全纯Hartree-Fock理论：双电子问题的本质
化学物理
2018-01-15 v1
摘要
我们探究双电子问题中全纯限制Hartree-Fock（h-RHF）解的存在性与行为。借助代数几何，严格确定具有 个基函数的解的准确数目为 ，证明对所有分子几何构型必然存在这些态。随后对HZ（STO-3G）的h-RHF态的详细研究，展示了当几何或原子电荷变化时全纯解的守恒，以及在合并点处复h-RHF解的出现。利用突变理论，描述了这些合并点的本质，突出了分子对称性的影响。接着比较HHeH与HHeH（STO-3G）的h-RHF态，阐明双电子与双电子空穴系统间的同构。最后，我们将乙烯（STO-3G）的 电子视为双电子问题来探究其h-RHF态，并采用NOCI识别最低能单重态与三重态在垂直几何构型处的交叉。
引用
@article{arxiv.1801.04141,
title = {Holomorphic Hartree-Fock Theory: The Nature of Two-Electron Problems},
author = {Hugh G. A. Burton and Mark Gross and Alex J. W. Thom},
journal= {arXiv preprint arXiv:1801.04141},
year = {2018}
}
备注
This document is the unedited Author's version of a Submitted Work that was subsequently accepted for publication in Journal of Chemical Theory and Computation, copyright \copyright\ American Chemical Society after peer review. To access the final edited and published work see http://pubs.acs.org/journal/jctcce