Orientational correlations and entropy in liquid water

The molecular pair correlation function in water is a function of a distance and five angles. It is here separated into the radial distribution function (RDF), which is only a function of distance, and an orientational distribution function (ODF), which is a function of the five angles for each distance between the molecules. While the RDF can be obtained from computer simulations, this is not practical for the ODF due to its high dimensionality. Two approaches for obtaining an approximation to the ODF are introduced. The first uses a product of one‐ and two‐dimensional marginal distributions from computer simulations. The second uses the gas‐phase low‐density limit as a reference and applies corrections based on (a) the orientationally averaged interactions in the liquid calculated by simulations, and (b) the observed differences in the one‐ and two‐dimensional marginal distributions in the gas and in the liquid. The site superposition approximation was also tested and found to be inadequate for reproduc...

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