Instantaneous, parameter-free methods to define a solute's hydration shell

J Chem Phys. 2015 Dec 21;143(23):234501. doi: 10.1063/1.4937376.

Abstract

A range of methods are presented to calculate a solute's hydration shell from computer simulations of dilute solutions of monatomic ions and noble gas atoms. The methods are designed to be parameter-free and instantaneous so as to make them more general, accurate, and consequently applicable to disordered systems. One method is a modified nearest-neighbor method, another considers solute-water Lennard-Jones overlap followed by hydrogen-bond rearrangement, while three methods compare various combinations of water-solute and water-water forces. The methods are tested on a series of monatomic ions and solutes and compared with the values from cutoffs in the radial distribution function, the nearest-neighbor distribution functions, and the strongest-acceptor hydrogen bond definition for anions. The Lennard-Jones overlap method and one of the force-comparison methods are found to give a hydration shell for cations which is in reasonable agreement with that using a cutoff in the radial distribution function. Further modifications would be required, though, to make them capture the neighboring water molecules of noble-gas solutes if these weakly interacting molecules are considered to constitute the hydration shell.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Hydrogen Bonding
  • Molecular Dynamics Simulation
  • Noble Gases / chemistry*
  • Water / analysis*
  • Water / chemistry*

Substances

  • Noble Gases
  • Water