A quantum electrodynamical theory of three-center energy transfer for upconversion and downconversion in rare earth doped materials

Abstract

Three-center energy transfer affords the basic mechanism for a variety of multiphoton processes identified within materials doped with rare earths. Addressing the theory using quantum electrodynamics, general results are obtained for systems in which the fundamental photophysics engages three ions. Distinct cooperative and accretive mechanistic pathways are identified and the theory is formulated to elicit their role and features in energy transfer phenomena of pooling upconversion, sensitization, and downconversion or quantum cutting. It is shown that although the two mechanisms play significant roles in pooling and cutting, only the accretive mechanism is responsible for sensitization processes. Both mechanisms are shown to invoke Raman selection rules, which govern transitions of the mediator ions in the accretive mechanisms and transitions of the acceptor ions in the cooperative mechanisms. The local, microscopic level results are used to gauge the lattice response, encompassing concentration and structural effects. Attention is drawn to a general implication of implementing a multipolar description for the optical properties of doped solid-state ionic materials.