Zheng Jingjing, Zhao Yan, Truhlar Donald G
Department of Chemistry and Supercomputing Institute, University of Minnesota, 207 Pleasant Street S.E., Minneapolis, Minnesota 55455-0431, USA.
J Phys Chem A. 2007 May 31;111(21):4632-42. doi: 10.1021/jp070252n. Epub 2007 May 9.
Saddle point properties of three symmetric and one asymmetric hydrogen transfer and the energy of reaction of the asymmetric reactions are investigated in the present work. These reactions were calculated by various density functionals, many of which were developed in recent years, by coupled cluster theory, and by multicoefficient correlation methods based on wave function theory. Instead of comparing calculated results to "semi-experimental" values, we compared them to very accurate theoretical values (e.g., to values obtained by the Weizmann-1 method). Coupled cluster theory and the multicoefficient correlation methods MC-QCISD/3 and MCQCISD-MPW are very accurate for these reactions with mean unsigned errors below 0.94 kcal/mol. Diagnostics for multireference character add additional reliability to these results. The newly developed hybrid density functional M06-2X shows very good performance for these reactions with a mean unsigned error of only 0.77 kcal/mol; the BHandHLYP, MPW1K, and BB1K density functionals, can also predict these reactions well with mean unsigned errors less than 1.42 kcal/mol.
本文研究了三种对称和一种不对称氢转移的鞍点性质以及不对称反应的反应能量。这些反应通过各种密度泛函（其中许多是近年来发展的）、耦合簇理论以及基于波函数理论的多系数相关方法进行计算。我们没有将计算结果与“半实验”值进行比较，而是将它们与非常精确的理论值（例如通过魏茨曼-1方法获得的值）进行比较。耦合簇理论以及多系数相关方法MC-QCISD/3和MCQCISD-MPW对于这些反应非常精确，平均无符号误差低于0.94千卡/摩尔。多参考特征诊断为这些结果增添了额外的可靠性。新开发的杂化密度泛函M06-2X对于这些反应表现出非常好的性能，平均无符号误差仅为0.77千卡/摩尔；BHandHLYP、MPW1K和BB1K密度泛函也能够很好地预测这些反应，平均无符号误差小于1.42千卡/摩尔。
