X-ray Diffraction and Molecular Dynamics Study of Medium-range Order in Ambient and Hot Water

TL;DR

This study combines high-resolution x-ray diffraction and molecular dynamics simulations to analyze the medium-range order in water at different temperatures, supporting a two-state fluctuation model of water structure.

Contribution

It introduces a high-precision x-ray diffraction method and compares experimental data with MD simulations to explore water's structural fluctuations.

Findings

Experimental data accurately resolve shell structure up to 12 Å

MD simulations reproduce experimental shell structure well beyond 4 Å

Results support a two-state fluctuation model of water structure

Abstract

We have developed x-ray diffraction measurements with high energy-resolution and accuracy to study water structure at three different temperatures (7, 25 and 66 C) under normal pressure. Using a spherically curved Ge crystal an energy resolution better than 15 eV has been achieved which eliminates influence from Compton scattering. The high quality of the data allows a precise oxygen-oxygen pair correlation function (PCF) to be directly derived from the Fourier transform of the experimental data resolving shell structure out to ~12 {\AA}, i.e. 5 hydration shells. Large-scale molecular dynamics (MD) simulations using the TIP4P/2005 force-field reproduce excellently the experimental shell-structure in the range 4-12 {\AA} although less agreement is seen for the first peak in the PCF. The Local Structure Index [J. Chem. Phys. 104, 7671 (1996)] identifies a tetrahedral minority giving the intermediate-range oscillations in the PCF and a disordered majority providing a more featureless background in this range. The current study supports the proposal that the structure of liquid water, even at high temperatures, can be described in terms of a two-state fluctuation model involving local structures related to the high-density and low-density forms of liquid water postulated in the liquid-liquid phase transition hypothesis.