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: electron transfer transition metal complexes 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 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.

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; ; ;

Fecha de alta del registro: 2018-02-28

Página final: 869

Volumen de revista: 36

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

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

Programa de financiación: 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

DOI del artículo: 10.1002/jcc.23871

Entidad: Universitat Rovira i Virgili

Año de publicación de la revista: 2015

Página inicial: 861

Tipo de publicación: Article Artículo Article