Residual Entropy of Ordinary Ice from Multicanonical Simulations

TL;DR

This paper presents multicanonical simulation models to accurately estimate the residual entropy of ordinary ice, refining Pauling's classic value and challenging experimental measurements to improve precision.

Contribution

The authors develop simple lattice models and simulation methods that improve the accuracy of residual entropy estimates for ice I beyond previous theoretical results.

Findings

Residual entropy estimate within 0.1% of Nagle's analytical approximation

Refinement of Pauling's residual entropy value

Proposal for experimental verification with higher precision

Abstract

We introduce two simple models with nearest neighbor interactions on 3D hexagonal lattices. Each model allows one to calculate the residual entropy of ice I (ordinary ice) by means of multicanonical simulations. This gives the correction to the residual entropy derived by Linus Pauling in 1935. Our estimate is found to be within less than 0.1% of an analytical approximation by Nagle, which is an improvement of Pauling's result. We pose it as a challenge to experimentalists to improve on the accuracy of a 1936 measurement by Giauque and Stout by about one order of magnitude, which would allow one to identify corrections to Pauling's value unambiguously. It is straightforward to transfer our methods to other crystal systems.