Blitz, MA, Green, NJB, Shannon, RJ et al. (4 more authors) (2015) Reanalysis of rate data for the reaction CH3 + CH3 → C2H6 using revised cross sections and a linearized second-order master equation. Journal of Physical Chemistry A, 119 (28). 7668 - 7682. ISSN 1089-5639
Abstract
Rate coefficients for the CH3 + CH3 reaction, over the temperature range 300-900 K, have been corrected for errors in the absorption coefficients used in the original publication ( Slagle et al., J. Phys. Chem. 1988 , 92 , 2455 - 2462 ). These corrections necessitated the development of a detailed model of the B̃(2)A1' (3s)-X̃(2)A2″ transition in CH3 and its validation against both low temperature and high temperature experimental absorption cross sections. A master equation (ME) model was developed, using a local linearization of the second-order decay, which allows the use of standard matrix diagonalization methods for the determination of the rate coefficients for CH3 + CH3. The ME model utilized inverse Laplace transformation to link the microcanonical rate constants for dissociation of C2H6 to the limiting high pressure rate coefficient for association, k∞(T); it was used to fit the experimental rate coefficients using the Levenberg-Marquardt algorithm to minimize χ(2) calculated from the differences between experimental and calculated rate coefficients. Parameters for both k∞(T) and for energy transfer ⟨ΔE⟩down(T) were varied and optimized in the fitting procedure. A wide range of experimental data were fitted, covering the temperature range 300-2000 K. A high pressure limit of k∞(T) = 5.76 × 10(-11)(T/298 K)(-0.34) cm(3) molecule(-1) s(-1) was obtained, which agrees well with the best available theoretical expression.
Metadata
Item Type: | Article |
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Authors/Creators: |
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Copyright, Publisher and Additional Information: | (c) 2015, American Chemical Society. This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Physical Chemistry A, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/acs.jpca.5b01002 |
Dates: |
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Institution: | The University of Leeds |
Academic Units: | The University of Leeds > Faculty of Engineering & Physical Sciences (Leeds) > School of Chemistry (Leeds) > Physical Chemistry (Leeds) |
Depositing User: | Symplectic Publications |
Date Deposited: | 25 Aug 2015 09:13 |
Last Modified: | 03 Nov 2017 11:03 |
Published Version: | http://dx.doi.org/10.1021/acs.jpca.5b01002 |
Status: | Published |
Publisher: | American Chemical Society |
Identification Number: | 10.1021/acs.jpca.5b01002 |
Related URLs: | |
Open Archives Initiative ID (OAI ID): | oai:eprints.whiterose.ac.uk:89226 |