Resonance energy transfer: The unified theory revisited

Resonance energy transfer (RET) is the principal mechanism for the intermolecular or intramolecular redistribution of electronic energy following molecular excitation. In terms of fundamental quantum interactions, the process is properly described in terms of a virtual photon transit between the pre-excited donor and a lower energy (usually ground-state) acceptor. The detailed quantum amplitude for RET is calculated by molecular quantum electrodynamical techniques with the observable, the transfer rate, derived via application of the Fermi golden rule. In the treatment reported here, recently devised state-sequence techniques and a novel calculational protocol is applied to RET and shown to circumvent problems associated with the usual method. The second-rank tensor describing virtual photon behavior evolves from a Green's function solution to the Helmholtz equation, and special functions are employed to realize the coupling tensor. The method is used to derive a new result for energy transfer systems sensitive to both magnetic- and electric-dipole transitions. The ensuing result is compared to that of pure electric-dipole-electric-dipole coupling and is analyzed with regard to acceptable transfer separations. Systems are proposed where the electric-dipole-magnetic-dipole term is the leading contribution to the overall rate.