scholarly journals Effect of laser intensity on the determination of intermolecular electron transfer rate constants—Observation of Marcus inverted region in photoinduced back electron transfer reactions

1998 ◽  
Vol 109 (14) ◽  
pp. 5948-5956 ◽  
Author(s):  
Yu-Xiang Weng ◽  
Kwok-Chu Chan ◽  
Biing-Chiau Tzeng ◽  
Chi-Ming Che
Keyword(s):  
Electron Transfer ◽  
Transfer Rate ◽  
Laser Intensity ◽  
Transfer Reactions ◽  
Electron Transfer Rate ◽  
Intermolecular Electron Transfer ◽  
Inverted Region ◽  
Back Electron Transfer ◽  
Marcus Inverted Region

Diffusion of Solvent-Separated Ion Pairs Controls Back Electron Transfer Rate in Graphene Quantum Dots

2018 ◽  
Vol 122 (28) ◽  
pp. 15819-15825 ◽  
Author(s):  
Ayan Bhattacharyya ◽  
Soumalya Mukherjee ◽  
Anju Chadha ◽  
Edamana Prasad
Keyword(s):  
Quantum Dots ◽  
Electron Transfer ◽  
Transfer Rate ◽  
Ion Pairs ◽  
Graphene Quantum Dots ◽  
Electron Transfer Rate ◽  
Back 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.

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