Quantum mechanical calculations of the rate constant for the H2+OH→H+H2O reaction: Full-dimensional results and comparison to reduced dimensionality models

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Abstract
The cumulative reaction probability is calculated for the H2+OH→H+H2O reaction in its full (six) dimensionality for total angular momentum J=0. The calculation, which should give the (numerically) exact result for the assumed potential energy surface, yields the cumulative reaction probability directly, without having to solve the complete state‐to‐state reactive scattering problem. Higher angular momenta (J≳0) were taken into account approximately to obtain the thermal rate constant k(T) over the range 300°<T<700°. The result deviates significantly from the experimental rate constant, suggesting that the potential energy surface needs to be improved. A systematic series of reduced dimensionality calculations is carried out in order to characterize the behavior and reliability of these more approximate treatments; a comparison of the full dimensional results with previous reduced dimensionality calculations is also made.