Weighted-density functionals for cavity formation and dispersion energies in continuum solvation models

Sundararaman, Ravishankar; Gunceler, Deniz; Arias, T. A.

doi:10.1063/1.4896827

Cited by 32 publications

(64 citation statements)

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“…(See [15] for a full specification.) Briefly, G cav is completely constrained by bulk properties of the solvent including density, surface tension and vapor pressure, and reproduces the classical density functional and molecular dynamics predictions for the cavity formation free energy from [23] with no fit parameters.…”

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“…Recently, we correlated the dielectric cavity sizes for different solvents with the extent of nonlocality of the solvent response to enable a unified electron-density parametrization for multiple solvents [15], but the electron density threshold n c that determines the cavity size still required a fit to solvation energies of organic molecules. Joint density functional theory (JDFT) [16] combines a classical density functional description of the solvent with an electronic density functional description of the solute, naturally captures the nonlocal response of the fluid, and does not involve cavities that are fit to solvation energies.…”

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“…, where G cav is a non-local weighted density approximation to the cavity formation free energy and E disp empirically accounts for dispersion and the remaining contributions, exactly as in [15]. (See [15] for a full specification.)…”

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“…We first describe a method to estimate that initial distribution from the overlap of solute and solvent electron densities, and then show how to calculate the nonlocal linear response of the fluid using an angular momentum expansion. The addition of nonlocal cavity formation free energy and dispersion functionals derived from classical density functional theory [15] results in an accurate description of solvation free energies of neutral organic molecules as well as highly polar and ionic systems. Finally, we show that the nonlocal dependence of this model on the solute electron density enables self-consistent solvation in quantum MonteCarlo calculations, which was previously impractical due to statistical noise in the local electron density [17].…”

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“…Solvation energies -We implement the SaLSA solvation model in the open source density-functional software JDFTx [27], and perform calculations using normconserving pseudopotentials [20] at 30 E h plane-wave cutoff and the revTPSS meta-generalized-gradient exchangecorrelation functional [28]. For three solvents, water, chloroform and carbon tetrachloride, we fit the sole parameter s 6 to minimize the RMS error in the solvation energies of a small but representative set of neutral organic molecules with a variety of functional groups and chain lengths (same set for each solvent as in [15]). Table I summarizes the optimum values of s 6 and the corresponding RMS error in solvation energies.…”

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

Sundararaman

Schwarz

Letchworth‐Weaver

et al. 2015

The Journal of Chemical Physics

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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.Electronic density functional theory [1, 2] enables firstprinciples prediction of material properties at the atomic scale including structures and reaction mechanisms. Liquids play a vital role in many systems of technological and scientific interest, but the need for thermodynamic phasespace sampling complicates direct first-principles calculations. Further, absence of dispersion interactions and neglect of quantum-mechanical effects in the motion of protons limit the accuracy of ab initio molecular dynamics for solvents such as water [3,4].Continuum solvation models replace the effect of the solvent by the response of an empirically-determined dielectric cavity. Traditional solvation models [5-10] employ a large number of atom-dependent parameters, are highly accurate in the class of systems to which they are fit -typically organic molecules in solution, and have been tremendously successful in the evaluation of reaction mechanisms and design of molecular catalysts. Unfortunately, the large number of parameters precludes the extrapolation of these models to systems outside their fit set, such as metallic or ionic surfaces in solution. Recent solvation models that employ an electron-density based parametrization [11,12] require only two or three parameters and extrapolate more reliably, but still encounter difficulties for charged and highly polar systems [13,14].The need for empirical parameters in continuum solvation arises primarily because of the drastic simplification of the nonlocal and nonlinear response of the real liquid with that of a continuum dielectric cavity. Recently, we correlated the dielectric cavity sizes for different solvents with the extent of nonlocality of the solvent response to enable a unified electron-density parametrization for multiple solvents [15], but the electron density threshold n c that determines the cavity size still required a fit to solvation energies of organic molecules. Joint density functional theory (JDFT) [16] combines a classical de...

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