Exploring a New Regime of Molecular Orbital Physics in 4d Cluster Magnets with Resonant Inelastic X-Ray Scattering

Molecular orbital systems with clusters of heavy transition metal (TM) ions are one of the most important classes of model materials for studying the interplay between local physics and effects of itinerancy. Despite a large number of candidates identified in the family of 4d TM materials, an understanding of their physics from competing microscopic energy scales is still missing. We bridge this gap by reporting the first resonant inelastic x-ray scattering (RIXS) measurement on a well-known series of Ru cluster magnets with a 6H-perovskite structure Ba3MRu2O9 (M3+ = In3+; Y3+; La3+) comprised of Ru dimers. In addition to providing a microscopic explanation for their anomalous magnetic properties, our RIXS measurements combined with theoretical modeling uncover a new regime of molecular orbital physics where the combined effect of large hopping and small spin-orbit coupling results in highly fragile electronic states in the Ru-dimer compounds directly manifested as an abrupt change in the RIXS spectrum accompanying a tiny change in the local structure tuned by the M-site ion. This unique combination of energy scales found only in the 4d but not the 5d cluster magnets highlights the value of these materials as a new platform for studying quantum phase transition involving molecular orbitals.