Ewald sum corrections in simulations of ion and dipole solvation and electron transfer.

Abstract

Periodic boundary conditions and Ewald sums used in standard simulation protocols require finite-size corrections when the total charge of the simulated system is nonzero. Corrections for ion solvation were introduced by Hummer, Pratt, and García, [J. Chem. Phys. 107, 9275 (1997)]. The latter approach is extended here to derive finite-size correction for the Stokes-shift and reorganization energy applied to electron-transfer reactions. The same correction term, scaling inversely with the box size, adds to the reorganization energy from the energy-gap variance but is subtracted from the reorganization energy calculated from the Stokes shift. Finite-size corrections thus widen the gap between these two quantities, which were recently found to diverge for protein electron transfer. Corrections to the free energy of dipole solvation and the variance of the electric field scale as m2/L3 with the solute dipole m and the box size L.