Mediation of resonance energy transfer by two polarisable particles

The molecular quantum electrodynamics theory is employed to calculate the matrix element and Fermi golden rule rate for resonant transfer of electronic excitation energy between a donor and an acceptor in the vicinity of two neutral electric dipole polarizable particles, which play the role of bridging species. The emitter and absorber couple linearly to the electric displacement field via their electric dipole moments, while each mediator interacts quadratically with this field through its dynamic polarizability. This form of interaction Hamiltonian enables fourth-order perturbation theory to be used to compute the probability amplitude together with summation over 24 time-ordered diagrams representing a single virtual photon exchange between each pair of coupled particles. Expressions for the migration rate mediated by two inert molecules are obtained for an arbitrary arrangement of the four species that are in fixed mutual orientation or are freely tumbling. These formulae are valid for all interparticle separation distances outside the orbital overlap region. From the general result, rate equations applicable to an equidistant collinear configuration of the four bodies are evaluated. Near- and far-zone limiting forms of the transfer rate for the relay pathway are also calculated and exhibit inverse sixth and inverse square dependences on relative separation distances between pairs of particles, confirming the short-range (radiationless) and long-range (radiative) energy transfer mechanisms associated with two-body theory. The distance behavior of interference terms between two-, three-, and four-body terms is also examined, and the relative importance of each contribution to the total transfer rate is discussed.