scholarly journals Introducing a closed system approach for the investigation of chemical steps involving proton and electron transfer; as illustrated by a copper-based water oxidation catalyst

2017 ◽  
Vol 19 (6) ◽  
pp. 4208-4215 ◽  
Author(s):  
Jessica M. de Ruiter ◽  
Francesco Buda
Keyword(s):  
Molecular Dynamics ◽  
Electron Transfer ◽  
Reaction Mechanism ◽  
Ab Initio ◽  
Closed System ◽  
Water Oxidation ◽  
System Approach ◽  
Oxidation Catalyst ◽  
Proton Coupled Electron Transfer

We present an ab initio molecular dynamics approach to characterize proton-coupled electron transfer catalytic steps and identify the preferred reaction mechanism.

scholarly journals Design and synthesis of benzimidazole phenol-porphyrin dyads for the study of bioinspired photoinduced proton-coupled electron transfer

2019 ◽  
Vol 23 (11n12) ◽  
pp. 1336-1345
Author(s):  
S. Jimena Mora ◽  
Daniel A. Heredia ◽  
Emmanuel Odella ◽  
Uma Vrudhula ◽  
Devens Gust ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Excited State ◽  
Photosystem Ii ◽  
Proton Transfer ◽  
Water Oxidation ◽  
Oxidation Catalyst ◽  
Design And Synthesis ◽  
Proton Coupled Electron Transfer ◽  
Anchoring Groups ◽  
High Redox Potential

Benzimidazole phenol-porphyrin dyads have been synthesized to study proton-coupled electron transfer (PCET) reactions induced by photoexcitation. High-potential porphyrins have been chosen to model P680, the photoactive chlorophyll cluster of photosynthetic photosystem II (PSII). They have either two or three pentafluorophenyl groups at the meso positions to impart the high redox potential. The benzimidazole phenol (BIP) moiety models the Tyr[Formula: see text]-His190 pair of PSII, which is a redox mediator that shuttles electrons from the water oxidation catalyst to P680[Formula: see text]. The dyads consisting of a porphyrin and an unsubstituted BIP are designed to study one-electron one-proton transfer (E1PT) processes upon excitation of the porphyrin. When the BIP moiety is substituted with proton-accepting groups such as imines, one-electron two-proton transfer (E2PT) processes are expected to take place upon oxidation of the phenol by the excited state of the porphyrin. The bis-pentafluorophenyl porphyrins linked to BIPs provide platforms for introducing a variety of electron-accepting moieties and/or anchoring groups to attach semiconductor nanoparticles to the macrocycle. The triads thus formed will serve to study the PCET process involving the BIPs when the oxidation of the phenol is achieved by the photochemically produced radical cation of the porphyrin.

scholarly journals Determination of pKa Values via ab initio Molecular Dynamics and its Application to Transition Metal-Based Water Oxidation Catalysts

Inorganics ◽  
2019 ◽  
Vol 7 (6) ◽  
pp. 73 ◽  
Author(s):  
Mauro Schilling ◽  
Sandra Luber
Keyword(s):  
Molecular Dynamics ◽  
Reaction Mechanism ◽  
Transition Metal ◽  
Ab Initio ◽  
Water Oxidation ◽  
Ab Initio Molecular Dynamics ◽  
Oxidation Catalysts ◽  
Dynamics Simulations ◽  
Further Development

The p K a values are important for the in-depth elucidation of catalytic processes, the computational determination of which has been challenging. The first simulation protocols employing ab initio molecular dynamics simulations to calculate p K a values appeared almost two decades ago. Since then several slightly different methods have been proposed. We compare the performance of various evaluation methods in order to determine the most reliable protocol when it comes to simulate p K a values of transition metal-based complexes, such as the here investigated Ru-based water oxidation catalysts. The latter are of high interest for sustainable solar-light driven water splitting, and understanding of the underlying reaction mechanism is crucial for their further development.

scholarly journals Molecular dynamics and charge transport in organic semiconductors: a classical approach to modeling electron transfer

2017 ◽  
Vol 8 (4) ◽  
pp. 2597-2609 ◽  
Author(s):  
Kenley M. Pelzer ◽  
Álvaro Vázquez-Mayagoitia ◽  
Laura E. Ratcliff ◽  
Sergei Tretiak ◽  
Raymond A. Bair ◽  
...  
Keyword(s):  
Molecular Dynamics ◽  
Electron Transfer ◽  
Charge Transfer ◽  
Charge Transport ◽  
Ab Initio ◽  
Organic Semiconductors ◽  
Multiscale Approach ◽  
Classical Approach ◽  
Classical Molecular Dynamics

Using ab initio calculations of charges in PCBM fullerenes, a multiscale approach applies classical molecular dynamics to model charge transfer.

The role of proton coupled electron transfer in water oxidation

2012 ◽  
Vol 5 (7) ◽  
pp. 7704 ◽  
Author(s):  
Christopher J. Gagliardi ◽  
Aaron K. Vannucci ◽  
Javier J. Concepcion ◽  
Zuofeng Chen ◽  
Thomas J. Meyer
Keyword(s):  
Electron Transfer ◽  
Water Oxidation ◽  
Proton Coupled Electron Transfer

scholarly journals Atomically manipulated proton transfer energizes water oxidation on silicon carbide photoanodes

2018 ◽  
Vol 6 (47) ◽  
pp. 24358-24366 ◽  
Author(s):  
Hao Li ◽  
Huan Shang ◽  
Yuchen Shi ◽  
Rositsa Yakimova ◽  
Mikael Syväjärvi ◽  
...  
Keyword(s):  
Silicon Carbide ◽  
Electron Transfer ◽  
Proton Transfer ◽  
Water Oxidation ◽  
Proton Coupled Electron Transfer ◽  
Rate Limiting Step ◽  
Limiting Step ◽  
Rate Limiting

Preferential exposure of Si-face of SiC will mechanistically shift the rate limiting step of water oxidation from sluggish proton-coupled electron transfer on C-face to a more energy-favorable electron transfer.

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