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

Article's DOI: 10.1002/jcc.23871

Entity: Universitat Rovira i Virgili

Journal publication year: 2015

First page: 861

Publication Type: Article Artículo Article