Pathways and rate coefficients for the decomposition of vinoxy and acetyl radicals

The Journal of Physical Chemistry. a
Juan P SenosiainJames A Miller

Abstract

The potential in the vicinity of the stationary points on the surface for the decomposition of ground-state vinoxy and acetyl radicals has been calculated using the RQCISD(T) method extrapolated to the infinite-basis set limit. Rate coefficients for the decomposition pathways of these two radicals were computed using the master equation and variational transition state theory. Agreement between our calculated rate coefficients for H + CH(2)CO <--> CH(3) + CO and experimental data is very good, without the need for empirical adjustments to the ab initio energy barriers. Multireference configuration-interaction calculations indicate two competitive channels for vinoxy decomposition, with the channel leading to H + CH(2)CO being preferred at photodissociation energies. However, at typical combustion conditions, vinoxy decomposes primarily to CO and methyl. In contrast, decomposition of acetyl shows only one decomposition channel, leading to CO and methyl. The implications of a low-lying exit channel for the calculation of theoretical rate coefficients are discussed briefly.

References

Sep 15, 1988·Physical Review A: General Physics·A D Becke
Jul 13, 2006·The Journal of Physical Chemistry. a·Stephen J Klippenstein, James A Miller
Jul 13, 2006·The Journal of Physical Chemistry. a·Juan P SenosiainJames A Miller

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Citations

Sep 11, 2007·The Journal of Chemical Physics·Doran I G BennettHans-Joachim Werner
Jul 2, 2009·The Journal of Chemical Physics·Tara I YacovitchDaniel M Neumark
Dec 15, 2015·The Journal of Physical Chemistry Letters·Nicole J LabbeStephen J Klippenstein
Jun 19, 2015·Physical Chemistry Chemical Physics : PCCP·Jordy BouwmanPatrick Hemberger
Mar 21, 2015·The Journal of Physical Chemistry. a·Raghu SivaramakrishnanStephen J Klippenstein
Dec 25, 2010·Physical Chemistry Chemical Physics : PCCP·X YangR S Tranter
Dec 20, 2014·The Journal of Physical Chemistry. a·Brian J WarnerLaura R McCunn
Oct 10, 2018·Journal of Computational Chemistry·Anna S SavchenkovaAlexander M Mebel
Feb 12, 2009·Physical Chemistry Chemical Physics : PCCP·James A MillerNicholas J B Green
Oct 26, 2011·Physical Chemistry Chemical Physics : PCCP·Xueliang YangRobert S Tranter
Mar 13, 2014·Physical Chemistry Chemical Physics : PCCP·Christopher J AnnesleyRobert S Tranter
Feb 23, 2021·Journal of the American Chemical Society·Daniel P ZaleskiKirill Prozument
Jun 13, 2008·The Journal of Physical Chemistry. a·Tobias BentzMatthias Olzmann
Aug 22, 2008·The Journal of Physical Chemistry. a·James A MillerYuri Georgievskii
Dec 19, 2009·The Journal of Physical Chemistry. a·R SivaramakrishnanS J Klippenstein
Jul 3, 2009·The Journal of Physical Chemistry. a·Xueliang YangRobert S Tranter
Apr 23, 2021·Physical Chemistry Chemical Physics : PCCP·Denis P PorfirievAlexander M Mebel
Dec 23, 2017·Journal of the American Chemical Society·Colin A GrambowYury V Suleimanov
Oct 6, 2021·The Journal of Physical Chemistry. a·Ge SunJingsong Zhang

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