Grosfils Patrick, Lutsko James F
Microgravity Research Center, Chimie Physique E.P. CP 165/62, Université Libre de Bruxelles, Av.F.D.Roosevelt 50, 1050 Brussels, Belgium.
J Chem Phys. 2009 Feb 7;130(5):054703. doi: 10.1063/1.3072156.
The validity of the principle of corresponding states is investigated for the case of a potential with more than one intrinsic length scale. The planar surface tension of coexisting liquid and vapor phases of a fluid of Lennard-Jones atoms is studied as a function of the range of the potential using both Monte Carlo simulations and density functional theory (DFT). The interaction range is varied from r(c)() = 2.5 to r(c)() = 6 and the surface tension is determined for temperatures ranging from T(*) = 0.7 up to the critical temperature in each case. The simulation results are consistent with previous studies and are shown to obey the law of corresponding states even though the potential has two intrinsic length scales. It is further shown that the corresponding states principle can also be used to enhance the accuracy of some, but not all, DFT calculations of the surface tension. The results show that most of the cutoff dependence of the surface tension can be explained as a result of changes in the cutoff-dependent phase diagram and that corresponding states can be a useful tool for explaining differences between theory and simulation.
针对具有多个固有长度尺度的势场情形,研究了对应态原理的有效性。利用蒙特卡罗模拟和密度泛函理论(DFT),研究了 Lennard-Jones 原子流体共存液相和气相的平面表面张力与势场范围的函数关系。相互作用范围从 r(c)() = 2.5 变化到 r(c)() = 6,并在每种情况下确定了温度范围从 T(*) = 0.7 到临界温度时的表面张力。模拟结果与先前的研究一致,并且表明即使势场具有两个固有长度尺度,表面张力仍服从对应态定律。进一步表明,对应态原理还可用于提高部分(但不是全部)表面张力 DFT 计算的精度。结果表明,表面张力的大部分截止依赖性可以解释为截止依赖相图变化的结果,并且对应态可作为解释理论与模拟之间差异的有用工具。