Oct 1, 1986
Proceedings of the Indian Academy of Sciences - Chemical Sciences
Proton transfer is involved in many chemical reactions, including reactions of electrochemical interest. In this paper, an analysis is presented in which individual bond potential energy functions which operate between the migrating proton (or hydrogen atom) and the remainder of the molecular framework are used in the account of the rate of transfer. This work builds upon and extends an analysis which was introduced to account for the inversion of ammonia in terms of individual, discrete intramolecular atomic interactions. The role of the environment in the transfer is discussed in terms of Metropolis/Monte Carlo methods. Algorithms for the determination of the transition state are considered: in particular, saddle point methods. Techniques for handling the determination of the saddle point when the migrating species is represented as a quantum mechanical wave-packet are discussed in addition to the more familiar methods based on the direct differentiation of the potential energy function for the reactive system.