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Electronic reorganization triggered by electron transfer: The intervalence charge transfer of a Fe 3+ /Fe 2+ bimetallic complex
Author(s) -
Domingo Alex,
Angeli Celestino,
de Graaf Coen,
Robert Vincent
Publication year - 2015
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.23871
Subject(s) - chemistry , molecular orbital , electron transfer , atomic orbital , atomic physics , valence (chemistry) , chemical physics , ab initio , electron , electronic structure , charge (physics) , molecular orbital theory , molecular physics , computational chemistry , molecule , physics , organic chemistry , quantum mechanics
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 Fe 3+ /Fe 2+ 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.