基于双原子微分重叠近似的半经验分子轨道模型
Semiempirical Molecular Orbital Models based on the Neglect of Diatomic Differential Overlap Approximation
摘要：
基于忽略双原子微分重叠（NDDO）近似的半经验分子轨道（SEMO）模型通过相当激烈的近似有效地求解自洽场方程。计算效率的代价是电子-电子排斥积分的误差。误差可以通过引入参数表达式来补偿，以评估电子-电子排斥积分，单电子积分，和核心-核心排斥。我们回顾流行的NDDO-SEMO模型（如MNDO（/d），AM 1，PMx和OMx模型）的形式主义，在一个简洁和独立的方式。我们讨论的方法来隐式和显式描述电子相关效应内NDDO-SEMO模型，我们解剖的优点和缺点的不同的方法进行了详细的分析。为此，我们考虑最近的基准研究的结果。此外，我们应用自举进行MNDO模型中的参数选择的敏感性分析。我们还确定了系统的局限性NDDO-SEMO模型借鉴Kohn-Sham密度泛函理论的类比。
英文摘要：
Semiempirical molecular orbital (SEMO) models based on the neglect of diatomic differential overlap (NDDO) approximation efficiently solve the self-consistent field equations by rather drastic approximations. The computational efficiency comes at the cost of an error in the electron-electron repulsion integrals. The error may be compensated by the introduction of parametric expressions to evaluate the electron-electron repulsion integrals, the one-electron integrals, and the core-core repulsion. We review the resulting formalisms of popular NDDO-SEMO models (such as the MNDO(/d), AM1, PMx, and OMx models) in a concise and self-contained manner. We discuss the approaches to implicitly and explicitly describe electron correlation effects within NDDO-SEMO models and we dissect strengths and weaknesses of the different approaches in a detailed analysis. For this purpose, we consider the results of recent benchmark studies. Furthermore, we apply bootstrapping to perform a sensitivity analysis for a selection of parameters in the MNDO model. We also identify systematic limitations of NDDO-SEMO models by drawing on an analogy to Kohn--Sham density functional theory.
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