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Solvatochromism and Nonradiative Decay of Intramolecular Charge‐Transfer Excited States: Bands‐of‐Energy Model, Thermodynamics, and Self‐Organization
Author(s) -
Pavlovich Vladimir S.
Publication year - 2012
Publication title -
chemphyschem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.016
H-Index - 140
eISSN - 1439-7641
pISSN - 1439-4235
DOI - 10.1002/cphc.201200426
Subject(s) - solvatochromism , intramolecular force , excited state , chemistry , chemical physics , absorption spectroscopy , absorption (acoustics) , internal conversion , molecular electronic transition , marcus theory , photochemistry , solvent , spectral line , atomic physics , reaction rate constant , materials science , kinetics , organic chemistry , physics , quantum mechanics , composite material , astronomy
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.