双原子微分重叠近似近似的收敛性综合分析
Comprehensive Analysis of the Neglect of Diatomic Differential Overlap Approximation
摘要：
许多现代半经验分子轨道模型都是建立在忽略双原子微分重叠（NDDO）近似的基础上的。因此，深入了解这种近似是必不可少的合理化这些半经验分子轨道模型的成功，并开发进一步的改进。NDDO近似提供了一种基于在局部正交化基础上的更少数量的ERI在对称正交化基础上近似电子-电子排斥积分（ERI）的方法。我们首先分析的NDDO近似比较ERI在两个基地的选择的分子和选择的基组。我们发现Hartree-Fock和二阶Moller-Plesset微扰理论能量的误差随着基函数的数量大致线性增长。然后，我们研究不同的方法来纠正由NDDO近似引起的错误，并提出了一种策略，直接纠正他们在两个电子矩阵，进入Fock算子。
英文摘要：
Many modern semiempirical molecular orbital models are built on the neglect of diatomic differential overlap (NDDO) approximation. An in-depth understanding of this approximation is therefore indispensable to rationalize the success of these semiempirical molecular orbital models and to develop further improvements on them. The NDDO approximation provides a recipe to approximate electron-electron repulsion integrals (ERIs) in a symmetrically orthogonalized basis based on a far smaller number of ERIs in a locally orthogonalized basis. We first analyze the NDDO approximation by comparing ERIs in both bases for a selection of molecules and for a selection of basis sets. We find that the errors in Hartree-Fock and second-order Moller-Plesset perturbation theory energies grow roughly linearly with the number of basis functions. We then examine different approaches to correct for the errors caused by the NDDO approximation and propose a strategy to directly correct for them in the two-electron matrices that enter the Fock operator.
机构、总结、中文摘要均由AI分析而来，可能存在错误，请以论文正文为准。
