Thus, the polarization dependent RIXS intensity is an indicator of the shape and symmetry of the occupied MOs. For SF 6 in O h geometry, the occupied MOs of different character can either have local π or σ symmetry with respect to the S-F bond. As seen from FIG. , some of the transitions have intensities along vertical polarization were as others have intensity along the horizontal polarization. Based on symmetry arguments, t 1g , t 2g , and t 2u MOs have π symmetry and hence have higher intensity along horizontal polarization, whereas e g and a 1g MOs having σ symmetry has higher intensity along vertical polarization, see Table . However, the t 1u MOs are not uniquely defined in terms of σ and π symmetry and hence can give intensity of both horizontal or vertical polarization. In this particular case, the polarization dependence is related to the coefficient of the local F atomic-orbital's contribution to the t 1u MOs. We see from the MO displayed in SI, see FIG. in SI, that indeed 4t 1u and 5t 1u , which in these two cases have different polarization due to the orbital hybridization, see Table . and the restricted sub-space TD-DFT/CAM-B3LYP levels of theory for the |F1s -1 6a 1 1g resonance and with experimental spectrum obtained from Ref. . Both the TD-DFT and DFT-ROCIS computation were done with a localized F1s core-hole, and interference between different intermediate states are neglected. The polarization dependence was computed using Equation 10 in one-electron picture. The red spectra indicate spectra at horizontal polarization(χ = 0 0 ) and blue spectra represents vertical polarization (χ = 90 0 ).