The 1D rigid scan of the F 5 S-F dissociation has been carried out with TD-DFT/CAM-B3LYP and DFT-ROCIS/B3LYP. This was done to access the quality of different levels of theory in simulating the valence and core excited states and potential energy surfaces. Since the PES involve SF 5 -F bond dissociation, there the obvious threat of error being introduced by using single- Comparison of experimentally measured emission spectra obtained at different resonances and non-resonant condition highlighting the spectator shifts. The experimental spectra are reproduced from Ref. The vertical lines of different colors denote prominent peaks in the emission spectator. Each line of different color bend horizontally, i.e. representing the experimentally observed spectator shift, to align with the resonant emission peak position for the |F1s -1 6a 1 1g resonance to the corresponding non-resonant XE peak. The identification or association between the peaks in the |F1s -1 6a 1 1g RIXS spectrum and those in the XE spectrum has been motivated from the simulated spectra as shown in FIG. and. The spectator shift for the other resonant peaks are not marked as the shifts are rather small. The red shifts for the orange, violet and gray lines are 1.13, 1.30 and 1.65 eV respectively. Compare with Table A comparison between the TD-DFT and DFT-ROCIS diabatic states, clear shows that though there are overall similarities, the major disagreement comes in the shape