title: Analysis of charge-transfer absorption and emission spectra on an absolute scale: evaluation of free energies, matrix elements, and reorganization energies.
abstract: The relationship between the absorption and emission spectra of the charge-transfer complexes formed between a series of methyl-substituted benzene donors with 1,2,4,5-tetracyanobenzene as acceptor in 1,2-dichloroethane was examined in detail. The association constants for charge-transfer complex formation and the emission quantum yields for these complexes were used to place the experimental absorption and emission spectra on absolute scales. The simultaneous analysis of these spectra is valid only when the Mulliken two-state model is justified. For several of the complexes included in this study the electron-transfer parameters, including the electronic coupling matrix elements, obtained from the analysis of the individual absorption and emission spectra are in close agreement. The simultaneous analysis of the combined absorption and emission spectra leads to a well-defined set of electron-transfer parameters for these complexes. In other complexes, where the two-state model does not apply because of the influence of localized excited states on the absorption spectrum, analysis of the absorption and emission spectra led to significantly different sets of electron-transfer parameters. It is demonstrated that the electronic coupling matrix elements are a very sensitive indicator of the influence of localized excited states on these spectra.
authors.affiliation: Department of Chemistry and Biochemistry, University of Maryland, Baltimore County, 1000 Hilltop Circle, Baltimore, Maryland 21250, USA.
authors.forename: Dustin
authors.initials: D
authors.lastname: Levy
authors.forename: Bradley R
authors.initials: BR
authors.lastname: Arnold
mesh_terms: D001555:Benzene Derivatives / Q000737:chemistry*; D005025:Ethylene Dichlorides / Q000737:chemistry*; D008956:Models, Chemical; D009570:Nitriles / Q000737:chemistry; D011789:Quantum Theory; D012680:Sensitivity and Specificity; D013050:Spectrometry, Fluorescence / Q000379:methods; D013056:Spectrophotometry, Ultraviolet / Q000379:methods; D013816:Thermodynamics
chemical_list: C412109:1,2,4,5-tetracyanobenzene; D001555:Benzene Derivatives; D005025:Ethylene Dichlorides; D009570:Nitriles; C024565:ethylene dichloride