Proposed ordering of textured spin singlets in a bulk infinite layer nickelate (2007.03185v3)

Abstract: The infinite-layer structure nickelate Ba$2$NiO$_2$(AgSe)$_2$ (BNOAS) with $d^8$ Ni ions and a peculiar susceptibility $\chi(T)$ is studied with correlated density functional methods. The overriding feature of the calculations is violation of Hund's rule coupled with complete but unconventional spin-orbital polarization, leading to an unexpected low spin $^1B_1$, "off-diagonal singlet" (ODS) textured by an internal orbital structure of compensating $d{x^2-y^2}^{\uparrow}$ and $d_{z^2}^{\downarrow}$ spins. This unconventional configuration has lower energy than conventional high-spin or low-spin alternatives. An electronic transition is obtained at a critical Ni-O separation $d_c^{Ni-O}=$2.03 \AA, above which Ni becomes magnetic in square planar NiO$2$ compounds. We propose scenarios for the signature of magnetic reconstruction in $\chi(T)$ at $T{m}$=130 K without any Curie-Weiss background (no moment) that invoke ordering of Ni $d^8$ moieties that are largely this generalized Kondo singlet. The underlying physics of this system is modeled by a Kondo sieve model (2D Kondo necklace) of a "Kondo" $d_{z^2}$ spin on each site, coupled to a $d_{x^2-y^2}$ spin that is itself strongly coupled to neighboring like-spins within the layer. The observed magnetic order places BNOAS below the quantum critical point of the Kondo sieve model, providing a realization of the previously unreported long-range ordered near-singlet weak antiferromagnetic phase. We propose electron doping experiments that would drive the system toward a $d^{9-\delta}$ configuration and possible superconductivity with similarity to the recently reported Ba$2$CuO${3.2}$ that superconducts at 73 K.