Dynamics of excitions created by a single picosecond pulse.

A theoretical analysis of bimolecular annihilation in finite domains is presented. A Pauli master equation is formulated for the case of varying incident delta function excitation sources. Expressions for the quantum fluorescence yield and its time dependence are derived. The relationship between the fluorescence yield and the number of hits per domain depends on two parameters: the rate constant of bimolecular exciton annihilation and the dimension of the domain in which this annihilation occurs. Recent experimental results imply that the exciton diffusion constant (D) is large (D approximately to greater than 10(-3) cm2 S-1) and that the photosystem II domains may contain as many as five photosynthetic units. An analysis of the time decay of the fluorescence indicates that, for a few hits per domain, the decay may be considered as exponential but for many hits it becomes non-exponential. Thus the fluorescence decay depends on the intensity of the excitation source and/or on the dimension of the domains. Conditions which change the effective size of the domain may change the shape of the fluorescence decay. Some biological consequences and experimental applications of this theory are presented.