Journal of Physical Chemistry A, Vol.123, No.13, 2853-2860, 2019
Near-Zone Mediation of RET by One and Two Proximal Particles
The effect of two inert, electric dipole polarizable molecules in relaying electronic excitation energy resonantly between a donor-acceptor pair is studied within the framework of molecular QED theory. Since transfer is efficacious when the coupled particles are close to one another, the matrix element is calculated in the near-zone approximation by employing static dipolar interaction potentials and third-order diagrammatic perturbation theory. For isotropic species, the Fermi golden rule exchange rate exhibits a Forster-like inverse sixth power dependence on each pair separation distance, is proportional to the modulus squares of the transition electric dipole moments of donor and acceptor, and depends on the polarizabilities of the two mediators. Comparison is made with direct (2-body) and third- body mediated near-zone transfer. Matrix elements for these last two processes are used to evaluate contributions to the rate due to 2-body-3-body, 2-body-4-body, and 3-body-4-body interference terms. In each of these cases, an inverse cubic dependence on each of the relative particle displacements is found.