Improved potential energy surfaces for the reaction O(3P)+H2→OH+H

We present global 3A’ and 3A‘ potential energy surfaces for the reaction O(3P)+H2→OH+H and its isotopic analogs. The new surfaces are based in part on the surface of Lee et al. [J. Chem. Phys. 76, 3563 (1982)] for collinear O–H–H, which is modified to give accurate properties for reactants and products. The potentials for noncollinear O–H–H geometries are based on bending energies of Bowman et al. [J. Chem. Phys. 81, 1739 (1984)] as fit previously and called surface set M2 by two of the authors [B. C. Garrett and D. G. Truhlar, Int. J. Quantum Chem. 29, 1463 (1986)], and the potentials for H–O–H geometries are based on a new interpolation scheme. The new surfaces treat the approach of an O to either end of H2 equivalently. We used improved canonical variational transition state theory calculations with the least‐action ground‐state tunneling approximation (ICVT/LAG) to recalibrate the classical barrier height to 13.0 kcal/mol. The ICVT/LAG rate constants calculated using the new surfaces are in excellent ...

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