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

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.