Theory of clusterization in orbitally degenerate transition-metal compounds driven by lattice instabilities

Abstract

We derive an effective orbital-lattice model with quantum $S=1$ degrees of freedom for transition-metal compounds, providing a microscopic understanding of cluster formation driven by the cooperative interplay of spin, orbital, and lattice degrees of freedom. Motivated by the trimerized phases observed in LiVS$_2$ and LiVO$_2$, we consider a triangular-lattice three-orbital system with two electrons per site occupying the threefold-degenerate $t_{2g}$ manifold. Starting from a multiorbital Kanamori-Hubbard Hamiltonian, we project the low-energy sector onto the local $S=1$ triplet manifold, in which two electrons occupy different orbitals according to Hund's coupling. The resulting effective model exhibits exchange networks whose geometry is determined by the orbital configuration. However, the orbital-driven exchange interactions alone do not stabilize the experimentally observed trimer phase. We find that by incorporating ionic lattice displacements that modulate transfer integrals and induce bond-dependent exchange couplings on shortened and elongated bonds, the phase competition is qualitatively altered, leading to the robust stabilization of a trimerized ground state within a fully quantum-mechanical framework. We further show that a simplified orbital-lattice model, in which the spin-exchange energy is replaced by effective bond energies, faithfully reproduces the essential ground-state properties of the microscopic model. This reduced description enables large-scale finite-temperature simulations and reveals a rich sequence of thermal phase transitions, including first-order, second-order, and Kosterlitz-Thouless transitions into distinct spin-, orbital-, and lattice-ordered phases.