论文标题
关于对称性和全体形态hartree的现实 - 波形
On Symmetry and the Reality of Holomorphic Hartree--Fock Wavefunctions
论文作者
论文摘要
随着分子结构的变化，Hartree（HF）溶液的合并和消失已成为批评HF近似与势能表面的批评的普遍来源。但是，全体形态HF理论的最新发展表明，这种消失的行为只是传统HF方程阻止解决方案进行分析的方式的一种体现，但是目前尚不清楚哪些因素控制了这些失踪的存在和位置。在这项工作中，我们通过在电子结构计算上引入对称性约束的分类来探索其中的一些因素。这为我们构成了一个框架，可以系统地研究模型$ \ textrm {[h} _4 \ textrm {]}^{2+} $ System的几种分析性全态HF解决方案。然后讨论对自洽场HF搜索算法的含义。在本文中，现实一词是指具有真实分子轨道的全体形态HF溶液的质量。
The coalescence and disappearance of Hartree--Fock (HF) solutions as the molecular structure varies have been a common source of criticism for the breakdown of the HF approximation to the potential energy surfaces. However, recent developments in holomorphic HF theory show that this disappearing behavior is only a manifestation of the way conventional HF equations prevent solutions from being analytically continued, but it is unclear what factors govern the existence and the locations of these disappearances. In this work, we explore some of these factors from the perspective of spatial symmetry by introducing a classification for symmetry constraints on electronic-structure calculations. This forms a framework for us to systematically investigate several analytic holomorphic HF solutions of a model $\textrm{[H}_4\textrm{]}^{2+}$ system in STO-3G and demonstrate that, under appropriate conditions, spatial symmetry imposes strict requirements on the reality of certain solutions. The implications for self-consistent-field HF search algorithms are then discussed. Throughout this article, the term reality means the quality of a holomorphic HF solution having real molecular orbitals.
