Role of symmetry-forbidden transitions in resonant inelastic X-ray scattering emission from materials with trapped molecular O$_2$

Abstract

Oxygen resonant inelastic X-ray scattering has become a prominent tool for unveiling the electronic structure of solids, especially redox mechanisms in Li-rich cathode materials. A number of studies have observed a strong absorption feature at 531 eV associated with the anomalous capacity of Li-rich cathodes. The most prominent emission feature arising from absorption at 531 eV occurs at 523 eV and has been attributed to the $^3\Pi_\text{g}$ final state of molecular O$_2$. However, in many materials, this feature exhibits a secondary emission peak at a loss of 4.3 eV loss which is not seen in the spectrum of gas-phase oxygen. This study revisits the spectra of these materials and investigates transitions that are forbidden for an isolated O$_2$ molecule as a possible explanation for the secondary emission peak. A group theoretic analysis and simulation of RIXS cross-sections suggest that this feature is consistent with molecular oxygen in a low-symmetry environment owing to final states descending from the $^3\Sigma_\text{u}^+$ and $^3\Delta_\text{u}$ states of isolated O$_2$. Vibronic coupling and multi-molecule transitions are also discussed as possible mechanisms for enabling transitions to these final states even in a high-symmetry environment. These results support the assignment of the 531 eV absorption peak in these materials exclusively to molecular oxygen and suggest that in materials exhibiting the secondary emission peak, these molecules may reside in low-symmetry environments.