Computational characterization of single-electron transfer steps in water oxidation
de Aguirre, Adiran (Institut Català d'Investigació Química)
Funes-Ardoiz, Ignacio (Institut Català d'Investigació Química)
Maseras Cuní, Feliu (Universitat Autònoma de Barcelona. Departament de Química)

Date:	2019
Abstract:	The presence of single-electron transfer (SET) steps in water oxidation processes catalyzed by first-row transition metal complexes has been recently recognized, but the computational characterization of this type of process is not trivial. We report a systematic theoretical study based on density functional theory (DFT) calculations on the reactivity of a specific copper complex active in water oxidation that reacts through two consecutive single-electron transfers. Both inner-sphere (through transition state location) and outer-sphere (through Marcus theory) mechanisms are analyzed. The first electron transfer is found to operate through outer-sphere, and the second one through inner-sphere. The current work proposes a scheme for the systematic study of single-electron transfer in water oxidation catalysis and beyond.
Grants:	Ministerio de Economía y Competitividad CTQ2017-87792-R Ministerio de Economía y Competitividad BES-2015-073012 Ministerio de Economía y Competitividad SVP-2014-068662
Note:	Altres ajuts: CERCA Programme/Generalitat de Catalunya
Rights:	Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, la comunicació pública de l'obra i la creació d'obres derivades, fins i tot amb finalitats comercials, sempre i quan es reconegui l'autoria de l'obra original.
Language:	Anglès
Document:	Article ; recerca ; Versió publicada
Subject:	Marcus theory ; DFT ; Single-electron transfer ; Water oxidation ; Mechanisms
Published in:	Inorganics, Vol. 7, Issue 3 (March 2019) , art. 32, ISSN 2304-6740

DOI: 10.3390/INORGANICS7030032

11 p, 992.6 KB

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