Tunneling in the reaction of acetone with OH

Physical Chemistry Chemical Physics : PCCP
Françoise CaralpFrederic Bohr

Abstract

Based on recent detailed quantum mechanical computations of the mechanism of the title reaction and, this paper presents kinetics analysis of the overall rate constant and its temperature dependence, for which ample experimental data are available for comparison. The analysis confirms that the principal channel is the formation of acetonyl radical + H(2)O, while the channel leading to acetic acid is of negligible importance. It is shown that the unusual temperature dependence of the overall rate constant, as observed experimentally, is well accounted for by standard RRKM treatment that includes tunneling. This treatment is applied at the microcanonical level, with chemically activated distribution of entrance species, i.e. using a stationary rather than a thermal distribution that incorporates collisional energy transfer and competition between the redissociation and exit channel. A similar procedure is applied to the isotopic reaction acetone-d6 + OH with equally satisfying results, so that the experimental temperature dependence of the KIE (kinetic isotope effect) is perfectly reproduced. This very good agreement between calculation and experiment is obtained without any fitting to experimental values and without any adjustme...Continue Reading

References

Jul 13, 2006·The Journal of Physical Chemistry. a·Jonathan D RaffRonald A Hites

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Citations

Dec 22, 2016·Environmental Science. Processes & Impacts·Goran Kovacevic, Aleksandar Sabljic
Sep 15, 2010·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Julien DaranlotKevin M Hickson
Oct 29, 2008·Physical Chemistry Chemical Physics : PCCP·Françoise CaralpAstrid Bergeat
Jun 5, 2012·Chemical Society Reviews·Luc Vereecken, Joseph S Francisco
Mar 15, 2019·Physical Chemistry Chemical Physics : PCCP·Antonio J OcañaElena Jiménez
Nov 6, 2013·Journal of Computational Chemistry·Sébastien CanneauxEric Henon
Jul 8, 2017·Magnetic Resonance in Medicine : Official Journal of the Society of Magnetic Resonance in Medicine·Moritz ZaissKlaus Scheffler
Mar 31, 2015·The Journal of Physical Chemistry. a·Thanh Lam Nguyen, John F Stanton
Apr 7, 2015·Chemical Reviews·Luc VereeckenMichael J Pilling
Dec 8, 2006·The Journal of Physical Chemistry. a·Hua HouBaoshan Wang
Oct 21, 2006·Environmental Science & Technology·Estelle TurpinJean-Claude Galloo

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