Theoretical study of the crystal and electronic properties of $α$-RuI$_3$

Abstract

The material $α$-RuCl$_3$, with a two-dimensional Ru-honeycomb sublattice, has attracted considerable attention because it may be a realization of the Kitaev quantum spin liquid (QSL). Recently, a new honeycomb material, $α$-RuI$_3$, was prepared under moderate high-pressure and it is stable under ambient conditions. However, different from $α$-RuCl$_3$, $α$-RuI$_3$ was reported to be a paramagnetic metal without long-range magnetic order down to $0.35$ K. Here, the structural and electronic properties of the quasi-two-dimensional $α$-RuI$_3$ are theoretically studied. First, based on first-principles density functional theory (DFT) calculations, the ABC stacking honeycomb-layer $R\overline{3}$ (No. 148) structure is found to be the most likely stacking order for $α$-RuI$_3$ along the $c$-axis. Furthermore, both $R\overline{3}$ and $P\overline{3}1c$ are dynamically stable because no imaginary frequency modes were obtained in the phononic dispersion spectrum. Moreover, the different physical behavior of $α$-RuI$_3$ compared to $α$-RuCl$_3$ can be understood naturally. The strong hybridization between Ru $4d$ and I $5p$ orbitals decreases the effective atomic Hubbard repulsion $U$, leading the electrons of RuI$_3$ to be less localized than in RuCl$_3$. As a consequence, the effective repulsion $U$ is reduced from Cl to I, leading to the metallic nature of $α$-RuI$_3$. Based on the DFT+$U$ ($U_{\rm eff} = 2$ eV), plus spin-orbital coupling (SOC), we obtained a spin-orbit Mott insulating behavior for $α$-RuCl$_3$ and, by the same procedure, a metallic behavior for $α$-RuI$_3$, in good agreement with experimental results. Furthermore, when introducing a large (unrealistic) $U_{\rm eff} = 6$ eV, the spin-orbit Mott gap opens in $α$-RuI$_3$ as well, supporting the physical picture we are proposing.