The photoinduced electron transfer (ET) reaction between coumarin 314 (C314) and N,N-dimethylaniline  (DMA) at the water/DMA interface is investigated by molecular dynamics simulations.   The solvent free energy curves for the ET reaction between excited C314 and DMA molecules are calculated and compared with those calculated for a simple point charge model of the solute. It is found that the reorganization free energy is very small when the full molecular description of the solute is taken into account. An estimate of the ET rate constant is in reasonable agreement with experiment. The  rotational dynamics and the solvation dynamics of C314 at the liquid/liquid interface are also calculated and are  in reasonable agreement with available experimental data.The calculations suggest that the polarity of the surface �reported� by the solute, as reflected by solvation dynamics and the reorganization free energy, is strongly solute-dependent.

Theoretical study of the photo-induced excited state electron transfer at the water/N,N-dimethylaniline interface

247th National Meeting (2014)

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