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Charge disproportionation as a possible mechanism towards polar antiferromagnetic metal in molecular orbital crystal

Polar antiferromagnetic metals have recently garnered increasing interests due to their combined traits of both ferromagnets and antiferromagnets for spintronic applications. However, the inherently incompatible nature of antiferromagnet, metallicity and polarity pose a significant challenge. We propose that charge disproportionation can lead to this novel state in negative charge transfer gap regime in molecular orbital crystal by molecular orbital analyses of first-principles DFT+$U$ electronic band structure for representative Ruddlesden-Popper bilayer perovskite oxides Sr$_3$Co$_2$O$_7$, corroborated by Density Matrix Renormalization Group calculation. Due to the negative charge transfer nature of Co$^{4+}$ and imposed by strong interlayer coupling, localized molecular orbitals stemming from the hybridization of Co $d_{z^2}$ and $d_{xz/yz}$ orbitals through the apical oxygen $p$ orbitals are preferably emergent within each bilayer unit, which develop antiferromagnetic ordering by invoking Hubbard repulsion. Charge disproportionation driven by Hund's physics, makes an occupation imbalance with broken inversion symmetry in the remaining $d_{xy}$ and $d_{x^2-y^2}$ orbitals from distinct Co atoms within the bilayer unit, resulting in the polar metallicity. Meanwhile, this charge disproportionation scenario allows consequent conducting carriers to couple with interlayer local spins via Hund's coupling, giving rise to in-plane double-exchange ferromagnetism. Our molecular orbital formulation further provides a guide towards an effective Hamiltonian for modelling the unconventional synergy of metallicity, polarity and antiferromagnetism in Sr$_3$Co$_2$O$_7$, which may be a unified framework widely applicable to double-layer Ruddlesden-Popper perovskite oxides.