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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

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4947252· OSTI ID:1470767
 [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
+ Show Author Affiliations

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.

Research Organization:
Univ. of New Mexico, Albuquerque, NM (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Natural Science Foundation of China (NSFC)
Contributing Organization:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Grant/Contract Number:
FG02-05ER15694; 21373226
OSTI ID:
1470767
Alternate ID(s):
OSTI ID: 1249620
Journal Information:
Journal of Chemical Physics, Vol. 144, Issue 16; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

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Cited By (3)

Thermal rate coefficients and kinetic isotope effects of the reaction HO + H2O → H2O + OH journal August 2019
Tracking the energy flow in the hydrogen exchange reaction OH + H 2 O → H 2 O + OH journal January 2018
Mode-specific quantum dynamics and kinetics of the hydrogen abstraction reaction OH + H 2 O → H 2 O + OH journal January 2019

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Related Subjects

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