Joint density-functional theory for electronic structure of solvated systems

TL;DR

This paper presents a new density functional theory that combines quantum and classical approaches to accurately model solvated electronic systems without fitting parameters.

Contribution

It introduces a unified variational framework merging electron and liquid densities for ab initio solvation modeling, eliminating the need for empirical fitting.

Findings

Predicts solvation energies accurately without fitted parameters

Matches the performance of advanced quantum-chemical cavity methods

Provides a rigorous theoretical foundation for solvated systems

Abstract

We introduce a new form of density functional theory for the {\em ab initio} description of electronic systems in contact with a molecular liquid environment. This theory rigorously joins an electron density-functional for the electrons of a solute with a classical density-functional theory for the liquid into a single variational principle for the free energy of the combined system. A simple approximate functional predicts, without any fitting of parameters to solvation data, solvation energies as well as state-of-the-art quantum-chemical cavity approaches, which require such fitting.