Towards a generalized iso-density continuum model for molecular solvents in plane-wave DFT.

Implicit electron-density solvation models offer a computationally efficient solution to the problem of calculating thermodynamic quantities of solvated systems from first-principles quantum mechanics. However, despite much recent interest in such models, to date the applicability of such models in the plane-wave context to non-aqueous solvents has been limited because the determination of the model parameters requires fitting to a large database of experimental solvation energies for each new solvent considered. This work presents a simple approach to quickly find approximations to the non-electrostatic contributions to the solvation energy, allowing for development of new iso-density models for a large class of protic and aprotic solvents from only simple, single-molecule ab initio calculations and readily available bulk thermodynamic data. Finally, to illustrate the capabilities of the resulting theory, we also calculate the surface solvation energies of crystalline LiF in various different non-aqueous solvents, and discuss the observed trends and their relevance to lithium battery technology. [ABSTRACT FROM AUTHOR]