skip to main content

DOE PAGESDOE PAGES

Title: Communication: Equivalence between symmetric and antisymmetric stretching modes of NH 3 in promoting H + NH 3 → H 2 + NH 2 reaction

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 + NH 3 → H 2 + NH 2 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 NH 3 stretching modes, is demonstrated. In conclusion, it is further shown that nearly identical efficacies of the symmetric and antisymmetric stretching modes of NH 3 in promoting the reaction can be understood in terms of local-mode stretching vibrations of the reactant molecule.
Authors:
 [1] ;  [1] ;  [2]
  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
  2. Univ. of New Mexico, Albuquerque, NM (United States). Dept. of Chemistry and Chemical Biology
Publication Date:
Grant/Contract Number:
SC0015997; 21373266
Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 145; Journal Issue: 13; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Research Org:
Univ. of New Mexico, Albuquerque, NM (United States)
Sponsoring Org:
USDOE
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; Tunneling
OSTI Identifier:
1426164
Alternate Identifier(s):
OSTI ID: 1328473

Song, Hongwei, Yang, Minghui, and Guo, Hua. Communication: Equivalence between symmetric and antisymmetric stretching modes of NH3 in promoting H + NH3 → H2 + NH2 reaction. United States: N. p., Web. doi:10.1063/1.4963286.
Song, Hongwei, Yang, Minghui, & Guo, Hua. Communication: Equivalence between symmetric and antisymmetric stretching modes of NH3 in promoting H + NH3 → H2 + NH2 reaction. United States. doi:10.1063/1.4963286.
Song, Hongwei, Yang, Minghui, and Guo, Hua. 2016. "Communication: Equivalence between symmetric and antisymmetric stretching modes of NH3 in promoting H + NH3 → H2 + NH2 reaction". United States. doi:10.1063/1.4963286. https://www.osti.gov/servlets/purl/1426164.
@article{osti_1426164,
title = {Communication: Equivalence between symmetric and antisymmetric stretching modes of NH3 in promoting H + NH3 → H2 + NH2 reaction},
author = {Song, Hongwei and Yang, Minghui and Guo, Hua},
abstractNote = {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.},
doi = {10.1063/1.4963286},
journal = {Journal of Chemical Physics},
number = 13,
volume = 145,
place = {United States},
year = {2016},
month = {10}
}

Works referenced in this record:

Laser Control of Chemical Reactions
journal, March 1998