VARIATIONAL THEORY FOR LENNARD-JONES CHAINS

被引：28

作者：

OLENICK, R

CHIEW, YC

机构：

[1] Department of Chemical and Biochemical Engineering, Rutgers University, NJ, 08855-0909, Piscataway

来源：

MOLECULAR PHYSICS | 1995年 / 85卷 / 02期

关键词：

D O I：

10.1080/00268979500101091

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

The Helmholtz energy and pressure for Lennard-Jones chains are derived using a variational first-order perturbation theory. The reference system, comprising freely jointed tangent hard-sphere chains is solved in the Percus-Yevick approximation. The optimal diameter of segments in the hard-sphere chain reference is determined by minimizing the free energy through the Gibbs-Bogoliubov inequality. Unlike previous perturbation theories for non-aggregated Lennard-Jones spheres, the resulting hard-sphere segment diameter depends on chain length in addition to density and temperature. The resulting theory exhibits excellent agreement with MC simulation, over a wide range of conditions, without adjustable parameters.

引用

页码：257 / 269

页数：13

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