Ströker Philipp, Hellmann Robert, Meier Karsten
Institut für Thermodynamik, Helmut-Schmidt-Universität/Universität der Bundeswehr Hamburg, Holstenhofweg 85, 22043 Hamburg, Germany.
J Chem Phys. 2022 Sep 21;157(11):114504. doi: 10.1063/5.0107851.
Ten different thermodynamic properties of the noble gas krypton were calculated by Monte Carlo simulations in the isothermal-isobaric ensemble using a highly accurate ab initio pair potential, Feynman-Hibbs corrections for quantum effects, and an extended Axilrod-Teller-Muto potential to account for nonadditive three-body interactions. Fourteen state points at a liquid and a supercritical isotherm were simulated. To obtain results representative for macroscopic systems, simulations with several particle numbers were carried out and extrapolated to the thermodynamic limit. Our results agree well with experimental data from the literature, an accurate equation of state for krypton, and a recent virial equation of state (VEOS) for krypton in the region where the VEOS has converged. These results demonstrate that very good agreement between simulation and experiment can only be achieved if nonadditive three-body interactions and quantum effects are taken into account.
利用高精度的从头算对势、量子效应的费曼 - 希布斯修正以及扩展的阿西洛德 - 泰勒 - 武藤势来考虑非加和三体相互作用，在等温等压系综中通过蒙特卡罗模拟计算了稀有气体氪的十种不同热力学性质。模拟了液体和超临界等温线上的14个状态点。为了获得代表宏观系统的结果，进行了几个粒子数的模拟并外推到热力学极限。我们的结果与文献中的实验数据、氪的精确状态方程以及氪在维里状态方程（VEOS）收敛区域的最新维里状态方程非常吻合。这些结果表明，只有考虑非加和三体相互作用和量子效应，模拟和实验之间才能取得非常好的一致性。
