TIME-DEPENDENT CHEMICAL-REACTIONS - A REVISION OF MONOMER-EXCIMER KINETICS

From the kinetic point of view, the fundamental quantity of a chemical reaction is the rate constant. The abundance of chemical reactions is governed by first-order kinetics. However, in many cases the diffusion of molecules in the medium leads to a diffusion-controlled chemical reaction. Among many, the monomer-excimer kinetics frequently encountered in photophysical studies is a classical example. An analysis of the kinetics of the monomer-excimer diffusionally-controlled reaction has been presented. It was shown that the theoretical results previously obtained by us using a specific technique of convolutions are in direct relation to the differential kinetic equations, provided that their solution is obtained by means of ensemble averaging. It was shown that the convolution method does not represent by itself any new method and, that it is in strict relation to more fundamental differential kinetic equations. In order to establish this relation, one cannot rely on a simple formal mathematical analysis of the differential equations, and the importance of the averaging procedure while solving the differential kinetic equations is shown. A discussion of the several aspects of differential kinetic equations is also presented.