Vlasiuk Maryna, Frascoli Federico, Sadus Richard J
Centre for Molecular Simulation, Swinburne University of Technology, P.O. Box 218, Hawthorn, Victoria 3122, Australia.
Department of Mathematics, Swinburne University of Technology, P.O. Box 218, Hawthorn, Victoria 3122, Australia.
J Chem Phys. 2016 Sep 14;145(10):104501. doi: 10.1063/1.4961682.
The thermodynamic, structural, and vapor-liquid equilibrium properties of neon are comprehensively studied using ab initio, empirical, and semi-classical intermolecular potentials and classical Monte Carlo simulations. Path integral Monte Carlo simulations for isochoric heat capacity and structural properties are also reported for two empirical potentials and one ab initio potential. The isobaric and isochoric heat capacities, thermal expansion coefficient, thermal pressure coefficient, isothermal and adiabatic compressibilities, Joule-Thomson coefficient, and the speed of sound are reported and compared with experimental data for the entire range of liquid densities from the triple point to the critical point. Lustig's thermodynamic approach is formally extended for temperature-dependent intermolecular potentials. Quantum effects are incorporated using the Feynman-Hibbs quantum correction, which results in significant improvement in the accuracy of predicted thermodynamic properties. The new Feynman-Hibbs version of the Hellmann-Bich-Vogel potential predicts the isochoric heat capacity to an accuracy of 1.4% over the entire range of liquid densities. It also predicts other thermodynamic properties more accurately than alternative intermolecular potentials.
利用从头算、经验和半经典分子间势以及经典蒙特卡罗模拟，对氖的热力学、结构和汽液平衡性质进行了全面研究。还报道了针对两种经验势和一种从头算势的等容热容和结构性质的路径积分蒙特卡罗模拟。报告了等压和等容热容、热膨胀系数、热压力系数、等温及绝热压缩率、焦耳 - 汤姆逊系数和声速，并将其与从三相点到临界点的整个液体密度范围内的实验数据进行了比较。Lustig的热力学方法被正式扩展到温度依赖的分子间势。使用费曼 - 希布斯量子校正纳入量子效应，这使得预测的热力学性质的准确性有了显著提高。新的费曼 - 希布斯版本的赫尔曼 - 比希 - 沃格尔势在整个液体密度范围内将等容热容预测到1.4%的精度。它还比其他分子间势更准确地预测了其他热力学性质。
