| 摘要: | 摘要： The performance of two versions of the COSMO-SAC activity coefficient model is carefully examined based on eight sets of quantum chemical computations [VWN-BP/DNP, b3lyp/6-31G(d,p), b3lyp/6-31G(2d,p), b3lyp/6-31+G(d,p), b3lyp/6-311G(d,p), wb97xd/6-31G(d,p), wb97xd/6-31G(2d,p), and wb97xd/6-31+G(d,p)] and one semiempirical calculation (PM6). Furthermore, the effect of the molecular geometry is examined based on equilibrium structures determined both in a vacuum, representing a nonpolar environment, and in a conductor, representing a highly polar environment. The model parameters are reoptimized for each quantum chemical calculation method, and the performance is evaluated using a large set of databases covering the vapor–liquid equilibrium, liquid–liquid equilibrium, infinite-dilution activity coefficient of binary mixtures, and octanol–water partition coefficient (K ow; containing over 22000 data points). It is found that the original COSMO-SAC model is sensitive to the quantum chemical method used, whereas the revised COSMO-SAC model is not. For the original COSMO-SAC, a method that gives higher molecular polarity often results in a better prediction accuracy. The modifications introduced in the revised COSMO-SAC model not only improve the accuracy but also allow for the use of a lower-quality quantum computational theory without much loss of accuracy.
其他題名： Ind. Eng. Chem. Res
出版者： American Chemical Society
出版日期： 2016-08-31
出處： Industrial & engineering chemistry research, 2016-08, Vol.55 (34), p.9312-9322
資源來源： American Chemical Society Journals
版權： Copyright © 2016 American Chemical Society
識別號： ISSN: 0888-5885
識別號： ISSN: 1520-5045
識別號： EISSN: 1520-5045
識別號： DOI: 10.1021/acs.iecr.6b02345 |
