https://scholars.lib.ntu.edu.tw/handle/123456789/406870
標題: | A Critical Evaluation on the Performance of COSMO-SAC Models for Vapor-Liquid and Liquid-Liquid Equilibrium Predictions Based on Different Quantum Chemical Calculations | 作者: | Chen W.-L. Hsieh C.-M. Yang L. Hsu C.-C. Lin S.-T. |
公開日期: | 2016 | 卷: | 55 | 期: | 34 | 起(迄)頁: | 9312-9322 | 來源出版物: | Industrial and Engineering Chemistry Research | 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 (Kow; 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. ? 2016 American Chemical Society. |
URI: | https://scholars.lib.ntu.edu.tw/handle/123456789/406870 | ISSN: | 8885885 | DOI: | 10.1021/acs.iecr.6b02345 |
顯示於: | 化學工程學系 |
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