Autor segons l'article: Domingo, Alex; Angeli, Celestino; de Graaf, Coen; Robert, Vincent;
Departament: Química Física i Inorgànica
Autor/s de la URV: De Graaf, Cornelis
Paraules clau: 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
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.
Àrees temàtiques: 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
Accès a la llicència d'ús: https://creativecommons.org/licenses/by/3.0/es/
Adreça de correu electrònic de l'autor: coen.degraaf@urv.cat
Identificador de l'autor: 0000-0001-8114-6658
Data d'alta del registre: 2024-09-07
Versió de l'article dipositat: info:eu-repo/semantics/acceptedVersion
Enllaç font original: https://onlinelibrary.wiley.com/doi/full/10.1002/jcc.23871
URL Document de llicència: https://repositori.urv.cat/ca/proteccio-de-dades/
Referència a l'article segons font original: Journal Of Computational Chemistry. 36 (11): 861-869
Referència de l'ítem segons les normes 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
DOI de l'article: 10.1002/jcc.23871
Entitat: Universitat Rovira i Virgili
Any de publicació de la revista: 2015
Tipus de publicació: Journal Publications
Repositori URV