Tests of the empirical potential structure refinement method and a new method of application to neutron diffraction data on water

Abstract

Empirical potential structure refinement (EPSR) is a method for developing a structural model of a liquid for which diffraction measurements are available. The EPSR technique involves refining a starting interatomic potential energy function in a way that produces the best possible agreement between the simulated and measured site-site partial structure factors. Here a series of test simulations are performed to establish how well the EPSR method can recover the interatomic potential for a single component fluid of Lennard-Jones particles, and for a binary fluid consisting of charged atoms interacting at short range by a Lennard-Jones potential. Special attention is given to the problem of developing an accurate interatomic potential for water using these procedures. An alternative method for perturbing the starting potential is used to obtain the best possible fit to the diffraction data. The resulting parametrization of the water potential is in contrast to many existing effective potentials for water, and indicates that water molecules in the liquid at ambient conditions are highly polarized, as has been suggested in recent ‘first-principles’ simulations of water. Three-body correlation functions and spatial density functions derived from the EPSR simulations show excellent agreement with those obtained with the model potential simulations. However, the potentials extracted by EPSR are found to depend on the constraints applied to the hardness of the core potential and the energy and pressure of the simulation, even when the fits to the data are equally good. It is concluded that performing EPSR on diffraction data can be used as a good test for interatomic potentials and to derive reliable many-body structures in the liquid state, but cannot on its own be used to derive a reliable set of site-site pair potentials for a particular system.