从统计力学推导流体状态方程——方阱势硬球微扰理论的解析表达式

• 作 者: 张秉坚 侯虞钧
• 机 构: 浙江大学化工热力学研究室,浙江大学化工热力学研究室,
• 出 处: 物理化学学报
• 发表日期: 1986年06期
• 关键词: 方阱势 统计力学 微扰理论 硬球势 径向分布函数 级数 热力学性质 分子动力学 压缩因子 理论表达式

本文在Zwanzlg微扰理论的基础上,对二级以上的高级微扰项采用Barker与Henderson的近似方法,得到一个简单的微扰理论表达式。以硬球势为参考势,方阱势为微扰势,用一新的级数表达式(?)为径向分布函数,导出了自由能.内能、比热、压缩因子的级数表达式。为了检验理论的正确性,取g(R)级数的前四项代入各热力学性质的表达式,与Monte-Carlo(MC)及分子动力学(MD)计算机模拟数据作了比较,结果符合较好。

Based on the Zwanzlg perturbation theory, a simple perturbation theory expression is obtained by using the approximate method of Barker and Henderson for the second-level or higher-level perturbation terms. Taking the hard-ball potential as a reference potential, the square-well potential is a perturbation potential, and the free-form energy is deduced with a new series of expression (?) As radial distribution function. . In order to test the correctness of the theory, the first four terms of the g (R) series were substituted into expressions of various thermodynamic properties and compared with Monte-Carlo (MC) and molecular dynamics (MD) computer simulation data. it is good.