Mu Junju, Motokawa Ryuhei, Williams Christopher D, Akutsu Kazuhiro, Nishitsuji Shotaro, Masters Andrew J
School of Chemical Engineering and Analytical Science, The University of Manchester , Oxford Road, Manchester M13 9PL, UK.
Hierarchical Structure Research Group, Materials Sciences Research Center, Japan Atomic Energy Agency (JAEA) , Ibaraki 319-1195, Japan.
J Phys Chem B. 2016 Jun 16;120(23):5183-93. doi: 10.1021/acs.jpcb.6b00781. Epub 2016 Jun 8.
A refined model for tri-n-butyl phosphate (TBP), which uses a new set of partial charges generated from our ab initio density functional theory calculations, has been proposed in this study. Molecular dynamics simulations are conducted to determine the thermodynamic properties, transport properties, and the microscopic structures of liquid TBP, TBP/water mixtures, and TBP/n-alkane mixtures. These results are compared with those obtained from four other TBP models, previously described in the literature. We conclude that our refined TBP model appears to be the only TBP model from this set that, with reasonable accuracy, can simultaneously predict the properties of TBP in bulk TBP, in organic diluents, and in aqueous solution. The other models only work well for two of the three systems mentioned above. This new TBP model is thus appropriate for the simulation of liquid-liquid extraction systems in the nuclear extraction process, where one needs to simultaneously model TBP in both aqueous and organic phases. It is also promising for the investigation of the microscopic structure of the organic phase in these processes and for the characterization of third-phase formation, where TBP again interacts simultaneously with both polar and nonpolar molecules. Because the proposed TBP model uses OPLS-2005 Lennard-Jones parameters, it may be used with confidence to model mixtures of TBP with other species whose parameters are given by the OPLS-2005 force field.
本研究提出了一种磷酸三丁酯（TBP）的精确模型，该模型使用了由我们的从头算密度泛函理论计算生成的一组新的部分电荷。进行分子动力学模拟以确定液态TBP、TBP/水混合物以及TBP/正构烷烃混合物的热力学性质、传输性质和微观结构。将这些结果与文献中先前描述的其他四种TBP模型所获得的结果进行比较。我们得出结论，我们的精确TBP模型似乎是该组中唯一能够以合理的精度同时预测TBP在纯TBP、有机稀释剂和水溶液中的性质的TBP模型。其他模型仅对上述三个系统中的两个有效。因此，这种新的TBP模型适用于模拟核萃取过程中的液-液萃取系统，在该过程中需要同时对水相和有机相中的TBP进行建模。它对于研究这些过程中有机相的微观结构以及表征第三相形成也很有前景，在第三相形成过程中TBP再次同时与极性和非极性分子相互作用。由于所提出的TBP模型使用了OPLS - 2005 Lennard - Jones参数，因此可以放心地用于对TBP与其他由OPLS - 2005力场给出参数的物种的混合物进行建模。
