Riojas Amanda G, Wilson Angela K
Department of Chemistry and Center for Advanced Scientific Computing and Modeling (CASCaM), University of North Texas , Denton, Texas 76203-5017, United States.
J Chem Theory Comput. 2014 Apr 8;10(4):1500-10. doi: 10.1021/ct400908z. Epub 2014 Mar 12.
Direct theoretical methods are advantageous for the prediction of pKa, as relative methods rely upon the experimental values of reference acid molecules that can limit application of the method to well-characterized systems. Here, a direct route is introduced, which incorporates the SMD universal solvation model1 within the correlation consistent Composite Approach (ccCA). This Solv-ccCA methodology has been used for the prediction of theoretical pKa values for nitrogen-containing species to within a mean absolute deviation (MAD) of 1.0 pKa unit from experimental values by utilizing a thermodynamic cycle that combines gas-phase and solution-phase calculations. Several density functionals, including B3LYP, B97-1, B97-2, B98, BMK, M06, and M06-2X, were also evaluated for use with SMD and for comparison to Solv-ccCA.
直接理论方法对于预测pKa具有优势，因为相对方法依赖于参考酸分子的实验值，这可能会将该方法的应用限制在特征明确的体系中。在此，引入了一条直接途径，即在相关一致复合方法（ccCA）中纳入SMD通用溶剂化模型1。这种溶剂化ccCA方法已用于预测含氮物种的理论pKa值，通过结合气相和溶液相计算的热力学循环，与实验值的平均绝对偏差（MAD）在1.0 pKa单位以内。还评估了几种密度泛函，包括B3LYP、B97-1、B97-2、B98、BMK、M06和M06-2X，用于与SMD一起使用并与溶剂化ccCA进行比较。
