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Title: Temperature-dependent kinetic measurements and quasi-classical trajectory studies for the OH{sup +} + H{sub 2}/D{sub 2} → H{sub 2}O{sup +}/HDO{sup +} + H/D reactions

Abstract

We have measured the temperature-dependent kinetics for the reactions of OH{sup +} with H{sub 2} and D{sub 2} using a selected ion flow tube apparatus. Reaction occurs via atom abstraction to result in H{sub 2}O{sup +}/HDO{sup +} + H/D. Room temperature rate coefficients are in agreement with prior measurements and resulting temperature dependences are T{sup 0.11} for the hydrogen and T{sup 0.25} for the deuterated reactions. This work is prompted in part by recent theoretical work that mapped a full-dimensional global potential energy surface of H{sub 3}O{sup +} for the OH{sup +} + H{sub 2} → H + H{sub 2}O{sup +} reaction [A. Li and H. Guo, J. Phys. Chem. A 118, 11168 (2014)], and reported results of quasi-classical trajectory calculations, which are extended to a wider temperature range and initial rotational state specification here. Our experimental results are in excellent agreement with these calculations which accurately predict the isotope effect in addition to an enhancement of the reaction rate constant due to the molecular rotation of OH{sup +}. The title reaction is of high importance to astrophysical models, and the temperature dependence of the rate coefficients determined here should now allow for better understanding of this reaction at temperaturesmore » more relevant to the interstellar medium.« less

Authors:
; ; ;  [1]; ;  [2]
  1. Air Force Research Laboratory, Space Vehicles Directorate, Kirtland AFB, New Mexico 87117-5776 (United States)
  2. Department of Chemistry and Chemical Biology, University of New Mexico, Albuquerque, New Mexico 87131 (United States)
Publication Date:
OSTI Identifier:
22489608
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 143; Journal Issue: 11; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ATOMS; HEAVY WATER; HYDROGEN; OXONIUM IONS; POTENTIAL ENERGY; REACTION KINETICS; ROTATION; ROTATIONAL STATES; SPECIFICATIONS; SURFACES; TEMPERATURE DEPENDENCE; TEMPERATURE RANGE 0273-0400 K

Citation Formats

Martinez, Oscar, Ard, Shaun G., Shuman, Nicholas S., Viggiano, Albert A., E-mail: hguo@unm.edu, E-mail: afrl.rvborgmailbox@kirtland.af.mil, Li, Anyang, and Guo, Hua, E-mail: hguo@unm.edu, E-mail: afrl.rvborgmailbox@kirtland.af.mil. Temperature-dependent kinetic measurements and quasi-classical trajectory studies for the OH{sup +} + H{sub 2}/D{sub 2} → H{sub 2}O{sup +}/HDO{sup +} + H/D reactions. United States: N. p., 2015. Web. doi:10.1063/1.4931109.
Martinez, Oscar, Ard, Shaun G., Shuman, Nicholas S., Viggiano, Albert A., E-mail: hguo@unm.edu, E-mail: afrl.rvborgmailbox@kirtland.af.mil, Li, Anyang, & Guo, Hua, E-mail: hguo@unm.edu, E-mail: afrl.rvborgmailbox@kirtland.af.mil. Temperature-dependent kinetic measurements and quasi-classical trajectory studies for the OH{sup +} + H{sub 2}/D{sub 2} → H{sub 2}O{sup +}/HDO{sup +} + H/D reactions. United States. doi:10.1063/1.4931109.
Martinez, Oscar, Ard, Shaun G., Shuman, Nicholas S., Viggiano, Albert A., E-mail: hguo@unm.edu, E-mail: afrl.rvborgmailbox@kirtland.af.mil, Li, Anyang, and Guo, Hua, E-mail: hguo@unm.edu, E-mail: afrl.rvborgmailbox@kirtland.af.mil. Mon . "Temperature-dependent kinetic measurements and quasi-classical trajectory studies for the OH{sup +} + H{sub 2}/D{sub 2} → H{sub 2}O{sup +}/HDO{sup +} + H/D reactions". United States. doi:10.1063/1.4931109.
@article{osti_22489608,
title = {Temperature-dependent kinetic measurements and quasi-classical trajectory studies for the OH{sup +} + H{sub 2}/D{sub 2} → H{sub 2}O{sup +}/HDO{sup +} + H/D reactions},
author = {Martinez, Oscar and Ard, Shaun G. and Shuman, Nicholas S. and Viggiano, Albert A., E-mail: hguo@unm.edu, E-mail: afrl.rvborgmailbox@kirtland.af.mil and Li, Anyang and Guo, Hua, E-mail: hguo@unm.edu, E-mail: afrl.rvborgmailbox@kirtland.af.mil},
abstractNote = {We have measured the temperature-dependent kinetics for the reactions of OH{sup +} with H{sub 2} and D{sub 2} using a selected ion flow tube apparatus. Reaction occurs via atom abstraction to result in H{sub 2}O{sup +}/HDO{sup +} + H/D. Room temperature rate coefficients are in agreement with prior measurements and resulting temperature dependences are T{sup 0.11} for the hydrogen and T{sup 0.25} for the deuterated reactions. This work is prompted in part by recent theoretical work that mapped a full-dimensional global potential energy surface of H{sub 3}O{sup +} for the OH{sup +} + H{sub 2} → H + H{sub 2}O{sup +} reaction [A. Li and H. Guo, J. Phys. Chem. A 118, 11168 (2014)], and reported results of quasi-classical trajectory calculations, which are extended to a wider temperature range and initial rotational state specification here. Our experimental results are in excellent agreement with these calculations which accurately predict the isotope effect in addition to an enhancement of the reaction rate constant due to the molecular rotation of OH{sup +}. The title reaction is of high importance to astrophysical models, and the temperature dependence of the rate coefficients determined here should now allow for better understanding of this reaction at temperatures more relevant to the interstellar medium.},
doi = {10.1063/1.4931109},
journal = {Journal of Chemical Physics},
number = 11,
volume = 143,
place = {United States},
year = {Mon Sep 21 00:00:00 EDT 2015},
month = {Mon Sep 21 00:00:00 EDT 2015}
}