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Reanalysis of Rate Data for the Reaction CH3 + CH3 → C2H6 Using Revised Cross Sections and a Linearized Second-Order Master Equation

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Reanalysis of Rate Data for the Reaction CH3 + CH3 → C2H6 Using Revised Cross Sections and a Linearized Second-Order Master Equation. / Blitz, Mark A.; Green, Nicholas J. B.; Shannon, Robin J.; Pilling, Michael J.; Seakins, Paul W.; Western, Colin M.; Robertson, Struan H.

In: Journal of Physical Chemistry A, Vol. 119, No. 28, 16.07.2015, p. 7668-7682.

Research output: Contribution to journalArticle

Harvard

Blitz, MA, Green, NJB, Shannon, RJ, Pilling, MJ, Seakins, PW, Western, CM & Robertson, SH 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, vol. 119, no. 28, pp. 7668-7682. https://doi.org/10.1021/acs.jpca.5b01002

APA

Blitz, M. A., Green, N. J. B., Shannon, R. J., Pilling, M. J., Seakins, P. W., Western, C. M., & Robertson, S. H. (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. https://doi.org/10.1021/acs.jpca.5b01002

Vancouver

Blitz MA, Green NJB, Shannon RJ, Pilling MJ, Seakins PW, Western CM et al. 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. 2015 Jul 16;119(28):7668-7682. https://doi.org/10.1021/acs.jpca.5b01002

Author

Blitz, Mark A. ; Green, Nicholas J. B. ; Shannon, Robin J. ; Pilling, Michael J. ; Seakins, Paul W. ; Western, Colin M. ; Robertson, Struan H. / Reanalysis of Rate Data for the Reaction CH3 + CH3 → C2H6 Using Revised Cross Sections and a Linearized Second-Order Master Equation. In: Journal of Physical Chemistry A. 2015 ; Vol. 119, No. 28. pp. 7668-7682.

Bibtex

@article{58d72c49ed2f4cbab25bf3696ce8545e,
title = "Reanalysis of Rate Data for the Reaction CH3 + CH3 → C2H6 Using Revised Cross Sections and a Linearized Second-Order Master Equation",
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 B̃2A1′ (3s)–X̃2A2″ 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 χ2 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 cm3 molecule–1 s–1 was obtained, which agrees well with the best available theoretical expression.",
author = "Blitz, {Mark A.} and Green, {Nicholas J. B.} and Shannon, {Robin J.} and Pilling, {Michael J.} and Seakins, {Paul W.} and Western, {Colin M.} and Robertson, {Struan H.}",
year = "2015",
month = "7",
day = "16",
doi = "10.1021/acs.jpca.5b01002",
language = "English",
volume = "119",
pages = "7668--7682",
journal = "Journal of Physical Chemistry A",
issn = "1089-5639",
publisher = "American Chemical Society",
number = "28",

}

RIS - suitable for import to EndNote

TY - JOUR

T1 - Reanalysis of Rate Data for the Reaction CH3 + CH3 → C2H6 Using Revised Cross Sections and a Linearized Second-Order Master Equation

AU - Blitz, Mark A.

AU - Green, Nicholas J. B.

AU - Shannon, Robin J.

AU - Pilling, Michael J.

AU - Seakins, Paul W.

AU - Western, Colin M.

AU - Robertson, Struan H.

PY - 2015/7/16

Y1 - 2015/7/16

N2 - 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 B̃2A1′ (3s)–X̃2A2″ 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 χ2 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 cm3 molecule–1 s–1 was obtained, which agrees well with the best available theoretical expression.

AB - 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 B̃2A1′ (3s)–X̃2A2″ 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 χ2 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 cm3 molecule–1 s–1 was obtained, which agrees well with the best available theoretical expression.

U2 - 10.1021/acs.jpca.5b01002

DO - 10.1021/acs.jpca.5b01002

M3 - Article

C2 - 25992467

VL - 119

SP - 7668

EP - 7682

JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

SN - 1089-5639

IS - 28

ER -