Multiconfigurational Analysis of Local Electronic Structure of $\mathrm{RuO_2}$ Using Relativistic Embedded Clusters

Abstract

We present a multiconfigurational, relativistic embedded-cluster study of the local electronic structure of ruthenium dioxide ($\mathrm{RuO_2}$), a candidate altermagnetic material. Starting from free $\mathrm{Ru}$ ions, we progressively build up the local environment through a $\mathrm{Ru+Q_6}$ electrostatic model, a bare $\mathrm{[RuO_6]^{8-}}$ ligand model, and finally a high-accuracy $\mathrm{RuO_6}$@CTEP embedded cluster that reproduces the crystalline surroundings. All systems are treated at the SA-CASSCF and NEVPT2+SOC levels of theory to capture strong electron correlation and spin-orbit coupling on an equal footing. While the formal local site symmetry of the $\mathrm{Ru}$ sites in $\mathrm{RuO_2}$ is orthorhombic ($D_{2h}$), we find that the calculated $4d$-orbital energy spectrum and its splitting pattern behave much closer to the higher tetragonal ($D_{4h}$) symmetry, preserving a strong quasi-degeneracy among the relevant $4d$ orbitals. Since the local $xy$ quadrupolar order responsible for altermagnetic spin splitting in independent-particle models relies on this symmetry reduction, its suppression by orbital quasi-degeneracy offers a natural explanation for why altermagnetism is not observed in bulk $\mathrm{RuO_2}$ experiments, in contrast to the robust altermagnetic signatures reported in strained thin films.