โ Scribed by Xiang-Yuan Li; Ke-Xiang Fu
No coin nor oath required. For personal study only.
Considering the influences of electrostatic potential Phi upon the change of solute charge distribution deltarho and rho upon the change deltaPhi at the same time, a more reasonable integral formula of dG = (1/2) integral (V) (rhodeltaPhi + Phideltarho)dV is used to calculate the change of the electrostatic free energy in charging the solute-solvent system to a nonequilibrium state, instead of the one of dG = integral (V) PhideltarhodV used before. This modification improves the expressions of electrostatic free energy and solvation free energy, in which no quantity of the intermediate equilibrium state is explicitly involved. Detailed investigation reveals that the solvation free energy of nonequilibrium only contains the interaction energy between the field due to the solute charge in vacuum, and the dielectric polarization at the nonequilibrium state. The solvent reorganization energies of forward and backward electron transfer reactions have been redefined because the derivations lead to a remarkable feature that these quantities are direction-dependent, unlike the theoretical models developed before. The deductions are given in the electric field-displacement form. Relevant discussions on the reliability of theoretical models suggested in this work have also been presented.
๐ SIMILAR VOLUMES
## Abstract In this work the authors present some evidences of defects in the popular continuous medium theories for nonequilibrium solvation. Particular attention has been paid to the incorrect reversible work approach. After convincing reasoning, the nonequilibrium free energy has been formulated
On the basis of continuous medium theory, a model for evaluation of spectral shifts in solution has been developed in this work. The interaction energy between solute dipole and reaction field and the self-energy of the reaction field have been formulated through derivations. Applying the interactio