Energy-Transfer Theory for the Classical Decay Rates of Molecules at Rough Metallic Surfaces

摘要

The problem of the decay rates for molecules at rough metallic surfaces is considered, where the classical electromagnetic energy transfer theory of Chance, Prock and Silbey for a flat surface is generalized to the case of a rough boundary. A dynamical theory is constructed through the combination of the Sommerfield antenna theory and the integral equation formalism of Maxwell's equation at rough boundaries established mainly by Maradudin, Mills and Agarwal. Perturbative solutions are obtained and numerical results are given with reference to a shallow sinusoidal grating surface. The results, when compared with those previously from the application of the image field theory, show that this latter theory can be very inaccurate for cases involving highly-conducting substrates or large molecule-surface distances, consistent with previous observations for the case of flat surfaces. Keywords: Energy transfer, Classical decay rates, Molecules, Rough metallic surfaces, Sommerfield antenna theory, Maxwell's equations.