Auger energy shifts and core level relaxation energies in XeF2, XeF4, and XeF6

The energy shifts in 3d photoelectron and M4N4,5 N4,5 Auger spectra of Xe have been studied for HXeF2, XeF4, and XeF6 molecules in the gas phase. Using the Auger parameter method, the contributions of the initial state chemical and final state extra-atomic relaxation effects to the observed shifts have been estimated. The relaxation part has found to be significant both in the binding energy (up to 1.8 eV for XeF6) and especially in the Auger shifts. The ground state shifts are thus larger than the 3d binding energy shifts reported earlier. Calculated atomic charges are also now in better agreeement with theory and other experimental values.