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Bimolecular recombination reactions: K-adiabatic and K-active forms of the bimolecular master equations and analytic solutions

Ghaderi, Nima (2016) Bimolecular recombination reactions: K-adiabatic and K-active forms of the bimolecular master equations and analytic solutions. Journal of Chemical Physics, 144 (12). Art. No. 124114. ISSN 0021-9606. http://resolver.caltech.edu/CaltechAUTHORS:20160422-160647088

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Abstract

Expressions for a K-adiabatic master equation for a bimolecular recombination rate constant k_(rec) are derived for a bimolecular reaction forming a complex with a single well or complexes with multiple well, where K is the component of the total angular momentum along the axis of least moment of inertia of the recombination product. The K-active master equation is also considered. The exact analytic solutions, i.e., the K-adiabatic and K-active steady-state population distribution function of reactive complexes, g(EJK) and g(EJ), respectively, are derived for the K-adiabatic and K-active master equation cases using properties of inhomogeneous integral equations (Fredholm type). The solutions accommodate arbitrary intermolecular energy transfer models, e.g., the single exponential, double exponential, Gaussian, step-ladder, and near-singularity models. At the high pressure limit, the k_(rec) for both the K-adiabatic and K-active master equations reduce, respectively, to the K-adiabatic and K-active bimolecular Rice–Ramsperger–Kassel–Marcus theory (high pressure limit expressions). Ozone and its formation from O + O_2 are known to exhibit an adiabatic K. The ratio of the K-adiabatic to the K-active recombination rate constants for ozone formation at the high pressure limit is calculated to be ∼0.9 at 300 K. Results on the temperature and pressure dependence of the recombination rate constants and populations of O_3 will be presented elsewhere.


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http://dx.doi.org/10.1063/1.4944082DOIArticle
http://scitation.aip.org/content/aip/journal/jcp/144/12/10.1063/1.4944082PublisherArticle
Additional Information:© 2016 AIP Publishing LLC. Received 13 October 2015; accepted 3 March 2016; published online 29 March 2016. It is a great pleasure and an honor for the author to acknowledge Professor Rudolph A. Marcus for valuable discussions, comments, and noting a great teacher, the incredible erudition and venerable depth ever present. The constructive comments of the anonymous reviewers are also appreciated very much. N.G. would also like to thank Mrs. Monavareh Vojdani (grandmother) for inquiries, stimulating discussions on bimolecular reactions and kind encouragement, with much appreciation imparted.
Record Number:CaltechAUTHORS:20160422-160647088
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20160422-160647088
Official Citation:Bimolecular recombination reactions: K-adiabatic and K-active forms of the bimolecular master equations and analytic solutions Ghaderi, Nima, The Journal of Chemical Physics, 144, 124114 (2016), DOI:http://dx.doi.org/10.1063/1.4944082
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:66432
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:22 Apr 2016 23:49
Last Modified:22 Apr 2016 23:49

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