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On the theory of the reaction rate of vibrationally excited CO molecules with OH radicals

Chen, Wei-Chen and Marcus, R. A. (2006) On the theory of the reaction rate of vibrationally excited CO molecules with OH radicals. Journal of Chemical Physics, 124 (2). Art. No. 024306. ISSN 0021-9606. doi:10.1063/1.2148408.

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The dependence of the rate of the reaction CO+OH-->H+CO2 on the CO-vibrational excitation is treated here theoretically. Both the Rice-Ramsperger-Kassel-Marcus (RRKM) rate constant kRRKM and a nonstatistical modification knon [W.-C. Chen and R. A. Marcus, J. Chem. Phys. 123, 094307 (2005).] are used in the analysis. The experimentally measured rate constant shows an apparent (large error bars) decrease with increasing CO-vibrational temperature Tv over the range of Tv's studied, 298–1800 K. Both kRRKM(Tv) and knon(Tv) show the same trend over the Tv-range studied, but the knon(Tv) vs Tv plot shows a larger effect. The various trends can be understood in simple terms. The calculated rate constant kv decreases with increasing CO vibrational quantum number v, on going from v=0 to v=1, by factors of 1.5 and 3 in the RRKM and nonstatistical calculations, respectively. It then increases when v is increased further. These results can be regarded as a prediction when v state-selected rate constants become available.

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Marcus, R. A.0000-0001-6547-1469
Additional Information:©2006 American Institute of Physics (Received 13 October 2005; accepted 10 November 2005; published online 10 January 2006) It is a pleasure to acknowledge the support of this research by the National Science Foundation.
Subject Keywords:carbon compounds; oxygen compounds; reaction rate constants; molecule-molecule reactions; reaction kinetics theory; free radical reactions; vibrational states; excited states
Issue or Number:2
Record Number:CaltechAUTHORS:CHEjcp06
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Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:2169
Deposited By: Archive Administrator
Deposited On:13 Mar 2006
Last Modified:08 Nov 2021 19:45

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