Coupled-cluster approach to vibronic effects in resonant inelastic x-ray scattering of quantum materials: Application to a $5d^1$ rhenium oxide

TL;DR

This paper develops an advanced coupled-cluster computational approach to analyze vibronic effects in resonant inelastic x-ray scattering of quantum materials, successfully applying it to a rhenium oxide and revealing detailed vibronic interactions.

Contribution

The work introduces the application of the equation-of-motion coupled-cluster method to model spin-orbit-lattice entangled vibronic states in RIXS spectra, providing accurate interaction parameters and insights into vibronic couplings.

Findings

EOM-CC yields interaction parameters with less than 5% error.

Vibronic coupling to T2g modes causes a shoulder on the elastic peak.

Both T2g and Eg vibronic couplings are necessary to explain RIXS spectral features.

Abstract

First-principles analysis of the spectroscopic signatures of correlated quantum materials poses significant challenges due to the interplay between spin-orbit and vibronic couplings, as well as the need to describe both dynamic and static electron correlation to reach decent accuracy. In this work, we apply the equation-of-motion coupled-cluster (EOM-CC) method to derive the spin-orbit-lattice entangled vibronic states and predict the Re $L_3$ edge resonant inelastic x-ray scattering (RIXS) spectra of Ba$_2$MgReO$_6$. The EOM-CC yields interaction parameters in close agreement with those extracted from RIXS spectra, with errors of less than 5\%. In particular, the EOM-CC method allowed us to determine the weak vibronic coupling to the $T_{2g}$ vibrations, which is difficult to address experimentally. The simulated spectra indicate that vibronic coupling to the $T_{2g}$ modes gives rise to a shoulder on the elastic peak. Going beyond the conventional treatment, which focuses solely on $E_g$ modes, we show that vibronic couplings to both $T_{2g}$ and $E_g$ modes are required to account for the fine structure of the RIXS spectra. This work demonstrates that the EOM-CC method is a powerful tool for accurately predicting the complex local states at metal sites and spectroscopic signatures of correlated insulating materials.