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 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.

Effect of external pressure on photoinduced electron-transfer reactions in the Marcus inverted region

1991 ◽  
Vol 95 (20) ◽  
pp. 7752-7757 ◽  
Author(s):  
Wen Sheng Chung ◽  
Nicholas J. Turro ◽  
Ian R. Gould ◽  
Samir Farid
Keyword(s):  
Electron Transfer ◽  
Photoinduced Electron Transfer ◽  
External Pressure ◽  
Transfer Reactions ◽  
Inverted Region ◽  
Electron Transfer Reactions ◽  
Marcus Inverted Region

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

Observation of the Marcus Inverted Region for Bimolecular Photoinduced Electron-Transfer Reactions in Viscous Media

2014 ◽  
Vol 118 (36) ◽  
pp. 10704-10715 ◽  
Author(s):  
Manoj Kumbhakar ◽  
Arpan Manna ◽  
Mhejabeen Sayed ◽  
Anil Kumar ◽  
Haridas Pal
Keyword(s):  
Electron Transfer ◽  
Photoinduced Electron Transfer ◽  
Transfer Reactions ◽  
Inverted Region ◽  
Electron Transfer Reactions ◽  
Marcus Inverted Region ◽  
Viscous Media

Intramolecular Electron-Transfer of Covalently-Linked Polypyridine Ruthenium(II)/Rhodium(III) Binuclear Complexes in the Excited State. Observation of the Marcus Inverted Region

1990 ◽  
Vol 19 (11) ◽  
pp. 2065-2068 ◽  
Author(s):  
Masaoki Furue ◽  
Masumi Hirata ◽  
Shuichi Kinoshita ◽  
Takashi Kushida ◽  
Mikiharu Kamachi
Keyword(s):  
Electron Transfer ◽  
Excited State ◽  
Intramolecular Electron Transfer ◽  
Binuclear Complexes ◽  
Inverted Region ◽  
State Observation ◽  
Marcus Inverted Region ◽  
Covalently Linked

Electron transfer in the Marcus inverted region: Experiment and adiabatic tunneling mechanism

1994 ◽  
Vol 101 (8) ◽  
pp. 6640-6647 ◽  
Author(s):  
Yu. I. Dakhnovskii ◽  
Robert Doolen ◽  
John D. Simon
Keyword(s):  
Electron Transfer ◽  
Inverted Region ◽  
Tunneling Mechanism ◽  
Marcus Inverted Region
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