Coupled-cluster study of dynamic Jahn-Teller effect in a 5d² W antifluorite

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In correlated insulators, the interplay among coexisting charge, spin, orbital, and lattice degrees of freedom gives rise to rich quantum phenomena, while unraveling the interplay is not straightforward. In the family of cubic 5d² double perovskites, the ground spin-orbit coupled electronic states of 5d metal sites are degenerate and couple to the Jahn-Teller active vibrations, whereas no experimental evidence of the symmetry-lowering in the low-temperature ordered phases has been reported. To quantitatively unravel the nature of 5d² centers, we apply equation-of-motion coupled cluster (EOM-CC) theory to analyze the vibronic and magnetic properties of 5d² W sites of Cs₂WCl₆. We derive the electronic and vibronic model Hamiltonians, calculate the W L₃ edge resonant inelastic x-ray scattering (RIXS) spectra, and determine the effective magnetic moment. The simulated RIXS spectra show that vibronic coupling makes several peaks asymmetric. The effective magnetic moments exhibit a temperature dependence similar to that observed experimentally, confirming the validity of the calculated distribution of low-energy levels. Our calculations indicate that the Jahn-Teller effect in Cs₂WCl₆ is in a weak regime, and noticeable deformation would not occur, whereas the dynamic Jahn-Teller effect modulates the shapes of the RIXS spectra and affects the magnetic moment. This work demonstrates the usefulness of the EOM-CC method for predicting physical phenomena on metal sites in correlated insulating materials.