National University of Shipbuilding, Geroyev Stalingrada Avenue 9, Mykolayiv 54025, Ukraine.
J Chem Phys. 2013 Mar 7;138(9):094309. doi: 10.1063/1.4793407.
An accurate expression for the cluster expansion of the configuration integral has been considered based on the Gibbs single-phase approach without additional assumptions and approximations. The computational results for the Lennard-Jones fluid demonstrate the beginning of the condensation process at the singularity points of the isothermal compressibility. It has also been shown that the accuracy boundary of the virial equation of state corresponds to these points, not the virial series singularities. At the high density regime, the inappropriate behavior of the cluster expansion has been discovered that may be related to the infinite limits of the cluster integrals, i.e., their independency on the density.
已经基于没有额外假设和近似的 Gibbs 单相方法考虑了构型积分的集团展开的精确表达式。对于 Lennard-Jones 流体的计算结果表明在等压压缩率的奇点处开始发生冷凝过程。还表明，状态方程的维里方程的精度边界对应于这些奇点，而不是维里级数奇点。在高密度区域，发现了集团展开的不适当行为，这可能与集团积分的无穷极限有关，即它们与密度无关。
