Kinetics of geminate recombination of subdiffusing particles in the presence of interparticle interaction

The kinetics of geminate subdiffusion-assisted reactions (SDARs) of interacting particles is analyzed in detail with the use of the non-Markovian fractional Smoluchowki equation (FSE). It is suggested that the interparticle interaction potential is of the shape of potential well and reactivity is located within the well. The reaction kinetics is studied in the limit of deep well, in which the FSE can be solved analytically. This solution enables one to obtain the kinetics in a simple analytical form. The analytical expression shows that the SDAR kinetics fairly substantially depends on the mechanism of reactivity within the well. Specific features of the kinetics are thoroughly analyzed in two models of reactivity: the subdiffusion assisted activated rate model and the first order reaction model. The theory developed is applied to the interpretation of experimental kinetics of photoluminescence decay in amorphous $a$-Si:H semiconductors governed by geminate recombination of electrons and holes which are recently found to undergo subdiffusive relative motion. Analysis of results demonstrates that the subdiffusion assisted activated rate mechanism of reaction is closer to reality as applied to amorphous $a$-Si:H semiconductors. Comparison of experimental and theoretical kinetics allowed for obtaining some kinetic parameters of the systems under study: the rate of escaping from the well and the parameter characterizing the deviation of the subdiffusive motion from the conventional one.

A. I. Shushin · 2008