First Principles Free-Energy Theory of Solvation with Atomic Scale Liquid Structure

TL;DR

This paper introduces a joint density-functional theory approach that accurately predicts solvation free energies and atomic-scale liquid structures efficiently, enabling realistic simulations of chemical processes in solutions.

Contribution

It develops a universal description for electron-liquid interactions within JDFT, making it a practical tool for modeling solvation phenomena without refitting.

Findings

Accurately predicts solvation free energies across multiple solvents.

Reproduces atomic-scale liquid structures consistent with experimental data.

Demonstrates effectiveness at the solid/liquid interface with reduced computational cost.

Abstract

Quantum-chemical processes in liquid environments impact broad areas of science, from molecular biology to geology to electrochemistry. While density-functional theory (DFT) has enabled efficient quantum-mechanical calculations which profoundly impact understanding of atomic-scale phenomena, realistic description of the liquid remains a challenge. Here, we present an approach based on joint density-functional theory (JDFT) which addresses this challenge by leveraging the DFT approach not only for the quantum mechanics of the electrons in a solute, but also simultaneously for the statistical mechanics of the molecules in a surrounding equilibrium liquid solvent. Specifically, we develop a new universal description for the interaction of electrons with an arbitrary liquid, providing the missing link to finally transform JDFT into a practical tool for the realistic description of chemical processes in solution. This approach predicts accurate solvation free energies and surrounding atomic-scale liquid structure for molecules and surfaces in multiple solvents without refitting, all at a fraction of the computational cost of methods of comparable detail and accuracy. To demonstrate the potential impact of this method, we determine the structure of the solid/liquid interface, offering compelling agreement with more accurate (but much more computationally intensive) theories and with X-ray reflectivity measurements.