Autor segons l'article: De Graaf, C. Domingo, A. Angeli, C. Robert, V.
Departament: Química Física i Inorgànica
Autor/s de la URV: DE GRAAF ., CORNELIS Domingo, A. Angeli, C. Robert, V.
Paraules clau: Ab initio electron transfer electronic structure
Resum: 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.
Grup de recerca: Química Quàntica
Àrees temàtiques: Química Química Chemistry
Accès a la llicència d'ús: https://creativecommons.org/licenses/by/3.0/es/
ISSN: 0192-8651
Identificador de l'autor: 0000-0001-8114-6658 0000-0002-9162-8076 n/a n/a
Data d'alta del registre: 2015-04-27
Versió de l'article dipositat: info:eu-repo/semantics/acceptedVersion
Enllaç font original: http://onlinelibrary.wiley.com/doi/10.1002/jcc.23871/full
URL Document de llicència: https://repositori.urv.cat/ca/proteccio-de-dades/
DOI de l'article: 10.1002/jcc.23871
Entitat: Universitat Rovira i Virgili
Any de publicació de la revista: 2015
Tipus de publicació: Article Artículo Article
Repositori URV