The Angular Localization Function (ALF): a practical tool to measure solvent angular order with Molecular Density Functional Theory

TL;DR

The paper introduces the Angular Localization Function (ALF), a new tool derived from molecular density functional theory, to quantify local angular order of solvents around solutes, enhancing interpretation of solvent structure.

Contribution

It presents ALF as a novel, entropy-based measure for analyzing solvent angular order, filling a gap in the interpretation of molecular density functional theory results.

Findings

ALF provides detailed insights into solvent angular distribution.

ALF complements existing measures like polarization and charge density.

Application to water, octanol, and clay minerals demonstrates its utility.

Abstract

Molecular density functional theory is a powerful technique for efficiently computing the spatially and orientationally dependent equilibrium density of a molecular solvent around an arbitrary solute. This density encodes the detailed solvent structure, but contains so much information that it is difficult to interpret comprehensively. Although spatial dependence is frequently analyzed through orientationally integrated number density, angular information remains poorly exploited. The present work addresses this gap by introducing a function that provides a local measure of the angular order: the Angular Localization Function (ALF), derived from the ideal free energy functional, which quantifies the entropy. We discuss the connections between ALF and well known statistical functions. We illustrate the utility of ALF by discussing the solvent structure for three systems immersed in water: water as a solute, an octanol molecule, and three clay minerals (talc, fluorotalc and pyrophyllite) with small differences in their structure leading to subtle effects on their interactions with water. ALF provides information complementary to quantities such as the average polarization or charge density to characterize the local orientational distribution of solvent molecules around solutes and next to surfaces. It also offers a convenient visualization tool akin to the Electronic Localization Function (ELF) used to analyze bonding in quantum chemistry.