Reorganization energy and pre-exponential factor from temperature-dependent experiments in electron transfer reactions. A typical example: the reduction of tert-nitrobutane

2012 ◽  
Vol 14 (5) ◽  
pp. 1581-1584 ◽  
Author(s):  
Cyrille Costentin ◽  
Cyril Louault ◽  
Marc Robert ◽  
Vincent Rogé ◽  
Jean-Michel Savéant
Keyword(s):  
Electron Transfer ◽  
Reorganization Energy ◽  
Transfer Reactions ◽  
Temperature Dependent ◽  
Exponential Factor ◽  
Electron Transfer Reactions

Singlet and triplet energy splitting in the radical ion pairs generated by photoinduced electron-transfer reactions

2001 ◽  
Vol 73 (3) ◽  
pp. 519-523 ◽  
Author(s):  
Shozo Tero-Kubota
Keyword(s):  
Electron Transfer ◽  
Photoinduced Electron Transfer ◽  
Continuous Wave ◽  
Ion Pairs ◽  
Reorganization Energy ◽  
Transfer Reactions ◽  
Triplet States ◽  
Energy Splitting ◽  
Triplet Energy ◽  
Electron Transfer Reactions

Chemically induced dynamic electron polarization (CIDEP) spectra generated by photoinduced electron-transfer reactions have been studied using continuous-wave time-resolved EPR and FTEPR spectroscopy. It has been suggested that the energy difference (DEST) between the singlet and triplet states of radical ion pairs (RIPs) is dependent on the charge recombination free energy (­DGCR) and reorganization energy (l). The result is interpreted in terms of the spin-selective stabilization or destabilization of RIP states by electronic coupling with the S0 and locally excited triplet states of the donor­acceptor pair at equilibrium distance in the reaction coordinate. It has been verified that a charge transfer-type exchange interaction governs the DEST. Magnitudes as well as the sign of DEST can be predicted at the distance of the solvent-separated RIP based on DGCR and l values.

scholarly journals Converting the bis-FeIV state of the diheme enzyme MauG to Compound I decreases the reorganization energy for electron transfer

2015 ◽  
Vol 473 (1) ◽  
pp. 67-72
Author(s):  
Brian A. Dow ◽  
Victor L. Davidson
Keyword(s):  
Electron Transfer ◽  
Reorganization Energy ◽  
Transfer Reactions ◽  
Compound I ◽  
Electron Transfer Reactions ◽  
Charge Delocalization ◽  
Redox Center ◽  
High Valent ◽  
Redox Centers

The extent of charge delocalization throughout the diheme redox center of MauG influences the reorganization energy associated with the electron transfer reactions to the high-valent hemes. This explains how enzymes can optimize various reactions by utilizing different high-valent redox centers.

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