A superconvergent representation of the Gersten-Nitzan and Ford-Webber nonradiative rates

Abstract

An alternative representation of the quasistatic nonradiative rates of Gersten and Nitzan [J. Chem. Phys. 1981, 75, 1139] and Ford and Weber [Phys. Rep. 1984, 113, 195] is derived for the respective parallel and perpendicular dipole orientations. Given the distance d of a dipole from a sphere surface of radius a, the representations comprise four elementary analytic functions and a modified multipole series taking into account residual multipole contributions. The analytic functions could be arranged hierarchically according to decreasing singularity at the short distance limit d ---> 0, ranging from d^{-3} over d^{-1} to ln (d/a). The alternative representations exhibit drastically improved convergence properties. On keeping mere residual dipole contribution of the modified multipole series, the representations agree with the converged rates on at least 99.9% for all distances, arbitrary particle sizes and emission wavelengths, and for a broad range of dielectric constants. The analytic terms of the representations reveal a complex distance dependence and could be used to interpolate between the familiar d^{-3} short-distance and d^{-6} long-distance behaviors with an unprecedented accuracy. Therefore, the representations could be especially useful for the qualitative and quantitative understanding of the distance behavior of nonradiative rates of fluorophores and semiconductor quantum dots involving nanometal surface energy transfer in the presence of metallic nanoparticles or nanoantennas. As a byproduct, a complete short-distance asymptotic of the quasistatic nonradiative rates is derived. The above results for the nonradiative rates translate straightforwardly to the so-called image enhancement factors Delta, which are of relevance for the surface-enhanced Raman scattering.