Generalizing Continuum Solvation in Crystal to Nonaqueous Solvents: Implementation, Parametrization, and Application...

We present an extension of a generalized finite-difference Poisson-Boltzmann (FDPB) continuum solvation model based on a self-consistent reaction field treatment to nonaqueous solvents. Implementation and reparametrization of the cavitation, dispersion, and structural (CDS) effects nonelectrostatic model are presented in CRYSTAL, with applications to both finite and infinite periodic systems. For neutral finite systems, computed errors with respect to available experimental data on free energies of solvation of 2523 solutes in 91 solvents, as well as 144 transfer energies from water to 14 organic solvents are on par with the reference SM12 solvation model for which the CDS parameters have been developed. Calculations performed on a TiO₂ anatase surface and compared to VASPsol data revealed an overall very good agreement of computed solvation energies, surface energies, as well as band structure changes upon solvation in three different solvents, validating the general applicability of the reparametrized FDPB approach to neutral nonperiodic and periodic solutes in aqueous and nonaqueous solvents. For ionic species, while the reparametrized CDS model led to large errors on free energies of solvation of anions, addition of a corrective term based on Abraham's acidity of the solvent significantly improved the accuracy of the proposed continuum solvation model, leading to errors on aqueous pK_a of a test set of 83 solutes divided by a factor of 4 compared to the reference solvation model based on density (SMD). Overall, therefore, these encouraging results demonstrate that the generalized FDPB continuum solvation model can be applied to a broad range of solutes in various solvents, ranging from finite neutral or charged solutes to extended periodic surfaces.