Autor según el artículo: De Graaf, C. Domingo, A. Angeli, C. Robert, V.

Departamento: Química Física i Inorgànica

Autor/es de la URV: DE GRAAF ., CORNELIS Domingo, A. Angeli, C. Robert, V.

Palabras clave: Ab initio electron transfer electronic structure

Resumen: 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.

Grupo de investigación: Química Quàntica

Áreas temáticas: Química Química Chemistry

Acceso a la licencia de uso: https://creativecommons.org/licenses/by/3.0/es/

ISSN: 0192-8651

Identificador del autor: 0000-0001-8114-6658 0000-0002-9162-8076 n/a n/a

Fecha de alta del registro: 2015-04-27

Versión del articulo depositado: info:eu-repo/semantics/acceptedVersion

Enlace a la fuente original: http://onlinelibrary.wiley.com/doi/10.1002/jcc.23871/full

DOI del artículo: 10.1002/jcc.23871

Entidad: Universitat Rovira i Virgili

Año de publicación de la revista: 2015

Tipo de publicación: Article Artículo Article