Hadj-Kali Mohamed Kamel, Gerbaud Vincent, Joulia Xavier, Lacaze-Dufaure Corinne, Mijoule Claude, Ungerer Philippe
Université de Toulouse, Laboratoire de Génie Chimique, UMR 5503 CNRS-UPS-INPT, BP 1301, 5 Rue Paulin Talabot, 31106, Toulouse Cedex 1, France.
J Mol Model. 2008 Jul;14(7):571-80. doi: 10.1007/s00894-008-0301-4. Epub 2008 May 14.
An extension of the anisotropic united atoms intermolecular potential model is proposed for nitriles. The electrostatic part of the intermolecular potential is calculated using atomic charges obtained by a simple Mulliken population analysis. The repulsion-dispersion interaction parameters for methyl and methylene groups are taken from transferable AUA4 literature parameters [Ungerer et al., J. Chem. Phys., 2000, 112, 5499]. Non-bonding Lennard-Jones intermolecular potential parameters are regressed for the carbon and nitrogen atoms of the nitrile group (-C[triple bound] N) from experimental vapor-liquid equilibrium data of acetonitrile. Gibbs Ensemble Monte Carlo simulations and experimental data agreement is very good for acetonitrile, and better than previous molecular potential proposed by Hloucha et al. [J. Chem. Phys., 2000, 113, 5401]. The transferability of the resulting potential is then successfully tested, without any further readjustment, to predict vapor-liquid phase equilibrium of propionitrile and n-butyronitrile.
针对腈类化合物，提出了一种各向异性联合原子分子间势模型的扩展形式。分子间势的静电部分使用通过简单的穆利肯布居分析得到的原子电荷来计算。甲基和亚甲基的排斥 - 色散相互作用参数取自可转移的AUA4文献参数[翁热雷尔等人，《化学物理杂志》，2000年，第112卷，第5499页]。根据乙腈的实验气液平衡数据，对腈基（-C≡N）的碳和氮原子的非键合伦纳德 - 琼斯分子间势参数进行回归。吉布斯系综蒙特卡罗模拟结果与乙腈的实验数据吻合得非常好，并且比赫洛查等人[《化学物理杂志》，2000年，第113卷，第5401页]先前提出的分子势更好。然后，在没有任何进一步调整的情况下，成功测试了所得势的可转移性，以预测丙腈和正丁腈的气液相平衡。
