Classical Rate of Unimolecular Isomerization of Cyclobutanone

This paper presents calculations of the rate constant for the unimolecular isomerization of cyclobutanone using the theory of Gray and Rice as extended by Zhao and Rice. Such calculations are also carried out from classical trajectory and from local Lyapunov function analysis. The results of the calculations as a function of energy are compared, and the agreement is found to be uniformly good. The present approach is considered as a computationally feasible alternative to Davis' turnstile approach to the calculations of intramolecular energy transfer.