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Communication: Equivalence between symmetric and antisymmetric stretching modes of NH3 in promoting H + NH3 → H2 + NH2 reaction

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4963286· OSTI ID:1426164
 [1];  [2];  [3]
  1. Chinese Academy of Sciences, 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; 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
  2. Chinese Academy of Sciences, 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. of New Mexico, Albuquerque, NM (United States). Dept. of Chemistry and Chemical Biology
+ Show Author Affiliations

Vibrational excitations of reactants sometimes promote reactions more effectively than the same amount of translational energy. Such mode specificity provides insights into the transition-state modulation of reactivity and might be used to control chemical reactions. We report here a state-ofthe- art full-dimensional quantum dynamical study of the hydrogen abstraction reaction H + NH3 → H2 + NH2 on an accurate ab initio based global potential energy surface. This reaction serves as an ideal candidate to study the relative efficacies of symmetric and degenerate antisymmetric stretching modes. Strong mode specificity, particularly for the NH3 stretching modes, is demonstrated. In conclusion, it is further shown that nearly identical efficacies of the symmetric and antisymmetric stretching modes of NH3 in promoting the reaction can be understood in terms of local-mode stretching vibrations of the reactant molecule.

Research Organization:
Univ. of New Mexico, Albuquerque, NM (United States)
Sponsoring Organization:
USDOE
Grant/Contract Number:
SC0015997
OSTI ID:
1426164
Alternate ID(s):
OSTI ID: 1328473
Journal Information:
Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 13 Vol. 145; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English

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Cited By (6)

Ab initio thermal rate coefficients for H + NH 3 ⇌ H 2 + NH 2 journal February 2019
Tracking the energy flow in the hydrogen exchange reaction OH + H 2 O → H 2 O + OH journal January 2018
Understanding mode-specific dynamics in the local mode representation journal January 2018
Dynamics and kinetics of the reaction OH + H 2 S → H 2 O + SH on an accurate potential energy surface journal January 2018
Nonthermal rate constants for CH4* + X → CH 3 + HX, X = H, O, OH, and O 2 journal March 2019
Full dimensional quantum mechanical calculations of the reaction probability of the H + NH 3 collision based on a mixed Jacobi and Radau description journal May 2019

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