Spicing up continuum solvation models with SaLSA: the spherically-averaged liquid susceptibility ansatz

Abstract

Continuum solvation models enable electronic structure calculations of systems in liquid environments, but because of the large number of empirical parameters, they are limited to the class of systems in their fit set (typically organic molecules). Here, we derive a solvation model with no empirical parameters for the dielectric response by taking the linear response limit of a classical density functional for molecular liquids. This model directly incorporates the nonlocal dielectric response of the liquid using an angular momentum expansion, and with a single fit parameter for dispersion contributions it predicts solvation energies of neutral molecules with an RMS error of 1.3 kcal/mol in water and 0.8 kcal/mol in chloroform and carbon tetrachloride. We show that this model is more accurate for strongly polar and charged systems than previous solvation models because of the parameter-free electric response, and demonstrate its suitability for ab initio solvation, including self-consistent solvation in quantum Monte Carlo calculations.

5 pages, 4 figures

References in corpus (6)

• Nuclear quantum effects in water
• Continuum variational and diffusion quantum Monte Carlo calculations
• Smooth relativistic Hartree-Fock pseudopotentials for H to Ba and Lu to Hg
• Norm-conserving Hartree-Fock pseudopotentials and their asymptotic behavior
• Joint density-functional theory for electronic structure of solvated systems
• Weighted-density functionals for cavity formation and dispersion energies in continuum solvation models

Cited by in corpus (5)

• Grand canonical electronic density-functional theory: algorithms and applications to electrochemistry
• JDFTx: software for joint density-functional theory
• The charge-asymmetric nonlocally-determined local-electric (CANDLE) solvation model
• First-principles electrostatic potentials for reliable alignment at interfaces and defects
• Simulation of many-electron systems that exchange matter with the environment