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 1, 2000

Author(s)

F Louis, Carlos A. Gonzalez, Robert E. Huie, Michael J. Kurylo III

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

Pub Type

Journals

Keywords

ab initio, atmospheric lifetime, halomethanes, hydroxyl radical, radiative forcing

Citation

Louis, F. , Gonzalez, C. , Huie, R. and Kurylo III, M. (2000), 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, Journal of Physical Chemistry A (Accessed April 20, 2024)