Pressure-induced formation of rhodium zigzag chains in the honeycomb rhodate Li${}_2$RhO${}_3$

Abstract

We use powder x-ray diffraction to study the effect of pressure on the crystal structure of the honeycomb rhodate Li${}_2$RhO${}_3$. We observe low-pressure ($P$$<$$P_{c1}$ = 6.5 GPa) and high-pressure ($P$$>$$P_{c2}$ = 14 GPa) regions corresponding to the monoclinic $C2/m$ symmetry, while a phase mixture is observed at intermediate pressures. At $P$$>$$P_{c2}$, the honeycomb structure becomes distorted and features short Rh--Rh bonds forming zigzag chains stretched along the crystallographic $a$ direction. This is in contrast to dimerized patterns observed in triclinic high-pressure polymorphs of $\alpha$-Li${}_2$IrO${}_3$ and $\alpha$-RuCl${}_3$. Density-functional theory calculations at various pressure conditions reveal that the observed rhodium zigzag-chain pattern is not expected under hydrostatic pressure but can be reproduced by assuming anisotropic pressure conditions.

arXiv comment11 pages, 11 figures

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