Computational Studies of the Geometry and Electronic Structure of an All-Inorganic and Homogeneous Tetra-Ru-Polyoxotungstate Catalyst for Water Oxidation and Its Four Subsequent One-Electron Oxidized Forms

2010 ◽  
Vol 114 (1) ◽  
pp. 535-542 ◽  
Author(s):  
David Quiñonero ◽  
Alexey L. Kaledin ◽  
Aleksey E. Kuznetsov ◽  
Yurii V. Geletii ◽  
Claire Besson ◽  
...  
Keyword(s):  
Electronic Structure ◽  
Water Oxidation ◽  
Computational Studies

scholarly journals Electronic Structure of Tyrosyl D Radical of Photosystem II, as Revealed by 2D-Hyperfine Sublevel Correlation Spectroscopy

2021 ◽  
Vol 7 (9) ◽  
pp. 131
Author(s):  
Maria Chrysina ◽  
Georgia Zahariou ◽  
Nikolaos Ioannidis ◽  
Yiannis Sanakis ◽  
George Mitrikas
Keyword(s):  
Electronic Structure ◽  
Photosystem Ii ◽  
Water Oxidation ◽  
Spinacia Oleracea ◽  
Higher Plants ◽  
Correlation Spectroscopy ◽  
Oxygen Evolving Complex ◽  
Higher Plant ◽  
Proton Coupled Electron Transfer ◽  
S Oxidation

The biological water oxidation takes place in Photosystem II (PSII), a multi-subunit protein located in thylakoid membranes of higher plant chloroplasts and cyanobacteria. The catalytic site of PSII is a Mn4Ca cluster and is known as the oxygen evolving complex (OEC) of PSII. Two tyrosine residues D1-Tyr161 (YZ) and D2-Tyr160 (YD) are symmetrically placed in the two core subunits D1 and D2 and participate in proton coupled electron transfer reactions. YZ of PSII is near the OEC and mediates electron coupled proton transfer from Mn4Ca to the photooxidizable chlorophyll species P680+. YD does not directly interact with OEC, but is crucial for modulating the various S oxidation states of the OEC. In PSII from higher plants the environment of YD• radical has been extensively characterized only in spinach (Spinacia oleracea) Mn- depleted non functional PSII membranes. Here, we present a 2D-HYSCORE investigation in functional PSII of spinach to determine the electronic structure of YD• radical. The hyperfine couplings of the protons that interact with the YD• radical are determined and the relevant assignment is provided. A discussion on the similarities and differences between the present results and the results from studies performed in non functional PSII membranes from higher plants and PSII preparations from other organisms is given.

Tuning Surface Electronic Structure of Two‐Dimensional Cobalt‐Based Hydroxide Nanosheets for Highly Efficient Water Oxidation

ChemCatChem ◽  
2020 ◽  
Vol 12 (10) ◽  
pp. 2823-2832 ◽  
Author(s):  
Chen Qiao ◽  
Souleymen Rafai ◽  
Tai Cao ◽  
Zhitao Wang ◽  
Haoyu Wang ◽  
...  
Keyword(s):  
Electronic Structure ◽  
Water Oxidation ◽  
Two Dimensional ◽  
Highly Efficient ◽  
Surface Electronic Structure

Selenium vacancy triggered atomic disordering of Co0.85Se nanoparticles towards a highly-active electrocatalyst for water oxidation

2020 ◽  
Vol 56 (92) ◽  
pp. 14451-14454
Author(s):  
Jiahao Zhang ◽  
Qiucheng Xu ◽  
Yanjie Hu ◽  
Hao Jiang ◽  
Chunzhong Li
Keyword(s):  
Electronic Structure ◽  
Water Oxidation ◽  
Highly Active

A moderate VSe degree can optimize the atomic disordering and electronic structure of Co-centers, remarkably enhancing the alkaline OER performance of Co0.85Se.

Sulfonamide vs. sulfonimide: tautomerism and electronic structure analysis of N-heterocyclic arenesulfonamides

2017 ◽  
Vol 41 (16) ◽  
pp. 8118-8129 ◽  
Author(s):  
Sumit S. Chourasiya ◽  
Dhara R. Patel ◽  
C. M. Nagaraja ◽  
Asit K. Chakraborti ◽  
Prasad V. Bharatam
Keyword(s):  
Electronic Structure ◽  
Structure Analysis ◽  
Computational Studies

Experimental and computational studies suggest a preference toward the sulfonimide tautomer in N-heterocyclic arenesulfonamide.

scholarly journals Imido Cobalt Complexes with Imidyl Character

2021 ◽  
Author(s):  
alexander Reckziegel ◽  
Manjinder Kour ◽  
Beatrice Battistella ◽  
Stefan Mebs ◽  
Katrin Beuthert ◽  
...  
Keyword(s):  
Electronic Structure ◽  
Spin Density ◽  
High Spin ◽  
Bond Activation ◽  
High Spin State ◽  
Cobalt Complexes ◽  
Spectroscopic Methods ◽  
Computational Studies ◽  
Ancillary Ligand ◽  
Unpaired Spin

We report on the synthesis of a variety of trigonal imido cobalt complexes [Co(NAryl)L<sub>2</sub>)<sup>–</sup>, (L = N(Dipp)SiMe<sub>3</sub>), Dipp = 2,6-diisopropylphenyl) bearing very long Co–NAryl bonds of around 1.75 Å. The electronic structure was interrogated using a variety of physical and spectroscopic methods indicating the first authenticated examples of cobalt bound imidyl species. Computational studies corroborate these findings and reveal that the high-spin state of these complexes gives rise to unpaired spin-density on the imide nitrogen and leads to its imidyl character. Obtained complexes are capable of intermolecular H atom abstraction from C–H bonds that yields the corresponding cobalt amides. Exchange of the Dipp-substituent on the imide by the smaller mesityl function (2,4,6-trimethylphenyl) effectuates the unexpected Me<sub>3</sub>Si shift from the ancillary ligand set to the imide nitrogen, followed by intramolecular C–H bond activation.<br>

scholarly journals How ab initio Molecular Dynamics Can Change the Understanding on Transition Metal Catalysed Water Oxidation

2021 ◽  
Vol 75 (3) ◽  
pp. 195-201
Author(s):  
Mauro Schilling ◽  
Rangsiman Ketkaew ◽  
Sandra Luber
Keyword(s):  
Transition Metal ◽  
Ab Initio ◽  
Water Oxidation ◽  
Ab Initio Molecular Dynamics ◽  
Computational Studies ◽  
Chemical Complexity ◽  
Oxygen Oxygen ◽  
Wide Range ◽  
Solvent Environment

Artificial water splitting is a promising technology that allows the storage of renewable energy in the form of energy-rich compounds. This mini-review showcases how theoretical studies contribute to the under-standing of existing water oxidation catalysts (WOCs) as well as inspiring the development of novel WOCs. In order to understand the chemical complexity of transition metal complexes and their interaction with the solvent environment, the use of sophisticated simulation protocols is necessary. As an illustration, a family of ruthe- nium-based WOCs is presented which were investigated employing a wide range of forefront computational methods with emphasis on ab initiomolecular dynamic based approaches. In those studies a base assisted oxygen–oxygen bond formation was identified as the energetically most favourable reaction mechanism. By examining the role of local environmental effects at ambient temperature and the effect of modifications in the ligand framework, a comprehensible picture of the WOCs can be given, where the latter can serve as a guideline for further experimental and computational studies. In this mini-review, we provide a description of the methods, and the findings of our previous computational studies in compacted form, aimed at scientists with a theoretical as well as experimental background.

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