Research School of Chemistry, Australian National University, Canberra, Australian Capital Territory 0200, Australia.
J Chem Phys. 2011 Jun 14;134(22):224103. doi: 10.1063/1.3599937.
We have constructed the unrestricted Hartree-Fock (UHF), restricted Hartree-Fock (RHF), and full configuration interaction (FCI) position and momentum intracules and holes for H···H at bond lengths R from 1 to 10 bohrs. We trace the recently discovered inversion of the UHF position hole at intermediate R to over-localization of the spin-orbitals, and support this by a correlation energy component analysis. The RHF and UHF momentum holes are found to be more complicated; however their features are explained through decomposition of electron correlation effects. The UHF momentum hole is also found to invert and exhibits interesting behavior at large R. The RHF (but not UHF) and FCI momentum intracules exhibit Young-type interference patterns related to recent double photoionization experiments. Our analyses yield the most comprehensive picture to date of the behavior of the electrons during homolytic bond fission.
我们构建了无限制 Hartree-Fock（UHF）、限制 Hartree-Fock（RHF）和完全组态相互作用（FCI）位置和动量内插和空穴，用于研究 H···H 在从 1 到 10 bohrs 的键长处的相互作用。我们追踪了最近发现的 UHF 位置空穴在中间 R 处的反转，这归因于自旋轨道的过度局域化，并通过相关能量分量分析对此进行了支持。RHF 和 UHF 动量空穴被发现更为复杂；然而，通过电子相关效应的分解，可以解释它们的特征。UHF 动量空穴也被发现反转，并在大 R 处表现出有趣的行为。RHF（但不是 UHF）和 FCI 动量内插表现出与最近的双光电离实验相关的 Young 型干涉模式。我们的分析提供了迄今为止最全面的关于均裂键断裂过程中电子行为的图像。
