Theoretical study of the crystal and electronic properties of α - RuI 3
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. Recently, a new honeycomb material, α-RuCl 3 , was prepared under moderately 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 calculations, the ABC stacking honeycomb-layer R$\bar{3}$ (No. 148) structure is found to be the most likely stacking order for α-RuI 3 along the c axis. Furthermore, both R$\bar{3}$ and P$\bar{3}$1c are dynamically stable because no imaginary frequency modes were obtained in the phononic dispersion spectrum without Hubbard U. 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, leading the electrons of RuI3 to be less localized than in RuCl 3 . As a consequence, the effective electronic correlation is reduced from Cl to I, leading to the metallic nature of α-RuI 3 . Based on the DFT+U (Ueff=2 eV) plus spin-orbital coupling, we obtained a spin-orbit Mott insulating behavior for α-RuCl 3 and, with the same procedure, a metallic behavior for α-RuI 3 , in good agreement with experimental results. Furthermore, when introducing large (unrealistic) U eff =6 eV, the spin-orbit Mott gap opens in α-RuI 3 as well, supporting the physical picture we are proposing. Our results provide guidance to experimentalists and theorists working on two-dimensional transition metal tri-iodide layered materials.