Journal of the American Chemical Society, Vol.127, No.50, 17867-17876, 2005
Solvent friction effect on intramolecular electron transfer
U-shaped donor-bridge-acceptor molecules with different electronic couplings have been investigated as a function of temperature in solvents with slow polarization relaxation, in particular, N-methylacetamide (NMA) and N-methylpropionamide (NMP). At high temperature, the electron-transfer rate is well described by a nonadiabatic model; however, the rate at low temperature is controlled by the solvent friction. The change of the electron-transfer mechanism is discussed and compared with theoretical models.