Yu Yang-Xin, Wu Jianzhong, Xin Yu-Xuan, Gao Guang-Hua
Department of Chemical Engineering, Tsinghua University, Beijing 100084, People's Republic of China.
J Chem Phys. 2004 Jul 15;121(3):1535-41. doi: 10.1063/1.1763142.
The structures of nonuniform binary hard-sphere mixtures and the correlation functions of uniform ternary hard-sphere mixtures were studied using a modified fundamental-measure theory based on the weight functions of Rosenfeld [Rosenfeld, Phys. Rev. Lett. 63, 980 (1989)] and Boublik-Mansoori-Carnahan-Starling-Leland equation of state [Boublik, J. Chem. Phys. 53, 471 (1970); Mansoori et al., J. Chem. Phys. 54, 1523 (1971)]. The theoretical predictions agreed very well with the molecular simulations for the overall density profiles, the local compositions, and the radial distribution functions of uniform as well as inhomogeneous hard-sphere mixtures. The density functional theory was further extended to represent the structure of a polydisperse hard-sphere fluid near a hard wall. Excellent agreement was also achieved between theory and Monte Carlo simulations. The density functional theory predicted oscillatory size segregations near a hard wall for a polydisperse hard-sphere fluid of a uniform size distribution.
利用基于罗森菲尔德权重函数[罗森菲尔德，《物理评论快报》63, 980 (1989)]和布布利克-曼苏里-卡纳汉-斯塔林-利兰状态方程[布布利克，《化学物理杂志》53, 471 (1970); 曼苏里等人，《化学物理杂志》54, 1523 (1971)]的修正基本度量理论，研究了非均匀二元硬球混合物的结构以及均匀三元硬球混合物的关联函数。对于均匀和非均匀硬球混合物的整体密度分布、局部组成以及径向分布函数，理论预测与分子模拟结果非常吻合。密度泛函理论进一步扩展，以描述硬壁附近多分散硬球流体的结构。理论与蒙特卡罗模拟之间也取得了极好的一致性。密度泛函理论预测，对于具有均匀尺寸分布的多分散硬球流体，在硬壁附近会出现振荡尺寸分离。
