster theory journal January 2018
Understanding mode-specific dynamics in the local mode representation journal January 2018
Imaging pair-correlated reaction cross sections in F + CH 3 D( ν b = 0, 1) → CH 2 D( ν 4 = 1) + HF( ν ) journal January 2019
Detailed benchmark ab initio mapping of the potential energy surfaces of the X + C 2 H 6 [X = F, Cl, Br, I] reactions journal January 2019
Natural reaction channels in H + CHD 3 → H 2 + CD 3 journal January 2018
Vibronically and spin-orbit coupled diabatic potentials for X(P) + CH 4 → HX + CH 3 reactions: General theory and application for X(P) = F( 2 P) journal February 2019
Counter-propagating wave packets in the quantum transition state approach to reactive scattering journal May 2019
Vibronically and spin-orbit coupled diabatic potentials for X( 2 P) + CH 4 → HX + CH 3 reactions: Neural network potentials for X = Cl journal June 2019
Vibronic coupling in the F·CH 4 prereactive complex journal September 2019

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