Competing spin-orbital singlet states in the 4$d^4$ honeycomb ruthenate Ag${}_3$LiRu${}_2$O${}_6$

Abstract

When spin-orbit-entangled $d$-electrons reside on a honeycomb lattice, rich quantum states are anticipated to emerge, as exemplified by the $d^5$ Kitaev materials. Distinct yet equally intriguing physics may be realized with a $d$-electron count other than $d^5$. We found that the layered ruthenate Ag${}_3$LiRu${}_2$O${}_6$ with $d^4$ Ru${}^{4+}$ ions at ambient pressure forms a honeycomb lattice of spin-orbit-entangled singlets, which is a playground for frustrated excitonic magnetism. Under pressure, the singlet state does not develop the expected excitonic magnetism but experiences two successive transitions to other nonmagnetic phases, first to an intermediate phase with moderate distortion of honeycomb lattice, and eventually to a high-pressure phase with very short Ru-Ru dimer bonds. While the strong dimerization in the high-pressure phase originates from a molecular orbital formation as in the sister compound Li${}_2$RuO${}_3$, the intermediate phase represents a spin-orbit-coupled $J$-dimer state which is stabilized by the admixture of upper-lying $J_{\mathrm{eff}}=1$-derived states. We argue that the $J$-dimer state is induced by a pseudo-Jahn-Teller effect associated with the low-lying spin-orbital excited states and is unique to spin-orbit-entangled $d^4$ systems. The discovery of competing singlet phases demonstrates rich spin-orbital physics of $d^4$ honeycomb compounds and paves the way for realization of unconventional magnetism.

12 pages, 5 figures

References in corpus (8)

• Mott Insulators in the Strong Spin-Orbit Coupling Limit: From Heisenberg to a Quantum Compass and Kitaev Models
• Spin-orbit-entangled electronic phases in 4$d$ and 5$d$ transition-metal compounds
• Magnetic state of pyrochlore Cd2Os2O7 emerging from strong competition of ligand distortions and longer-range crystalline anisotropy
• Effect of structural disorder on the Kitaev magnet Ag${}_3$LiIr${}_2$O${}_6$
• Nonmagnetic $J=0$ State and Spin-Orbit Excitations in K${}_2$RuCl${}_6$
• Highly frustrated magnetism in relativistic ${\mathbf{d}}^4$ Mott insulators: Bosonic analog of Kitaev honeycomb model
• Unconventional magnetism in the 4d${}^4$ based ($S=1$) honeycomb system Ag${}_3$LiRu${}_2$O${}_6$
• Complex pressure-temperature structural phase diagram of honeycomb iridate Cu${}_2$IrO${}_3$

Cited by in corpus (7)

• Vibronic excitations in resonant inelastic x-ray scattering spectra of K${}_2$RuCl${}_6$
• Pressure tuning of competing interactions on a honeycomb lattice
• Fluctuation-induced first order phase transitions in Kitaev-like $d^4$ honeycomb magnet
• (H,Li)${}_6$Ru${}_2$O${}_6$ : a possible zero-field Ru${}^{3+}$-based Kitaev Quantum Spin Liquid
• Hidden covalent insulator and spin excitations in SrRu${}_2$O${}_6$
• Local site behavior of the 5d and 4f ions in the frustrated pyrochlore Ho2Os2O7
• Effect of Ti-doping on the dimer transition in Lithium Ruthenate