In this study, we integrate experimental observations and theoretical models to elucidate the complex phenomena observed in the resonant S 𝐾-edge KLL Auger scattering spectra of the SF6 molecule. A two-dimensional spectral map, constructed of incident photon energy and kinetic energy of the emitted Auger electron, is shown to be a versatile tool for understanding a character of the core-excited potential energy surface and change of the molecular geometry. Our findings reveal how the distinct dispersion behavior of multiple spectral lines enables mapping of ultrafast dynamics within the short-lived core-excited states. Our results confirm the presence of nuclear dynamics in the S1𝑠−16𝑎1 1𝑔 and S1𝑠−16𝑡1 1𝑢 core-excited states, while dynamics is absent in the S1𝑠−17𝑡1 1𝑢 state. Using a combination of ab initio analysis, simulations with Coulomb model potentials, and a simple analytical approximation, we qualitatively demonstrate how the varying characteristics of spectral dispersion—classified as Raman, non-Raman, and anti-Raman—mirror the relative gradients of the intermediate and final states in the resonant x-ray scattering process. This insight allows for the effective mapping of molecular potential energy curves, offering a prospective tool on the underlying mechanisms of resonant Auger scattering and its potential for probing molecular dynamics.
