Calculation of the melting point of alkali halides by means of computer simulations

• Published in: arXiv.org
• Main Authors: Aragones, J L, Sanz, E, Valeriani, C, Vega, C
• Format: Paper Journal Article
• Language: English
• Published: Ithaca Cornell University Library, arXiv.org 17.09.2012
• Subjects: Alkali halides; Computer simulation; Halides; Mathematical models; Melt temperature; Melting points; Physics - Chemical Physics; Physics - Computational Physics; Physics - Statistical Mechanics
• ISSN: 2331-8422
• DOI: 10.48550/arxiv.1209.3692

In this manuscript we study the liquid-solid coexistence of NaCl-type alkali halides, described by interaction potentials such as Tosi-Fumi (TF), Smith-Dang (SD) and Joung-Cheatham (JC), and compute their melting temperature (Tm) at 1 bar via three independent routes: 1) liquid/solid direct coexistence, 2) free-energy calculations and 3) Hamiltonian Gibbs-Duhem integration. The melting points obtained by the three routes are consistent with each other. The calculated Tm of the Tosi-Fumi model of NaCl is in good agreement with the experimental value as well as with other numerical calculations. However, the other two models considered for NaCl, SD and JC, overestimate the melting temperature of NaCl by more than 200 K. We have also computed the melting temperature of other alkali halides using the Tosi-Fumi interaction potential and observed that the predictions are not always as close to the experimental values as they are for NaCl. It seems that there is still room for improvement in the area of force-fields for alkaline halides, given that so far most models are still unable to describe a simple yet important property such as the melting point.