Ferrari E S, Burton R C, Davey R J, Gavezzotti A
School of Chemical Engineering and Analytical Science, University of Manchester, P.O. Box 88, Manchester M60 1QD, UK.
J Comput Chem. 2006 Aug;27(11):1211-9. doi: 10.1002/jcc.20433.
Standard molecular dynamics simulations have been carried out on pure alcohols and alcohol/water mixtures. A simple atom-atom force field consisting of Lennard-Jones potentials plus coulombic terms over atomic point charges, but without explicit polarization terms, has been specifically fitted to reproduce several experimental properties of the pure alcohols, and has been used for mixtures by developing combination rules with the TIP3P water model. Densities, enthalpies of vaporization, radial distribution functions, self-diffusion coefficients, and rotational correlation functions of the pure alcohols are well reproduced and compare favorably with those from more sophisticated force fields. Some key aspects of the phase behaviour are correctly reproduced by the molecular dynamics simulation, showing a distinct demixing process for the n-butanol/water mixture as opposed to the stability of the t-butanol/water mixtures. The results demonstrate the ability of a molecular dynamics simulation, even in its standard form and with easily accessible time ranges, but with a carefully optimized force field, to simulate and, to a certain extent, predict the properties of binary mixtures.
已对纯醇类和醇/水混合物进行了标准分子动力学模拟。一个简单的原子-原子力场，由 Lennard-Jones 势加上原子点电荷上的库仑项组成，但没有明确的极化项，已专门进行拟合以再现纯醇类的几种实验性质，并通过与 TIP3P 水模型开发组合规则用于混合物。纯醇类的密度、汽化焓、径向分布函数、自扩散系数和旋转相关函数得到了很好的再现，与更复杂力场得到的结果相比具有优势。分子动力学模拟正确地再现了相行为的一些关键方面，显示出正丁醇/水混合物有明显的分层过程，而异丁醇/水混合物则具有稳定性。结果表明，即使是标准形式且时间范围易于获取，但具有精心优化力场的分子动力学模拟，也能够模拟并在一定程度上预测二元混合物的性质。
