Signatures of Solvation Thermodynamics in Spectra of Intermolecular Vibrations.

ABSTRACT: This study explores the thermodynamic and vibrational properties of water in the three-dimensional environment of solvated ions and small molecules using molecular simulations. The spectrum of intermolecular vibrations in liquid solvents provides detailed information on the shape of the local potential energy surface, which in turn determines local thermodynamic properties such as the entropy. Here, we extract this information using a spatially resolved extension of the two-phase thermodynamics method to estimate hydration water entropies based on the local vibrational density of states (3D-2PT). Combined with an analysis of solute-water and water-water interaction energies, this allows us to resolve local contributions to the solvation enthalpy, entropy, and free energy. We use this appro

SUBMITTER: Persson RAX 

PROVIDER: S-EPMC5607457 | biostudies-literature | 2017 Sep

REPOSITORIES: biostudies-literature