Strongly anisotropic electronic and magnetic structures in oxide dichlorides RuOCl$_2$ and OsOCl$_2$

TL;DR

This study uses advanced computational methods to reveal strongly anisotropic electronic and magnetic properties in RuOCl$_2$ and OsOCl$_2$, showing they are spin-1 systems with antiferromagnetic order along chains.

Contribution

It provides a detailed theoretical analysis of the electronic and magnetic structures of RuOCl$_2$ and OsOCl$_2$, highlighting their anisotropic properties and spin states, which differ from previous studies on similar materials.

Findings

No ferroelectric instability along the a-axis.

Disappearance of Peierls distortion leading to undistorted phase.

Staggered antiferromagnetic order along the a-axis.

Abstract

Here, using density functional theory and density matrix renormalization group methods, we investigate the electronic and magnetic properties of RuOCl$_2$ and OsOCl$_2$ with $d^4$ electronic configurations. Different from a previous study using VOI$_2$ with $d^1$ configuration, these systems with $4d^4$ or $5d^4$ do not exhibit a ferroelectric instability along the $a$-axis. Due to the fully-occupied $d_{xy}$ orbital in RuOCl$_2$ and OsOCl$_2$, the Peierls instability distortion disappears along the $b$-axis, leading to an undistorted I${\rm mmm}$ phase (No. 71). Furthermore, we observe strongly anisotropic electronic and magnetic structures along the $a$-axis. The large crystal-field splitting energy (between $d_{xz/yz}$ and $d_{xy}$ orbitals) and large hopping between nearest-neighbor Ru and Os atoms suppresses the spin-orbital effect in $M$OCl$_2$ ($M$ = Ru or Os) with electronic density $n = 4$, resulting in a spin-1 system instead of a $J = 0$ singlet ground state. Moreover, we find staggered antiferromagnetic order with $\pi$ wavevector along the $M$-O chain direction ($a$-axis) while the magnetic coupling along the $b$-axis is weak. Based on Wannier functions from first-principles calculations, we calculated the relevant hopping amplitudes and crystal-field splitting energies of the $t_{2g}$ orbitals for the Os atoms to construct a multi-orbital Hubbard model for the $M$-O chains. Staggered AFM with $\uparrow$-$\downarrow$-$\uparrow$-$\downarrow$ spin structure dominates in our DMRG calculations, in agreement with DFT calculations.