Decreased Interfacial Charge Recombination Rate Constants with N3-Type Sensitizers

2010 ◽  
Vol 1 (11) ◽  
pp. 1725-1728 ◽  
Author(s):  
Maria Abrahamsson ◽  
Patrik G. Johansson ◽  
Shane Ardo ◽  
Andrew Kopecky ◽  
Elena Galoppini ◽  
...  
2000 ◽  
Vol 39 (17) ◽  
pp. 3765-3770 ◽  
Author(s):  
Donald V. Scaltrito ◽  
Craig A. Kelly ◽  
Mark Ruthkosky ◽  
Mark C. Zaros ◽  
Gerald J. Meyer

2008 ◽  
Vol 36 (6) ◽  
pp. 1165-1168 ◽  
Author(s):  
Amandine Maréchal ◽  
W. John Ingledew ◽  
Peter R. Rich

Vibrational changes associated with CO recombination to ferrous horseradish peroxidase were investigated by rapid-scan FTIR (Fourier-transform IR) spectroscopy in the 1200–2200 cm−1 range. At pH 6.0, two conformers of bound CO are present that appear as negative bands at 1905 and 1934 cm−1 in photolysis spectra. Their recombination rate constants are identical, confirming that they arise from two substates of bound CO that are in rapid thermal equilibrium, rather than from heterogeneous protein sites. A smaller positive band at 2134 cm−1 also appears on photolysis and decays with the same rate constant, indicative of an intraprotein geminate site involved in recombination or, possibly, a weak-affinity surface CO-binding site. Other signals arising from protein and haem in the 1700–1200 cm−1 range can also be time-resolved with similar kinetics.


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.


1987 ◽  
Vol 53 (3) ◽  
pp. 1054-1057 ◽  
Author(s):  
I. E. Zabelinskii ◽  
O. P. Shatalov

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