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首页> 外文期刊>The Journal of Chemical Physics >Do independent-particle-model broken-symmetry solutionscontain more physics than the symmetry-adapted ones?The case of homonuclear diatomics
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Do independent-particle-model broken-symmetry solutionscontain more physics than the symmetry-adapted ones?The case of homonuclear diatomics

机译：独立粒子模型的破对称解是否比适应对称的解包含更多的物理学？同核双原子

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摘要

We explore spin-preserving, singlet stability of restricted Hartree–Fock (RHF) solutions for anumber of closed-shell, homonuclear diatomics in the entire relevant range of internuclearseparations. In the presence of such instabilities we explore the implied broken-symmetry (bs)solutions and check their stability. We also address the occurrence of vanishing roots rendered by thestability problem in the case of bs solutions. The RHF bs solutions arise primarily due to thesymmetry breaking of the relevant, mostly frontier, molecular orbitals, which approach atomic-typeorbitals in the dissociation limit. The resulting bs RHF solutions yield more realistic potential energycurves (PECs) than do the symmetry adapted (sa) solutions. These PECs are shown to be verysimilar to those rendered by the density functional theory (DFT). Moreover, the sa DFT solutions arefound to be stable in a much wider range of internuclear separations than are the RHF solutions, andtheir bs analogs differ very little from the sa ones. Finally, we examine a possible usefulness of bsRHF solutions in post-HF correlated approaches to the many-electron problem, specifically in thelimited configuration interaction and coupled-cluster methods.
机译：我们探索了在整个核相互分离范围内的许多闭壳同核双原子分子的受限Hartree-Fock（RHF）解决方案的自旋保持，单重态稳定性。在存在这种不稳定性的情况下，我们探索隐含的对称性（bs）解并检查其稳定性。我们还解决了在bs解的情况下由稳定性问题导致的根消失的情况。 RHF bs解决方案的出现主要是由于相关的，大多是前沿的分子轨道的对称性断裂，该分子轨道在解离极限内接近原子型轨道。所得的bs RHF解决方案比对称适应的（sa）解决方案产生更现实的势能曲线（PEC）。这些PEC显示与密度泛函理论（DFT）所提供的非常相似。而且，发现sa DFT解决方案在比RHF解决方案更广泛的核间分离范围内是稳定的，并且它们的bs类似物与sa的区别很小。最后，我们检查了bsRHF解决方案在解决多电子问题的HF后相关方法中的可能用途，特别是在有限配置相互作用和耦合簇方法中。

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