In this study, we simulate RIXS processes involving final states which are both valence-excited and vibrationally excited. A final (ground or valence-excited) state, |V E i , is populated if the RIXS channel to the final state is allowed from the initial (ground) state, |V E 0 , via the intermediate (core-excited) state, |CE i , i.e. if the transitions involved |V E 0 → |CE i and |CE i → |V E i are both simultaneously allowed. Thus symmetry selection rules play a pivotal role in the formation of a RIXS spectrum, and can be analyzed both in terms of dipole transition moments and point group symmetry. Often if |V E 0 → |V E i is forbidden as a direct transition, the corresponding RIXS channel may be allowed in the three level scattering process . This opens up an avenue to observe optical dark states. However the purely electronic symmetry selection and propensity rules can be broken in the presence of vibronic couplings as has been extensively discussed earlier . The effect of breakage and restoration of these symmetry rules are most interesting and profound in molecules having inversion symmetry, of which SF 6 is a particularly interesting example. . This breakage of symmetry can not only be brought on by vibronic coupling at small distortions from the Franck-Condon region, but may even involve ultrafast bond dissociation, due to strong forces in the core-excited state in the Franck-Condon region of the ground state. If a system involving light nuclei populates an intermediate state which has a dissociative potential with a large gradient, the system undergoes an ultra-fast bond cleavage dynamics on the same time scale as the relaxation to final state . Thus the RIXS signal contains information about changes in electronic structure and chemical bonding during ultra-fast dynamics in the intermediate or final states. Moreover, with high enough energy resolution, RIXS can probe the vibrational quantum levels in the final states, and thus in principle shed light on the structure of the potential energy surface along that particular degree of freedom, associated with vibrational excitations . Quasielastic scattering back into the electronic ground state is a particularly powerful probe of vibrational structure, since the quasi-elastic vibrational progression is usually nicely separated from the electronically inelastic RIXS bands . A particular effect observed in the presence of vibronic coupling or ultra-fast dissociation is core-hole localization, which has been observed in simple diatomics and other symmetric molecules . It is important to notice that the vibronic coupling of coreexcited states and related localization of the core-hole in symmetric polyatomic molecules can have very strong influence due to intrinsic near-degeneracy of core-hole states. This motivates us to use a model based on the localization of the core-hole in one of the F atoms of the SF 6 molecule . In spite of the symmetry breaking in the core-excited state we assign in the text the RIXS transitions using the conventional notations of the O h group, owing to the inherent O h symmetry of the SF 6 molecule.. SF 6 has been investigated extensively using X-ray spectroscopic techniques. These include studies done at the sulfur K-and L-edges and the fluorine K-edge . The dissociation dynamics of SF 6 following a soft ionization has also been measured using time-resolved sulfur L-edge X-ray absorption (XA) spectroscopy . Electron vibrational coupling in SF 6 has been investigated using soft X-ray spectroscopy . Additionally, vibrational wave packets in SF 6 molecule have recently been investigated using soft-transient X-ray absorption . Recently there also has been measurements of non-resonant XE and RIXS at the fluorine Kedge . SF 6 in its equilibrium structure has six equivalent F atoms singly bonded to the sulfur for all vertices in an octahedron. Also in O h symmetry, each frontier molecular orbital (MO) can be classified locally into having σ and π symmetry around the S-F bonds. Ekholm et al. showed using non-resonant XE measurements and computation of the dissociative dynamics along the F 5 S-F bond, how peaks associated with S-F bonds vanish with only the σ and π features from the dissociating ionized F atom remain, as the S-F bond dissociates. The S-F bond dissociation following a F 1 s → 6a 1g transition has been studied by observing Auger-Doppler effect using circularly polarized X-ray. It has also been suggested in that study that the sharp feature observed in the RIXS spectra at the lowest resonance, i.e. |F1s -1 6a 1 1g , in the F1s XA spectrum can be associated with ultra-fast S-F bond elongation and dissociation, similar to atomic and pseudo-atomic features in HBr and H 2 O . This accounted for the sharpness and enhanced intensity of the main peak, and also shows that the rest of the peak originate from the MOs associated with shorter S-F bond distances. It was also demonstrated that how polarization dependent F1s RIXS can shed light upon this local σ and π symmetry. It was observed that though resonant emission eliminated higher energy satellite peaks that was observed in the non-resonant XE spectrum, the overall spectra was preserved at the t 1u , t 2g , and e g resonances at 694.6 eV, 699.8 eV, and 713.1 eV, respectively, signifying a rather small electron-hole coupling for these resonances. A weak dependence of the emission intensity was observed for the peaks corresponding to 4t 1u and 1t 2g state, which marginally gained intensity over the other upon excitation at the t 1u and 2t 2g resonance, signifying that the overall inversion symmetry of the molecule does affect the initial excitation, in spite of the fact that there is a dominant effect of core-hole localization via symmetry breaking vibronic coupling channels.