Intermolecular electron transfer between coumarin dyes and aromatic amines in Triton-X-100 micellar solutions: Evidence for Marcus inverted region

2004 ◽  
Vol 120 (6) ◽  
pp. 2824-2834 ◽  
Author(s):  
Manoj Kumbhakar ◽  
Sukhendu Nath ◽  
Tulsi Mukherjee ◽  
Haridas Pal
2017 ◽  
Vol 19 (7) ◽  
pp. 5658-5673 ◽  
Author(s):  
Yeduru Venkatesh ◽  
Venkatesan Munisamy ◽  
Bheerappagari Ramakrishna ◽  
Pippara Hemant Kumar ◽  
Haraprasad Mandal ◽  
...  

We demonstrated intrinsic, non-stationary and diffusion controlled photo-induced bimolecular electron transfer follow 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 ◽  
...  

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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