Hall Michelle Lynn, Zhang Jing, Bochevarov Arteum D, Friesner Richard A
Department of Chemistry, Columbia University, 3000 Broadway, New York, NY, 10027.
J Chem Theory Comput. 2010 Dec 14;6(12):3647-3663. doi: 10.1021/ct100418n.
Our previous works have demonstrated the ability of our localized orbital correction (LOC) methodology to greatly improve the accuracy of various thermochemical properties at the stationary points of the Density Functional Theory (DFT) reaction coordinate (RC). Herein we extend this methodology from stationary points to the entire RC connecting any stationary points by developing continuous localized orbital corrections (CLOCs). We show that the resultant method, DFT-CLOC, is capable of producing RCs with far greater accuracy than uncorrected DFT and yet requires negligible computational cost beyond the uncorrected DFT calculations. Various post-Hartree-Fock (post-HF) reaction coordinate profiles were used, including a sigmatropic shift, Diels-Alder reaction, electrocyclization, carbon radical and three hydrogen radical reactions to show that this method is robust across multiple reaction types of general interest.
我们之前的工作已经证明了我们的定域轨道校正（LOC）方法能够极大地提高密度泛函理论（DFT）反应坐标（RC）驻点处各种热化学性质的准确性。在此，我们通过开发连续定域轨道校正（CLOCs）将该方法从驻点扩展到连接任何驻点的整个RC。我们表明，由此产生的方法DFT-CLOC能够生成比未校正的DFT精度高得多的RC，而且除了未校正的DFT计算之外，所需的计算成本可以忽略不计。使用了各种后Hartree-Fock（post-HF）反应坐标剖面图，包括一个σ迁移反应、狄尔斯-阿尔德反应（双烯加成反应）、电环化反应、碳自由基和三个氢自由基反应，以表明该方法在多种普遍感兴趣的反应类型中都很稳健。
