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分子链表面张力的普适标度行为。

Universal scaling behaviour of surface tension of molecular chains.

机构信息

Departamento de Física Aplicada, Universidad de Huelva, 21071 Huelva, Spain.

出版信息

J Chem Phys. 2012 Jul 14;137(2):024702. doi: 10.1063/1.4731660.

Abstract

We use and extend the universal relationship recently proposed by Galliero [G. Galliero, J. Chem. Phys. 133, 074705 (2010)], based on a combination of the corresponding-states principle of Guggenheim [E. A. Guggenheim, J. Chem. Phys. 13, 253 (1945)] and the parachor approach of Macleod [J. Macleod, Trans. Faraday Soc. 19, 38 (1923)], to predict the vapour-liquid surface tension of fully flexible chainlike Lennard-Jones molecules. In the original study of Galliero, the reduced surface tension of short-chain molecules formed by up to five monomers is expressed as a unique function of the difference between the liquid and vapour coexistence densities. In this work, we extend the applicability of the recipe and demonstrate that it is also valid for predicting the surface tension of two different chainlike molecular models, namely, linear tangent chains that interact through the Lennard-Jones intermolecular potential and fully flexible chains formed by spherical segments interacting through the square-well potential. Computer simulation data for vapour-liquid surface tension of fully flexible and rigid linear Lennard-Jones, and fluid flexible square-well chains is taken from our previous works. Our results indicate that the universal scaling relationship is able to correlate short- and long-chain molecules with different degrees of flexibility and interacting through different intermolecular potentials.

摘要

我们使用并扩展了 Galliero [G. Galliero, J. Chem. Phys. 133, 074705 (2010)] 最近提出的通用关系,该关系基于 Guggenheim [E. A. Guggenheim, J. Chem. Phys. 13, 253 (1945)] 的相应状态原理和 Macleod [J. Macleod, Trans. Faraday Soc. 19, 38 (1923)] 的 parachor 方法,用于预测完全柔性链状 Lennard-Jones 分子的汽液表面张力。在 Galliero 的原始研究中,由多达五个单体形成的短链分子的折合表面张力表示为液体和蒸汽共存密度差的唯一函数。在这项工作中,我们扩展了该方法的适用性,并证明它也适用于预测两种不同链状分子模型的表面张力,即通过 Lennard-Jones 分子间势能相互作用的线性相切链和通过方阱势能相互作用的球形段形成的完全柔性链。完全柔性和刚性线性 Lennard-Jones 以及流体柔性方阱链的汽液表面张力的计算机模拟数据来自我们之前的工作。我们的结果表明,通用缩放关系能够关联具有不同柔性程度和通过不同分子间势能相互作用的短链和长链分子。

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