Author, as appears in the article.: Domingo, Alex; Angeli, Celestino; de Graaf, Coen; Robert, Vincent;
Department: Química Física i Inorgànica
URV's Author/s: De Graaf, Cornelis
Keywords: Transition metal Molecular-orbitals Molecular orbitals Localization Iron-oxo proteins Excited-states Electronic structure Electron transfer Diiron complexes Density-functional theory Complete active space Chemistry Ab-initio Ab initio 2nd-order perturbation-theory molecular orbitals electronic structure electron transfer ab initio
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.
Thematic Areas: Saúde coletiva Química Materiais Interdisciplinar General medicine General chemistry Farmacia Engenharias iv Computational mathematics Ciências biológicas ii Ciências biológicas i Ciências agrárias i Ciência da computação Chemistry, multidisciplinary Chemistry (miscellaneous) Chemistry (all) Chemistry Astronomia / física
licence for use: https://creativecommons.org/licenses/by/3.0/es/
Author's mail: coen.degraaf@urv.cat
Author identifier: 0000-0001-8114-6658
Record's date: 2024-09-07
Papper version: info:eu-repo/semantics/acceptedVersion
Licence document URL: https://repositori.urv.cat/ca/proteccio-de-dades/
Papper original source: Journal Of Computational Chemistry. 36 (11): 861-869
APA: Domingo, Alex; Angeli, Celestino; de Graaf, Coen; Robert, Vincent; (2015). Electronic Reorganization Triggered by Electron Transfer: The Intervalence Charge Transfer of a Fe3+/Fe2+ Bimetallic Complex. Journal Of Computational Chemistry, 36(11), 861-869. DOI: 10.1002/jcc.23871
Entity: Universitat Rovira i Virgili
Journal publication year: 2015
Publication Type: Journal Publications
Repositori URV