Electron Transfer Reactions in Bacterial Photosynthesis: Charge Recombination Kinetics as a Structure Probe

Author(s):  
G. Feher ◽  
M. Okamura ◽  
D. Kleinfeld
Science ◽  
2019 ◽  
Vol 364 (6439) ◽  
pp. 471-475 ◽  
Author(s):  
Giovanny A. Parada ◽  
Zachary K. Goldsmith ◽  
Scott Kolmar ◽  
Belinda Pettersson Rimgard ◽  
Brandon Q. Mercado ◽  
...  

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.


2017 ◽  
Vol 46 (37) ◽  
pp. 12645-12654 ◽  
Author(s):  
Kei Sakakibara ◽  
Shou Nagino ◽  
Hajime Akanuma ◽  
Yuki Tsukada ◽  
Hirofumi Nakano ◽  
...  

Photoinduced intramolecular electron transfer and charge recombination reactions were investigated using various Zn(ii)-porphyrin dyads having a 2,2′-bipyridine moiety.


2016 ◽  
Vol 52 (7) ◽  
pp. 1424-1427 ◽  
Author(s):  
Graeme Copley ◽  
Juwon Oh ◽  
Kota Yoshida ◽  
Daiki Shimizu ◽  
Dongho Kim ◽  
...  

A2B-type meso-(4-nitrophenyl)-substituted subporphyrins have been synthesized and shown to undergo very fast photoinduced intramolecular charge separation (CS) and charge recombination (CR) between the subporphyrin core and the meso-4-nitrophenyl group in CH2Cl2 as probed by femtosecond time-resolved transient absorption spectroscopy.


1989 ◽  
Vol 111 (5) ◽  
pp. 1917-1919 ◽  
Author(s):  
Ian R. Gould ◽  
Jacques E. Moser ◽  
Bruce Armitage ◽  
Samir Farid ◽  
Joshua L. Goodman ◽  
...  

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