Author, as appears in the article.: De Graaf, C. ; Domingo, A; Angeli, C; Robert, V.
Department: Química Física i Inorgànica
URV's Author/s: DE GRAAF , CORNELIS; Domingo, A; Angeli, C; Robert, V.
Keywords: electron transfer transition metal complexes electronic structure
Abstract: The key role of the molecular orbitals in describing electron transfer processes is put in evidence for the intervalence charge transfer (IVCT) of a synthetic non-haem binuclear mixed-valence Fe3+/Fe2+ compound. The electronic reorganization induced by the IVCT can be quantified by controlling the adaptation of the molecular orbitals to the charge transfer process. We evaluate the transition energy and its polarization e¿ects on the molecular orbital by means of ab initio calculations. The resulting energetic profile of the IVCT shows strong similarities to the Marcus¿ model, suggesting a response behaviour of the ensemble of electrons analogue to that of the solvent. We quantify the extent of the electronic reorganization induced by the IVCT process to be 11.74 eV, a very large e¿ect that induces the crossing of states reducing the total energy of the transfer to 0.89 eV.
Research group: Química Quàntica
Thematic Areas: Química Química Chemistry
licence for use: https://creativecommons.org/licenses/by/3.0/es/
ISSN: 0192-8651
Author identifier: 0000-0001-8114-6658; ; ;
Record's date: 2018-02-28
Last page: 869
Journal volume: 36
Papper version: info:eu-repo/semantics/acceptedVersion
Link to the original source: http://onlinelibrary.wiley.com/doi/10.1002/jcc.23871/abstract
Funding program: altres; Agence Nationale de la Recherche; ANR-2010-BLAN-703 altres; excellence network Chemistry of Complex Systems; LabEx CSC, ANR-10-LABX-0026 CSC) plan; Excelencia; CTQ 2011-23140 altres; Grupos consolidados; 2009SGR462
Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
Article's DOI: 10.1002/jcc.23871
Entity: Universitat Rovira i Virgili
Journal publication year: 2015
First page: 861
Publication Type: Article Artículo Article
Repositori URV