Relationships between Molecular Structural Order Parameters and Equilibrium Water Dynamics in Aqueous Mixtures

• Published in: The journal of physical chemistry. B 2023-05, Vol.127 (20), p.4577-4594
• Main Authors: Robinson Brown, Dennis Charles, Webber, Thomas R., Jiao, Sally, Rivera Mirabal, Daniela M., Han, Songi, Shell, M. Scott
• Format: Article
• Language: English
• Subjects: B: Liquids; Chemical and Dynamical Processes in Solution; Chemistry
• ISSN: 1520-6106; 1520-5207
• DOI: 10.1021/acs.jpcb.3c00826

Water’s unique thermophysical properties and how it mediates aqueous interactions between solutes have long been interpreted in terms of its collective molecular structure. The seminal work of Errington and Debenedetti [Nature 2001, 409, 318–321] revealed a striking hierarchy of relationships among the thermodynamic, dynamic, and structural properties of water, motivating many efforts to understand (1) what measures of water structure are connected to different experimentally accessible macroscopic responses and (2) how many such structural metrics are adequate to describe the collective structural behavior of water. Diffusivity constitutes a particularly interesting experimentally accessible equilibrium property to investigate such relationships because advanced NMR techniques allow the measurement of bulk and local water dynamics in nanometer proximity to molecules and interfaces, suggesting the enticing possibility of measuring local diffusivities that report on water structure. Here, we apply statistical learning methods to discover persistent structure–dynamic correlations across a variety of simulated aqueous mixtures, from alcohol–water to polypeptoid–water systems. We investigate a variety of molecular water structure metrics and find that an unsupervised statistical learning algorithm (namely, sequential feature selection) identifies only two or three independent structural metrics that are sufficient to predict water self-diffusivity accurately. Surprisingly, the translational diffusivity of water across all mixed systems studied here is strongly correlated with a measure of tetrahedral order given by water’s triplet angle distribution. We also identify a separate small number of structural metrics that well predict an important thermodynamic property, the excess chemical potential of an idealized methane-sized hydrophobe in water. Ultimately, we offer a Bayesian method of inferring water structure by using only structure–dynamics linear regression models with experimental Overhauser dynamic nuclear polarization (ODNP) measurements of water self-diffusivity. This study thus quantifies the relationships among several distinct structural order parameters in water and, through statistical learning, reveals the potential to leverage molecular structure to predict fundamental thermophysical properties. In turn, these findings suggest a framework for solving the inverse problem of inferring water’s molecular structure using experimental measurements su