Articles producció científica> Química Física i Inorgànica

Electronic Reorganization Triggered by Electron Transfer: The Intervalence Charge Transfer of a Fe3+/Fe2+ Bimetallic Complex

  • Identification data

    Identifier: imarina:5128665
    Authors:
    Domingo, AlexAngeli, Celestinode Graaf, CoenRobert, Vincent
    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.
  • Others:

    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
    Link to the original source: https://onlinelibrary.wiley.com/doi/full/10.1002/jcc.23871
    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
    Article's DOI: 10.1002/jcc.23871
    Entity: Universitat Rovira i Virgili
    Journal publication year: 2015
    Publication Type: Journal Publications
  • Keywords:

    Chemistry,Chemistry (Miscellaneous),Chemistry, Multidisciplinary,Computational Mathematics
    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
    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
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