Quantum-chemical insights into mixed-valence systems: within and beyond the Robin-Day scheme

dc.contributor.authorParthey, M.
dc.contributor.authorKaupp, M.
dc.date.accessioned2016-06-22T08:05:31Z
dc.date.available2016-06-22T08:05:31Z
dc.date.issued2014
dc.description.abstractIn mixed-valence (MV) systems essentially identical, more or less electronically coupled, redox centres are brought into formally different oxidation states by removal or addition of an electron. Depending on the strength of electronic coupling, an electron or a hole is either concentrated on one of the redox centres, or it is symmetrically delocalised onto several sites, or the situation is somewhere in between, which leads to the classification system for MV systems introduced by Melvin Robin and Peter Day. These different characteristics are of fundamental importance for the understanding of electron transfer processes. Applications of quantum-chemical methods to aid the classification and to unravel the nature of the electronic structure and spectroscopic data of both organic and transition-metal MV systems, have gained tremendous importance over the last two decades. In this review, we emphasise the prerequisites the quantum-chemical methods need to fulfill to successfully describe MV systems close to the borderline between Robin–Day classes II and III. These are, in particular, a balanced treatment of exchange, dynamical and non-dynamical correlation effects, as well as consideration of the crucial influence of the (solvent or solid-state) environment on the partial localisation of charge. A large variety of applications of quantum-chemical methods to both organic and inorganic MV systems are critically appraised here in view of these prerequisites. Practical protocols based on a combination of suitable density functional methods with continuum or non-continuum solvent models provided good agreement with experimental data for the ground states and the electronic excitations of a large range of MV systems close to the borderline. Recent applications of such methods have highlighted the crucial importance of conformational effects on electronic coupling, all the way to systems where conformational motion may cause a thermal mixing of class II and class III situations in one system.en
dc.description.sponsorshipDFG, EXC 314, Unifying Concepts in Catalysisen
dc.description.sponsorshipDFG, GRK 1221, Steuerung elektronischer Eigenschaften von Aggregaten pi-konjugierter Moleküleen
dc.identifier.eissn0306-0012
dc.identifier.pmid24781049
dc.identifier.urihttps://depositonce.tu-berlin.de/handle/11303/5595
dc.identifier.urihttp://dx.doi.org/10.14279/depositonce-5224
dc.language.isoen
dc.rights.urihttps://creativecommons.org/licenses/by/3.0/
dc.subject.ddc540 Chemie und zugeordnete Wissenschaftende
dc.titleQuantum-chemical insights into mixed-valence systems: within and beyond the Robin-Day schemeen
dc.typeArticleen
dc.type.versionpublishedVersionen
dcterms.bibliographicCitation.doi10.1039/c3cs60481k
dcterms.bibliographicCitation.issue14
dcterms.bibliographicCitation.journaltitleChemical Society reviewsen
dcterms.bibliographicCitation.originalpublishernameRoyal Society of Chemistryde
dcterms.bibliographicCitation.originalpublisherplaceCambridgede
dcterms.bibliographicCitation.pageend5088
dcterms.bibliographicCitation.pagestart5067
dcterms.bibliographicCitation.volume43
tub.accessrights.dnbfree
tub.affiliationFak. 2 Mathematik und Naturwissenschaften::Inst. Chemie::FG Technische Chemiede
tub.affiliation.facultyFak. 2 Mathematik und Naturwissenschaftende
tub.affiliation.groupFG Technische Chemiede
tub.affiliation.instituteInst. Chemiede
tub.publisher.universityorinstitutionTechnische Universität Berlin

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