Mulliken Center for Theoretical Chemistry, Institut für Physikalische und Theoretische Chemie der Universität Bonn, Beringstr. 4, D-53115, Bonn, Germany.
J Comput Chem. 2013 Jul 15;34(19):1672-85. doi: 10.1002/jcc.23317. Epub 2013 May 14.
A quantum chemical method based on a Hartree-Fock calculation with a small Gaussian AO basis set is presented. Its main area of application is the computation of structures, vibrational frequencies, and noncovalent interaction energies in huge molecular systems. The method is suggested as a partial replacement of semiempirical approaches or density functional theory (DFT) in particular when self-interaction errors are acute. In order to get accurate results three physically plausible atom pair-wise correction terms are applied for London dispersion interactions (D3 scheme), basis set superposition error (gCP scheme), and short-ranged basis set incompleteness effects. In total nine global empirical parameters are used. This so-called Hartee-Fock-3c (HF-3c) method is tested for geometries of small organic molecules, interaction energies and geometries of noncovalently bound complexes, for supramolecular systems, and protein structures. In the majority of realistic test cases good results approaching large basis set DFT quality are obtained at a tiny fraction of computational cost.
本文提出了一种基于 Hartree-Fock 计算和小高斯原子轨道基组的量子化学方法。其主要应用领域是计算巨大分子体系的结构、振动频率和非共价相互作用能。该方法被建议作为半经验方法或密度泛函理论（DFT）的部分替代方法，特别是在自相互作用误差严重时。为了得到准确的结果，应用了三个物理上合理的原子对修正项来修正伦敦色散相互作用（D3 方案）、基组叠加误差（gCP 方案）和短程基组不完备效应。总共使用了九个全局经验参数。这种所谓的 Hartree-Fock-3c（HF-3c）方法在小分子的几何形状、非共价键合复合物的相互作用能和几何形状、超分子体系和蛋白质结构等方面进行了测试。在大多数实际测试案例中，以极小的计算成本获得了接近大基组 DFT 质量的良好结果。
