Structural and thermodynamic information content of water three-body angle distributions: predicting liquid anomalies and solvation thermodynamics from solvent structure alone

Jacob Monroe
Jacob Monroe
Engineering 2, Room 1519

 

Water is widely known to adopt transient tetrahedral order in the liquid state, leading to many of its anomalous behaviors, such as a maximum in density as a function of temperature and a maximum in diffusivity at fixed temperature as a function of density. I will present a detailed examination of the behavior of the three-body angle distribution, which describes this tetrahedral order, both for bulk water at various temperatures and densities, as well as in the hydration shells of model solutes. Perturbations to this distribution are first used to map out boundaries for anomalous water behavior, then as the basis for preliminary empirical models of the thermodynamics of the solvation process. The former results contribute to a more fundamental understanding of water physics, while the latter represent a promising avenue for rapidly yet rigorously computing solvation free energies and free energies of binding.