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Main Title: Computational and spectroscopic studies of organic mixed-valence compounds: where is the charge?
Author(s): Kaupp, Martin
Renz, Manuel
Parthey, Matthias
Stolte, Matthias
Würthner, Frank
Lambert, Christoph
Type: Article
Language Code: en
Abstract: This article discusses recent progress by a combination of spectroscopy and quantum-chemical calculations in classifying and characterizing organic mixed-valence systems in terms of their localized vs.delocalized character. A recently developed quantum-chemical protocol based on non-standard hybrid functionals and continuum solvent models is evaluated for an extended set of mixed-valence bis-triarylamine radical cations, augmented by unsymmetrical neutral triarylamine-perchlorotriphenylmethyl radicals. It turns out that the protocol is able to provide a successful assignment to class II or class III Robin-Day behavior and gives quite accurate ground- and excited-state properties for the radical cations. The limits of the protocol are probed by the anthracene-bridged system8, where it is suspected that specific solute–solvent interactions are important and not covered by the continuum solvent model. Intervalence charge-transfer excitation energies for the neutral unsymmetrical radicals are systematically overestimated, but dipole moments and a number of other properties are obtained accurately by the protocol.
Issue Date: 2011
Date Available: 1-Jul-2016
DDC Class: 540 Chemie und zugeordnete Wissenschaften
Sponsor/Funder: DFG, GRK 1221, Steuerung elektronischer Eigenschaften von Aggregaten pi-konjugierter Moleküle
Journal Title: Physical chemistry, chemical physics
Publisher: Royal Society of Chemistry
Publisher Place: Cambridge
Volume: 13
Issue: 38
Publisher DOI: 10.1039/c1cp21772k
Page Start: 16973
Page End: 16986
EISSN: 1463-9084
ISSN: 1463-9076
Notes: Dieser Beitrag ist mit Zustimmung des Rechteinhabers aufgrund einer (DFG geförderten) Allianz- bzw. Nationallizenz frei zugänglich.
This publication is with permission of the rights owner freely accessible due to an Alliance licence and a national licence (funded by the DFG, German Research Foundation) respectively.
Appears in Collections:FG Theoretische Chemie » Publications

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