The emission from 3e g and 1t 2g overlap with each other in the RIXS spectra whereas they are well separated in the XE spectrum by almost ∼0.8 eV. Experimentally since only one peak for both XE spectrum and |F1s -1 6a 1 1g resonance can be identified, for this particular case should be attributed to an average value between the two emissions. Experimentally this shift turns out to be 1.3 eV. For the simulated spectra the spectator shift for 3e g and 1t 2g emission turns out to be 2.04 and 1.09 respectively, with the average to be 1.565 eV.For the 4t 1u emission energies the experimental spectator shift turns out to be 1.65 eV, as compared to the simulated value of 1.91 eV. Interestingly we see that if we consider that there is an error of ∼0.38-0.35 eV in computing the spectator shift, as demonstrated earlier, then the adjusted value ob-tained from the simulated spectra for the |F1s -1 6/7t The RIXS spectra for the |F1s -1 6a 1 1g resonance of SF 6 , at the ground state equilibrium geometry, has been already simulated are the DFT-ROCIS/B3LYP and TD-DFT/CAM-B3LYP levels of theory, as shown in FIG. . However, the F1s core excitation gives dramatic changes in the electronic structure and chemical bonding, since according to the equivalent core principle, the valence electrons effectively experience the F1s 1 core like that of Ne1s 2 . Hence, it induces vibrational excitations leading even to dissociative dynamics, which can play a significant role for the RIXS signal . For the wave packet dynamics of the RIXS spectrum the |F1s -1 6a 1 1g resonance, we performed a rigid scan along F 5 S-F bond elongation and calculated a one dimensional cut in the potential energy surfaces of the ground, valence-excited and core-excited states. The dissociation of the F 5 S-F bond transform the symmetry of the system from O h to C 4v symmetry. Thus, MOs transform accordingly, breaking the inversion symmetry and lifting degeneracy of states. This is seen as a splitting of the one dimensional cuts in certain degenerate potential energy surfaces In Table , we show the correlation-diagram between the valence-excited states in O h symmetry and C 4v and the splitting of the degenerate states. Notably the triply degenerate states, in O h symmetry, split into doubly degenerate and single degenerate states, while the doubly degenerate states, in O h symmetry, split into two singly degenerate states. This gives associated dynamical effects in the RIXS spectrum.