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arXiv · 2106.04040

Exploring Spin Symmetry-Breaking Effects for Static Field Ionization of Atoms: Is There an Analog to the Coulson-Fischer Point in Bond Dissociation?

Leonardo A. Cunha·Joonho Lee·Diptarka Hait·C. William McCurdy·Martin Head-Gordon
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Abstract

Löwdin's symmetry dilemma is an ubiquitous issue in approximate quantum chemistry. In the context of Hartree-Fock (HF) theory, the use of Slater determinants with some imposed constraints to preserve symmetries of the exact problem may lead to physically unreasonable potential energy surfaces. On the other hand, lifting these constraints leads to the so-called broken symmetry solutions that usually provide better energetics, at the cost of losing information about good quantum numbers that describe the state of the system. This behavior has been previously extensively studied in the context of bond dissociation. This paper studies the behavior of different classes of Hartree-Fock spin polarized solutions (restricted, unrestricted, generalized) in the context of ionization by strong static electric fields. We find that, for simple two-electron systems, UHF is able to provide a qualitatively good description of states involved during the ionization process (neutral, singly-ionized and doubly ionized states), whereas RHF fails to describe the singly ionized state. For more complex systems, even though UHF is able to capture some of the expected characteristics of the ionized states, it is constrained to a single $M_s$ (diabatic) manifold in the energy surface as a function of field intensity. In this case a better qualitative picture can be painted by GHF as it is able to explore different spin manifolds and follow the lowest solution due to lack of collinearity constraints on the spin quantization axis.

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Leonardo A. Cunha, Joonho Lee, Diptarka Hait, C. William McCurdy, Martin Head-Gordon. 2021-06-08. Exploring Spin Symmetry-Breaking Effects for Static Field Ionization of Atoms: Is There an Analog to the Coulson-Fischer Point in Bond Dissociation?. https://doi.org/10.1063/5.0054387

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