Four-center energy transfer and interaction pairs: Molecular quantum electrodynamics

Abstract

In the photophysics of complex macromolecules, resonance energy transfer is the key mechanism for the migration of electronic excitation. As the ability to engineer specific architectures for such molecules improves, environments for new forms of energy migration are being envisioned. Set in this context, one of our aims in this paper is to expound a new, general way of representing complex energy transfer systems, to obviate semantic and conceptual problems in addressing multicenter interactions. The theory of four-center energy transfer is developed within this framework, through the application of molecular quantum electrodynamics. A variety of mechanisms is identified by which four-center energy transfer may proceed, and a recently developed diagrammatic technique is employed to calculate relevant quantum amplitudes. Symmetry considerations are addressed, and key features of the ensuing rate equations are discussed with regard to their potential exploitation in novel photoactive devices.