Resonance energy transfer between polar charge-transfer dyes: a focus on the limits of the dipolar approximation

Abstract

Resonance energy transfer (RET) is investigated in a pair of polar charge-transfer (CT) chromophores, adopting essential-state models and time dependent density functional theory (TDDFT) calculations. Essential-state models describe in an efficient way linear and nonlinear optical properties of CT dyes, and prove very useful to rationalize the effects of electrostatic interchromophoric interactions on optical properties of multichromophoric systems. In this paper we adopt the same strategy developed for multichromophoric systems to investigate interchromophoric interactions responsible for RET. In the late forties, Th. Förster proposed a powerful method, based on the dipolar approximation, that directly relates the rate of the RET process to experimental accessible quantities. Here we discuss the applicability of the dipolar approximation for RET between CT dyes. The results obtained with essential-state models are confirmed by TDDFT calculations.