DNRF Center Glass and Time, IMFUFA, Department of Sciences, Roskilde University, P.O. Box 260, DK-4000 Roskilde, Denmark.
J Chem Phys. 2009 Dec 21;131(23):234503. doi: 10.1063/1.3265955.
In this third paper of the series, which started with Bailey et al. [J. Chem. Phys. 129, 184507 (2008); ibid. 129, 184508 (2008)], we continue the development of the theoretical understanding of strongly correlating liquids--those whose instantaneous potential energy and virial are more than 90% correlated in their thermal equilibrium fluctuations at constant volume. The existence of such liquids was detailed in previous work, which identified them, based on computer simulations, as a large class of liquids, including van der Waals liquids but not, e.g., hydrogen-bonded liquids. We here discuss the following: (1) the scaling properties of inverse power-law and extended inverse power-law potentials (the latter includes a linear term that "hides" the approximate scale invariance); (2) results from computer simulations of molecular models concerning out-of-equilibrium conditions; (3) ensemble dependence of the virial/potential-energy correlation coefficient; (4) connection to the Grüneisen parameter; and (5) interpretation of strong correlations in terms of the energy-bond formalism.
在本系列的第三篇论文中，我们延续了对强关联液体的理论理解的研究。这一系列始于 Bailey 等人的工作[J. Chem. Phys. 129, 184507 (2008); ibid. 129, 184508 (2008)]，强关联液体是指在等容热平衡涨落中，其瞬时势能和维里的相关性超过 90%。在之前的工作中详细地讨论了这些液体的存在，这些工作基于计算机模拟，将它们确定为一大类液体，包括范德瓦尔斯液体，但不包括氢键液体等。我们在这里讨论了以下内容：（1）幂律和扩展幂律势的标度性质（后者包括一个“隐藏”了近似标度不变性的线性项）；（2）分子模型的计算机模拟结果，涉及非平衡条件；（3）维里/势能相关系数的系综依赖性；（4）与格林艾森参数的联系；（5）用能量-键合形式来解释强相关性。
