Computational Characterization of Single-Electron Transfer Steps in Water Oxidation

de Aguirre, Adiran; Funes-Ardoiz, Ignacio; Maseras, Feliu

doi:10.3390/inorganics7030032

Open AccessArticle

Computational Characterization of Single-Electron Transfer Steps in Water Oxidation

by

Adiran de Aguirre

^1,2

,

Ignacio Funes-Ardoiz

^1,3

and

Feliu Maseras

^1,4,*

¹

Institute of Chemical Research of Catalonia (ICIQ), The Barcelona Institute of Science and Technology, Avgda. Països Catalans, 16, 43007 Tarragona, Catalonia, Spain

²

Departament de Química Física i Inorgànica, Universitat Rovira i Virgili, Marcel·lí Domingo s/n, 43007 Tarragona, Catalonia, Spain

³

Institute of Organic Chemistry, RWTH Aachen University, Landoltweg 1, 52074 Aachen, Germany

⁴

Departament de Química, Universitat Autònoma de Barcelona, 08193 Bellaterra, Catalonia, Spain

^*

Author to whom correspondence should be addressed.

Inorganics 2019, 7(3), 32; https://doi.org/10.3390/inorganics7030032

Submission received: 15 January 2019 / Revised: 14 February 2019 / Accepted: 22 February 2019 / Published: 1 March 2019

(This article belongs to the Special Issue Recent Advances in Water Oxidation Catalysis)

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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.

Keywords: Marcus theory; DFT; single-electron transfer; water oxidation; mechanisms

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MDPI and ACS Style

de Aguirre, A.; Funes-Ardoiz, I.; Maseras, F. Computational Characterization of Single-Electron Transfer Steps in Water Oxidation. Inorganics 2019, 7, 32. https://doi.org/10.3390/inorganics7030032

AMA Style

de Aguirre A, Funes-Ardoiz I, Maseras F. Computational Characterization of Single-Electron Transfer Steps in Water Oxidation. Inorganics. 2019; 7(3):32. https://doi.org/10.3390/inorganics7030032

Chicago/Turabian Style

de Aguirre, Adiran, Ignacio Funes-Ardoiz, and Feliu Maseras. 2019. "Computational Characterization of Single-Electron Transfer Steps in Water Oxidation" Inorganics 7, no. 3: 32. https://doi.org/10.3390/inorganics7030032

APA Style

de Aguirre, A., Funes-Ardoiz, I., & Maseras, F. (2019). Computational Characterization of Single-Electron Transfer Steps in Water Oxidation. Inorganics, 7(3), 32. https://doi.org/10.3390/inorganics7030032

Note that from the first issue of 2016, this journal uses article numbers instead of page numbers. See further details here.

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Computational Characterization of Single-Electron Transfer Steps in Water Oxidation

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