Comment on the rate of isomerization of 3-phospholene.

We report calculations of the rate of isomerization of 3-phospholene based on the theory of Gray and Rice as extended by Zhao and Rice. This system is of interest for two reasons. First, the potential energy surface for motion in the isomerization coordinates is well known because of the spectroscopic studies of Harthcock and Laane. Second, the potential energy surface generates a Hamiltonian which has important off-diagonal kinetic energy coupling terms, which provides a different test of the accuracy of the approximations used in the Gray–Zhao–Rice theory than posed by previous applications. We find that the predictions of the Gary–Zhao–Rice theory are in good agreement with the results of simulations of the rate of isomerization of 3-phospholene. We also briefly discuss the relationship between the theory presented in this paper and the Reactive Island theory of isomerization. [ABSTRACT FROM AUTHOR]