Octahedral rotation instability in Ba$_2$IrO$_4$

TL;DR

This study reveals that Ba$_2$IrO$_4$ is dynamically unstable in its high-symmetry phase and that octahedral rotations are energetically favorable, significantly impacting its electronic and magnetic properties.

Contribution

First-principles phonon calculations identify unstable modes leading to octahedral rotations, challenging the assumption of a non-rotated high-symmetry structure for Ba$_2$IrO$_4$.

Findings

Unstable phonon branch along the Brillouin-zone boundary segment XP.

Rotated phases with octahedral rotations are energetically more favorable.

Rotations influence the electronic structure, hosting a narrow half-filled J_eff=1/2 manifold.

Abstract

Ba$_2$IrO$_4$ has been refined in the tetragonal $I4/mmm$ phase without octahedral rotations, and its physical properties have been interpreted in this high-symmetry structure. However, the dynamical stability of this undistorted phase has not previously been questioned. It is important to establish whether other lower-symmetry structures are energetically more favorable because octahedral rotations control electronic bandwidths and constrain which magnetic interactions are allowed by symmetry. Here I compute first-principles phonon dispersions of $I4/mmm$ Ba$_2$IrO$_4$ including spin-orbit interaction. I find a nearly-flat nondegenerate unstable branch along the Brillouin-zone boundary segment $XP$ associated with inplane rotations of the IrO$_6$ octahedra. Using group-theoretical analysis, I enumerate the symmetry-allowed distortions associated with the $X_2^+$ and $P_4$ instabilities and fully relax the resulting structures. Only five of the twelve possible distortions can be stabilized, and the energy gain scales with the number of layers that exhibit octahedral rotations: phases with rotations in every IrO$_6$ layer are lower by $-5.8$ meV/atom and are nearly degenerate with respect to the stacking phase. Electronic structure calculations show that these rotated phases host a narrow and well-separated half-filled $J_{\textrm{eff}} = 1/2$ manifold, whereas structures with rotations only in alternate layers have broader and more entangled bands. This motivates a reinvestigation of the crystal structure of Ba$_2$IrO$_4$ and indicates that octahedral rotations should be considered in modeling its correlated electronic and magnetic properties.