Resonant Auger electron spectroscopic study at the symmetry-forbidden 1 a 1 g -> 6 a 1 g excitation below the S K-shell threshold of SF 6 is reported. Partial electron yield and resonant K L L Auger spectra have been measured by using monochromatized undulator synchrotron radiation. By changing the photon energy in small steps, a so-called 2D map is produced. In this map, the dipole-forbidden transition exhibits spectral features (e.g., an S-shaped dispersion relation), which are well known and understood for dipole-allowed transitions. We validate by a theory that for the case of dipole-forbidden transitions, these spectral features can be analyzed in the same way as previously established for the dipole-allowed ones. This approach grants information on the nuclear dynamics in the K-shell core-excited states of SF 6 on the femtosecond (fs) timescale. In particular, for the potential-energy curves of the states S 1 s(-1) 6(a1g) and S 2p(-2)6a(1g), the slopes at the equilibrium distance of the ground state are derived. Symmetry breaking as a result of ultrafast vibronic coupling is revealed by the population of the electronically forbidden excited state. Published under an exclusive license by the AVS.