Microcanonical-ensemble computer simulation of the high-temperature expansion coefficients of the Helmholtz free energy of a square-well fluid

• Published in: Molecular physics Vol. 116; no. 3; pp. 351 - 360
• Main Authors: Sastre, Francisco, Moreno-Hilario, Elizabeth, Sotelo-Serna, Maria Guadalupe, Gil-Villegas, Alejandro
• Format: Journal Article
• Language: English
• Published: Abingdon Taylor & Francis 01.02.2018; Taylor & Francis Ltd
• Subjects: Computer simulation; Free energy; Monte Carlo computer simulations; Monte Carlo simulation; Perturbation expansion; Square-well fluids; Thermal expansion
• ISSN: 0026-8976; 1362-3028
• DOI: 10.1080/00268976.2017.1392051

The microcanonical-ensemble computer simulation method (MCE) is used to evaluate the perturbation terms A i of the Helmholtz free energy of a square-well (SW) fluid. The MCE method offers a very efficient and accurate procedure for the determination of perturbation terms of discrete-potential systems such as the SW fluid and surpass the standard NVT canonical ensemble Monte Carlo method, allowing the calculation of the first six expansion terms. Results are presented for the case of a SW potential with attractive ranges 1.1 ≤ λ ≤ 1.8. Using semi-empirical representation of the MCE values for A i , we also discuss the accuracy in the determination of the phase diagram of this system.