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Publication Citation: An Ab Initio Study of the Kinetics of the Reactions of Halomethanes With the Hydroxyl Radical. 2. A Comparison Between Theoretical and Experimental Values of the Kinetic Parameters for 12 Partially Halogenated Methanes

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Author(s): F Louis; Carlos A. Gonzalez; Robert E. Huie; Michael J. Kurylo III;
Title: An Ab Initio Study of the Kinetics of the Reactions of Halomethanes With the Hydroxyl Radical. 2. A Comparison Between Theoretical and Experimental Values of the Kinetic Parameters for 12 Partially Halogenated Methanes
Published: September 01, 2000
Abstract: Ab initio calculations have been performed for the H-atom abstraction reactions from a series of halogenated methanes by the hydroxyl radical. Geometry optimization and vibrational frequency calculations were performed for reactants, transition states and products at the MP2/6-311G(2d,2p) level of theory. Single-point energy calculations were carried out at the PMP2/6-311G(3df,2p) and PMP4/6-311++G(3df,3pd) levels. Canonical transition state theory was used to predict the rate constants as function of the temperature (250 K to 400 K) taking into account the tunneling correction. Atmospheric lifetimes and infrared radiative forcings of halomethanes were estimated based on results of these ab initio calculations.
Citation: Journal of Physical Chemistry A
Volume: 104
Issue: No. 38
Keywords: ab initio;atmospheric lifetime;halomethanes;hydroxyl radical;radiative forcing
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