scholarly journals Computational Characterization of Single-Electron Transfer Steps in Water Oxidation

Inorganics ◽  
2019 ◽  
Vol 7 (3) ◽  
pp. 32 ◽  
Author(s):  
Adiran de Aguirre ◽  
Ignacio Funes-Ardoiz ◽  
Feliu Maseras
Keyword(s):  
Electron Transfer ◽  
Water Oxidation ◽  
Density Functional ◽  
Outer Sphere ◽  
Oxidation Catalysis ◽  
Single Electron ◽  
Single Electron Transfer ◽  
Inner Sphere ◽  
Water Oxidation Catalysis

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.

scholarly journals Single Electron Transfer Steps in Water Oxidation Catalysis. Redefining the Mechanistic Scenario

ACS Catalysis ◽  
2017 ◽  
Vol 7 (3) ◽  
pp. 1712-1719 ◽  
Author(s):  
Ignacio Funes-Ardoiz ◽  
Pablo Garrido-Barros ◽  
Antoni Llobet ◽  
Feliu Maseras
Keyword(s):  
Electron Transfer ◽  
Water Oxidation ◽  
Oxidation Catalysis ◽  
Single Electron ◽  
Single Electron Transfer ◽  
Water Oxidation Catalysis

scholarly journals Effect of water frustration on water oxidation catalysis in the nanoconfined interlayers of layered manganese oxides birnessite and buserite

2021 ◽  
Author(s):  
Ravneet K. Bhullar ◽  
Michael J. Zdilla ◽  
Michael L. Klein ◽  
Richard C. Remsing
Keyword(s):  
Electron Transfer ◽  
Water Oxidation ◽  
Manganese Oxides ◽  
Reorganization Energy ◽  
Oxidation Catalysis ◽  
Water Molecules ◽  
Effect Of Water ◽  
Geometric Frustration ◽  
Water Oxidation Catalysis

Reacting out of frustration: unlike buserite, the nanoconfined interlayer of birnessite results in geometric frustration of water molecules, which decreases the Marcus reorganization energy of electron transfer and enhances water oxidation catalysis.

scholarly journals High-Throughput Screening and Rational Design to Drive Discovery in Molecular Water Oxidation Catalysis

2021 ◽  
Author(s):  
Michael Craig ◽  
Max Garcia-Melchor
Keyword(s):  
Density Functional Theory ◽  
Water Oxidation ◽  
High Throughput Screening ◽  
Density Functional ◽  
Rational Design ◽  
Oxidation Catalysis ◽  
Molecular Water ◽  
Future Research ◽  
Functional Theory ◽  
Water Oxidation Catalysis

In this work we study a library of 444 hypothetical complexes for the OER composed of distinct metals (Cr, Mn, Fe, Ru, Co & Ni) and ligand skeletons. These were analysed using density functional theory via different functionals to drive interesting insights and suggestions for future research of this reaction.

Nature of transients produced on hydrogen atom transfer from capsaicin

2018 ◽  
Vol 17 (05) ◽  
pp. 1850036
Author(s):  
Ravi Joshi
Keyword(s):  
Electron Transfer ◽  
Hydrogen Atom ◽  
Dissociation Energy ◽  
Density Functional ◽  
Hydrogen Atom Transfer ◽  
Single Electron ◽  
Basis Set ◽  
Atom Transfer ◽  
Field Calculation ◽  
Single Electron Transfer

Structure and energies of capsaicin and its probable transients formed in oxidation processes (single electron transfer and hydrogen atom transfer) have been investigated using theoretical calculations. Molecular geometries and energies of truncated and complete capsaicin structures have been optimized using density functional theory (DFT) with Becke three-parameter Lee-Yang-Parr (B3LYP) functional and 6–31[Formula: see text]G(d) basis set. The stable geometries have been confirmed by vibrational analysis. The calculations suggest that single-electron transfer takes place at phenolic O-atom in the first step followed by delocalization of positive charge over the whole molecule. Further, the first step of hydrogen atom abstraction should take place at phenolic group due to lowest dissociation energy but post-optimization bond dissociation energy is least for benzylic group in the side chain as compared to other transients. Effect of water as a solvent on the energies has also been studied using self-consistent reaction field calculation. Similar results are obtained for truncated and complete capsaicin structures. The present study also includes Mulliken spin, charge, vibrational frequencies and assignments of frequencies of the transients. The present study provides explanation for the observation of phenoxyl radical in fast kinetic studies using pulse radiolysis study and, formation of breakdown and dimeric products in other studies.

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