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Title: Mode specificity in bond selective reactions F + HOD → HF + OD and DF + OH

Abstract

The influence of vibrational excitations in the partially deuterated water (HOD) reactant on its bond selective reactions with F is investigated using a full-dimensional quantum wave packet method on an accurate global potential energy surface. Despite the decidedly early barrier of the F + H{sub 2}O reaction, reactant vibrational excitation in each local stretching mode of HOD is found to significantly enhance the reaction which breaks the excited bond. In the mean time, excitation of the HOD bending mode also enhances the reaction, but with much lower efficacy and weaker bond selectivity. Except for low collision energies, all vibrational modes are more effective in promoting the bond selective reactions than the translational energy. These results are compared with the predictions of the recently proposed sudden vector projection model.

Authors:
;  [1]
  1. Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 (United States)
Publication Date:
OSTI Identifier:
22415745
Resource Type:
Journal Article
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 142; Journal Issue: 17; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0021-9606
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CHEMICAL BONDS; COMPARATIVE EVALUATIONS; DEUTERATION; EXCITATION; HEAVY WATER; HYDROFLUORIC ACID; POTENTIAL ENERGY; SPECIFICITY; SURFACES; WAVE PACKETS

Citation Formats

Song, Hongwei, and Guo, Hua, E-mail: hguo@unm.edu. Mode specificity in bond selective reactions F + HOD → HF + OD and DF + OH. United States: N. p., 2015. Web. doi:10.1063/1.4919666.
Song, Hongwei, & Guo, Hua, E-mail: hguo@unm.edu. Mode specificity in bond selective reactions F + HOD → HF + OD and DF + OH. United States. doi:10.1063/1.4919666.
Song, Hongwei, and Guo, Hua, E-mail: hguo@unm.edu. Thu . "Mode specificity in bond selective reactions F + HOD → HF + OD and DF + OH". United States. doi:10.1063/1.4919666.
@article{osti_22415745,
title = {Mode specificity in bond selective reactions F + HOD → HF + OD and DF + OH},
author = {Song, Hongwei and Guo, Hua, E-mail: hguo@unm.edu},
abstractNote = {The influence of vibrational excitations in the partially deuterated water (HOD) reactant on its bond selective reactions with F is investigated using a full-dimensional quantum wave packet method on an accurate global potential energy surface. Despite the decidedly early barrier of the F + H{sub 2}O reaction, reactant vibrational excitation in each local stretching mode of HOD is found to significantly enhance the reaction which breaks the excited bond. In the mean time, excitation of the HOD bending mode also enhances the reaction, but with much lower efficacy and weaker bond selectivity. Except for low collision energies, all vibrational modes are more effective in promoting the bond selective reactions than the translational energy. These results are compared with the predictions of the recently proposed sudden vector projection model.},
doi = {10.1063/1.4919666},
journal = {Journal of Chemical Physics},
issn = {0021-9606},
number = 17,
volume = 142,
place = {United States},
year = {2015},
month = {5}
}