Proton-Coupled Electron Transfer in a Hydrogen-Bonded Charge-Transfer Complex

2016 ◽  
Vol 120 (41) ◽  
pp. 10780-10785 ◽  
Author(s):  
Sandeep Verma ◽  
Sunil Aute ◽  
Amitava Das ◽  
Hirendra N. Ghosh
Keyword(s):  
Electron Transfer ◽  
Charge Transfer ◽  
Charge Transfer Complex ◽  
Proton Coupled Electron Transfer ◽  
Hydrogen Bonded

Zur Theorie der Elektronenübergangsreaktionen in molekularen Komplexen / Theory of Electron Transfer Reactions in Molecular Complexes

1974 ◽  
Vol 29 (6) ◽  
pp. 880-887 ◽  
Author(s):  
P. P. Schmidt
Keyword(s):  
Activation Energy ◽  
Electron Transfer ◽  
Charge Transfer ◽  
Rate Constant ◽  
Reaction Rate ◽  
Charge Transfer Complex ◽  
Rate Theory ◽  
Transfer Step ◽  
Donor And Acceptor ◽  
Inner Sphere

This paper reports a theory of the inner sphere-type electron transfer reaction. Inner sphere reactions, as opposed to the outer sphere variety, require that the solvate or ligand shells surrounding the electron donor and acceptor species undergo considerable change in the course of the electron transfer. In this paper we assume that the electron transfer step takes place in a molecular complex which exists in equilibrium with the reactants. The electron transfer step occurs as a non-radiative charge transfer-type transition. In this manner we treat the charge transfer kinetics, in particular, the evaluation of the reaction rate constant, in the same manner as is usual for non-radiative problems. The analysis leading to the rate constant expression is based on Yamamoto’s general chemical reaction rate theory. The rate constant expressions obtained are quite general, they hold for any degree of strength of coupling between subsystems comprising the entire system. The activation energy, in the Arrhenius form for the rate constant, shows a dependence on the energy (work) of formation of the intermediate charge transfer complex, on vibrational shift energies associated with the molecular motions of the ligands, and on solvent repolarization energies. The activation energy also shows an important dependence on coupling terms which link the vibrations of the molecular inner shell with the polarization states of the (assumed) dielectric continuum which surrounds the charge transfer participants. The approach we take in developing this theory we believe points the way towards the development of a more complete theory capable of accounting for the dynamics of the molecular reorganization leading to the intermediate charge transfer complex as well as accounting for the electron transfer step itself.

Diffusive and non-diffusive photo-induced proton coupled electron transfer from hydrogen bonded phenols to meso-tetrakis-5,10,15,20-pentafluorophenyl porphyrin

2014 ◽  
Vol 16 (42) ◽  
pp. 23173-23181 ◽  
Author(s):  
P. Hemant Kumar ◽  
Y. Venkatesh ◽  
S. Prashanthi ◽  
D. Siva ◽  
B. Ramakrishna ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Movement Time ◽  
Proton Coupled Electron Transfer ◽  
Proton Movement ◽  
First Time ◽  
Hydrogen Bonded

Ultrafast photo-induced proton coupled electron transfer is observed for the first time from H-bonded phenols to pentafluorophenyl porphyrin indicating the proton movement time to be 40–60 ps depending on the base used.

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