Joint Density-functional Theory and its Application to Systems in Solution

Abstract

The physics of solvation, the interaction of water with solutes, plays a central role in chemistry and biochemistry, and it is essential for the very existence of life. Despite the central importance of water and the advent of the quantum theory early in the twentieth century, the link between the fundamental laws of physics and the observable properties of water remain poorly understood to this day. The central goal of this thesis is to develop a new formalism and framework to make the study of systems (solutes or surfaces) in contact with liquid water as practical and accurate as standard electronic structure calculations without the need for explicit averaging over large ensembles of configurations of water molecules.

The thesis introduces a new form of density functional theory for the 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.

Using the new form of density-functional theory for the ab initio description of electronic systems in contact with a molecular liquid environment, the thesis then presents the first detailed study of the impact of a solvent on the surface chemistry of Cr$_2$O$_3$, the passivating layer of stainless steel alloys. In comparison to a vacuum, we predict that the presence of water has little impact on the adsorption of chloride ions to the oxygen-terminated surface but has a dramatic effect on the binding of hydrogen to that surface.

The thesis then presents a density-functional theory for water which gives reasonable agreement with molecular dynamics simulation data for the solvation of hard spheres in water and sufficient agreement with experimental data for hydration of inert gas atoms.

By combining the previous ideas, the last study in the thesis presents a model density functional which includes a description of the coupling of the solvent to the electrons of the solute through a pseudopotential without any empirical fitting of parameters to solvation data.