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Title: A full-dimensional quantum dynamics study of the mode specificity in the H + HOD abstraction reaction

We employ the initial state-selected time-dependent wave packet approach to an atom-triatom reaction to study the H + HOD → OH + HD/OD + H{sub 2} reaction without the centrifugal sudden approximation, based on an accurate potential energy surface which was recently developed by neural network fitting to high level ab initio energy points. The total reaction probabilities and integral cross sections, which are the exact coupled-channel results, are calculated for the HOD reactant initially in the ground and several vibrationally excited states, including the bending excited state, OD stretching excited states, OH stretching excited states, and combined excitations of them. The reactivity enhancements from different initial states of HOD are presented, which feature strong bond-selective effects of the reaction dynamics. The current results for the product branching ratios, reactivity enhancements, and relative cross sections are largely improved over the previous calculations, in quantitatively good agreement with experiment. The thermal rate constant for the title reaction and the contributions from individual vibrational states of HOD are also obtained.
Authors:
;  [1]
  1. State Key Laboratory of Molecular Reaction Dynamics and Center for Theoretical and Computational Chemistry, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China)
Publication Date:
OSTI Identifier:
22416115
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 6; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; ATOMS; BRANCHING RATIO; COUPLED CHANNEL THEORY; EXCITATION; HEAVY WATER; HYDROGEN; INTEGRAL CROSS SECTIONS; NEURAL NETWORKS; POTENTIAL ENERGY; PROBABILITY; REACTION KINETICS; REACTIVITY; SPECIFICITY; SUDDEN APPROXIMATION; TIME DEPENDENCE; VIBRATIONAL STATES; WAVE PACKETS