Modeling solvatochromic shifts using the orbital-free embedding potential at statistically mechanically averaged...

The correspondence between the exact embedding potential and the pair of the electron densities--that of the embedded molecule and that of its environment [Wesolowski and Warshel, J. Phys. Chem. 1993, 97, 8050]--is used to generate the average embedding potential and to subsequently calculate the solvatochromic shifts in a number of organic chromophores in solvents of various polarities. The averaged embedding potential is evaluated at a fictitious electron density of the solvent, which is obtained by means of "dressing up" with electrons the classical site distributions derived from the statistical-mechanical, 3D molecular theory of solvation (aka 3D-RISM method) [Kovalenko In Molecular Theory of Solvation; Hirata, Ed.; Understanding Chemical Reactivity; 2003, Vol 24], self-consistently coupled with the electronic structure of the solute. The proposed approach to modeling solvatochromic shifts can be situated between the implicit and explicit type of models for the solvent. Numerical examples are given for the lowest-lying n --> pi* and pi --> pi* excitations.