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Title: Communication: Mode specific quantum dynamics of the F + CHD{sub 3} → HF + CD{sub 3} reaction

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4948547· OSTI ID:22657948
; ;  [1];  [2];  [3];  [4]
  1. Key Laboratory of Magnetic Resonance in Biological Systems, State Key Laboratory of Magnetic Resonance and Atomic and Molecular Physics, National Center for Magnetic Resonance in Wuhan, Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences, Wuhan 430071 (China)
  2. Departamento de Ciencia y Tecnología, Universidad Nacional de Quilmes, CONICET, Sáenz Peña 352, Bernal B1876BXD (Argentina)
  3. Theoretische Chemie, Fakultät für Chemie, Universität Bielefeld, Universitätsstr. 25, D-33615 Bielefeld (Germany)
  4. Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 (United States)

The mode specific reactivity of the F + CHD{sub 3} → HF + CD{sub 3} reaction is investigated using an eight-dimensional quantum dynamical model on a recently developed ab initio based full-dimensional potential energy surface. 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 CD{sub 3} umbrella mode has a relatively small impact on reactivity. On the other hand, the excitation of the C–H vibration (v{sub 1}) in CHD{sub 3} 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.

OSTI ID:
22657948
Journal Information:
Journal of Chemical Physics, Vol. 144, Issue 17; Other Information: (c) 2016 Author(s); Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
Country of Publication:
United States
Language:
English

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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
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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