Kinetics of fluorescence quenching for electron transfer and for energy transfer: Molecular dynamics tests for spherical molecules

Abstract

The Smoluchowski approach to description of fluorescence quenching is tested by comparing the theory with computer simulations for the case of spherical molecules. The distance dependent sink terms describing the electron transfer mechanism and the Forster model for the energy transfer are considered. It is shown that the agreement between the rate coefficient from the model and from simulations depends on the strength of the solute-solvent interactions as well as on the speed of reaction itself. Comparing results of simulations for different quencher concentrations we estimate the strength of quencher concentration dependence effect and the range of times the effect may be significant. In the long time limit the increase in quencher concentration decreased the rate coefficient.