Including anharmonicity in the calculation of rate constants. II. The OH+H2-->H2O+H reaction.
A recently developed method for calculating anharmonic vibrational energy levels at nonstationary points along a reaction path that is based on second-order perturbation theory in curvilinear coordinates is combined with variational transition state theory with semiclassical multidimensional tunneling approximations to calculate thermal rate constants for the title reaction. Two different potential energy surfaces were employed for these calculations, an improved version of the author's surface 5 and the WSLFH surface of Wu et al. [J. Chem. Phys. 113, 3150 (2000)]. We present detailed comparisons of rate constants computed for the two surfaces with and without anharmonicity and with various approximations for incorporating tunneling along the reaction path. The results for this system are quite sensitive to the surface employed, the choice of coordinates (curvilinear versus rectilinear), and the inclusion of anharmonicity. A comparison with experiment provides information on the accuracy of these surfaces.
Isaacson
Alan D
AD
Department of Chemistry and Biochemistry, Miami University, Oxford, Ohio 45056, USA. isaacsad@muohio.edu