Computational design of f -electron Kitaev magnets: Honeycomb and hyperhoneycomb compounds A2PrO3 ( A= alkali metals)

Abstract

The Kitaev spin model offers an exact quantum spin liquid in the ground state, which has stimulated exploration of its material realization over the last decade. Thus far, most of the candidates are found in $4d$- and $5d$-electron compounds, in which the low-spin $d^5$ electron configuration subject to strong spin-orbit coupling comprises a Kramers doublet with the effective angular momentum $j_{\rm eff}=1/2$ and gives rise to the bond-dependent anisotropic interactions in the Kitaev model. Here we theoretically investigate other candidates in $4f$-electron compounds with the $f^1$ electron configuration on both quasi-two-dimensional honeycomb and three-dimensional hyperhoneycomb structures, $A_2$PrO$_3$ with $A$=Li, Na, K, Rb, and Cs. Based on {\it ab initio} calculations, we show that the electronic structures of these compounds host a spin-orbital entangled Kramers doublet with $j_{\rm eff}=1/2$ in the $\Gamma_7$ state. By constructing the tight-binding Hamiltonian and performing a perturbation expansion, we find that the low-energy magnetic properties of $A_2$PrO$_3$ are well described by an effective spin model with the $J$-$K$-$\Gamma'$ model. The most remarkable feature is that the Kitaev interaction $K$ is antiferromagnetic, in contrast to the ferromagnetic one in the $d^5$ candidates at hand. The exchange interactions are systematically modulated by changing the $A$-site cations. As a consequence, the compounds with $A$=Li and Na may have a dominant antiferromagnetic $K$, but $J$ dominates $K$ and $\Gamma'$ in the cases with $A$=Rb and Cs. Also, by computing the ground states of the $J$-$K$-$\Gamma'$ model by using the exact diagonalization, we map out the systematic evolution of the model parameters in the phase diagram. Our results will stimulate material exploration of the antiferromagnetic Kitaev interaction in $f$-electron compounds.