An analytical formalism for the calculation of the solvent reorganization energy of electron transfer (ET) in a solute of arbitrary shape and arbitrary charge distribution, was reported. The formalism was realized in a computational algorithm which allowed the study of ET in large molecules with a computational cost comparable to that of dielectric continuum calculations. The results of the calculations on model ET systems agreed well with Monte Carlo simulations. The theory highlighted the difference in the mechanisms of ET activation by longitudinal and transverse polarization modes and by local density fluctuations of the solvent.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- Physical and Theoretical Chemistry