Solvatochromism and Nonradiative Decay of Intramolecular Charge‐Transfer Excited States: Bands‐of‐Energy Model, Thermodynamics, and Self‐Organization

Abstract

The fluctuations of orientation and induction interactions in solution and their impact on the broadening of absorption and fluorescence spectra are considered in terms of a bands-of-energy model. Also covered is the application of principles of thermodynamics and self-organization of systems for calculation of solvatochromic shift, among them a component owing to the work on electronic polarization of solvent at the instant of electronic transition in the solute. The findings on solvatochromic shift and spectral broadening open the way to the calculation of solvent effects on the rate constant of nonradiative transitions. As demonstrated herein for 15 fluorophores, the novel theory of nonradiative decay of the intramolecular charge-transfer excited states is carried out for dyes and organic compounds of different nature, both for polar and nonpolar media.