Banerjee, A.; Vaz Da Cruz, V.; Ekholm, V.; Såthe, C.; Rubensson, J.E.; Ignatova, N.; Gel'mukhanov, F.; Odelius, M.: Simulating fluorine K -edge resonant inelastic x-ray scattering of sulfur hexafluoride and the effect of dissociative dynamics. Physical Review A 108 (2023), p. 023103/1-18
10.1103/physreva.108.023103
Open Access Version
Abstract:
We report on a computational study of resonant inelastic x-ray scattering (RIXS), at different fluorine K-edge resonances of the SF6 molecule, and corresponding nonresonant x-ray emission. Previously measured polarization dependence in RIXS is reproduced and traced back to the local σ and π symmetry of the molecular orbitals and corresponding states involved in the RIXS process. Also electron-hole coupling energies are calculated and related to experimentally observed spectator shifts. The role of dissociative S-F bond dynamics is explored to model detuning of RIXS spectra at the |F1s−16a11g⟩ resonance, which shows challenges to accurately reproduce the required steepness for core-excited potential energy surface. We show that the RIXS spectra can only be properly described by considering breaking of the global inversion symmetry of the electronic wave function and core-hole localization, induced by vibronic coupling. Due to the core-hole localization we have symmetry forbidden transitions, which lead to additional resonances and changing width of the RIXS profile.