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: Ab initio electron transfer 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 nonheme 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 effects on the molecular orbitals 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 effect that induces the crossing of states reducing the total energy of the transfer to 0.89 eV. © 2015 Wiley Periodicals, Inc.
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 0000-0002-9162-8076 n/a n/a
Record's date: 2015-04-27
Papper version: info:eu-repo/semantics/acceptedVersion
Link to the original source: http://onlinelibrary.wiley.com/doi/10.1002/jcc.23871/full
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
Publication Type: Article Artículo Article
Repositori URV