scholarly journals Driving Force Dependence of Rates for Nonadiabatic Proton and Proton-Coupled Electron Transfer: Conditions for Inverted Region Behavior

2009 ◽  
Vol 113 (44) ◽  
pp. 14545-14548 ◽  
Author(s):  
Sarah J. Edwards ◽  
Alexander V. Soudackov ◽  
Sharon Hammes-Schiffer
Keyword(s):  
Electron Transfer ◽  
Driving Force ◽  
Inverted Region ◽  
Proton Coupled Electron Transfer

Driving force effects in proton coupled electron transfer

2000 ◽  
Vol 300-302 ◽  
pp. 186-190 ◽  
Author(s):  
Mauro C.M. Laranjeira ◽  
Rosemary A. Marusak ◽  
A.Graham Lappin
Keyword(s):  
Electron Transfer ◽  
Driving Force ◽  
Proton Coupled Electron Transfer

scholarly journals Concerted proton-electron transfer reactions in the Marcus inverted region

Science ◽  
2019 ◽  
Vol 364 (6439) ◽  
pp. 471-475 ◽  
Author(s):  
Giovanny A. Parada ◽  
Zachary K. Goldsmith ◽  
Scott Kolmar ◽  
Belinda Pettersson Rimgard ◽  
Brandon Q. Mercado ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Rate Constants ◽  
Charge Recombination ◽  
Transfer Reactions ◽  
Inverted Region ◽  
Electron Transfer Reactions ◽  
Proton Coupled Electron Transfer ◽  
Marcus Inverted Region ◽  
A Charge ◽  
Theory Yield

Electron transfer reactions slow down when they become very thermodynamically favorable, a counterintuitive interplay of kinetics and thermodynamics termed the inverted region in Marcus theory. Here we report inverted region behavior for proton-coupled electron transfer (PCET). Photochemical studies of anthracene-phenol-pyridine triads give rate constants for PCET charge recombination that are slower for the more thermodynamically favorable reactions. Photoexcitation forms an anthracene excited state that undergoes PCET to create a charge-separated state. The rate constants for return charge recombination show an inverted dependence on the driving force upon changing pyridine substituents and the solvent. Calculations using vibronically nonadiabatic PCET theory yield rate constants for simultaneous tunneling of the electron and proton that account for the results.

scholarly journals Evaluation of excited state bond weakening for ammonia synthesis from a manganese nitride: stepwise proton coupled electron transfer is preferred over hydrogen atom transfer

2019 ◽  
Vol 55 (39) ◽  
pp. 5595-5598 ◽  
Author(s):  
Florian Loose ◽  
Dian Wang ◽  
Lei Tian ◽  
Gregory D. Scholes ◽  
Robert R. Knowles ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Excited State ◽  
Hydrogen Atom ◽  
Visible Light ◽  
Driving Force ◽  
Ammonia Synthesis ◽  
Hydrogen Atom Transfer ◽  
Atom Transfer ◽  
Proton Coupled Electron Transfer ◽  
Manganese Nitride

Concepts for the thermodynamically challenging synthesis of weak N–H bonds by photoinduced proton coupled electron transfer are explored. By harvesting visible light as driving force, ammonia synthesis was achieved and mechanistically elucidated.

scholarly journals Solvent and Temperature Effects on Photoinduced Proton-Coupled Electron Transfer in the Marcus Inverted Region

2021 ◽  
Vol 125 (35) ◽  
pp. 7670-7684
Author(s):  
Laura F. Cotter ◽  
Belinda Pettersson Rimgard ◽  
Giovanny A. Parada ◽  
James M. Mayer ◽  
Leif Hammarström
Keyword(s):  
Electron Transfer ◽  
Temperature Effects ◽  
Inverted Region ◽  
Proton Coupled Electron Transfer ◽  
Marcus Inverted Region

scholarly journals Marcus-type driving force correlations reveal the mechanism of proton-coupled electron transfer for phenols and [Ru(bpy)3]3+ in water at low pH

2016 ◽  
Vol 7 (7) ◽  
pp. 4607-4612 ◽  
Author(s):  
Janne Soetbeer ◽  
Prateek Dongare ◽  
Leif Hammarström
Keyword(s):  
Electron Transfer ◽  
Driving Force ◽  
Laser Flash ◽  
Low Ph ◽  
Phenol Derivatives ◽  
Proton Coupled Electron Transfer

We examined PCET between a series of phenol derivatives and photogenerated [Ru(bpy)3]3+ in low pH (≤4) water using the laser flash-quench technique.

scholarly journals Theoretical analysis of the inverted region in photoinduced proton-coupled electron transfer

2019 ◽  
Vol 216 ◽  
pp. 363-378 ◽  
Author(s):  
Zachary K. Goldsmith ◽  
Alexander V. Soudackov ◽  
Sharon Hammes-Schiffer
Keyword(s):  
Electron Transfer ◽  
Theoretical Analysis ◽  
Energy Conversion ◽  
Rate Constant ◽  
Inverted Region ◽  
Significant Challenge ◽  
Proton Coupled Electron Transfer ◽  
Wide Range ◽  
Design Systems

Photoinduced proton-coupled electron transfer (PCET) plays a key role in a wide range of energy conversion processes, and understanding how to design systems to control the PCET rate constant is a significant challenge.

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