Energies and chemical shifts of the sulphur 1s level and the KL2L3(1D2) Auger line in H2S, SO2 and SF6

Abstract

Abstract The sulphur 1s binding energies and KL2L3(1D2) Auger energies have been measured in gaseous H2S, SO2 and SF6. The experimental data, including the chemical shifts, are compared with various theoretical ab initio results. Theoretical and experimental values agree within 1-2 eV for the chemical shift and the binding energy of the 1s level, provided in the latter case relaxation, relativistic and correlation corrections are applied. Likewise, Shirley's method20, which uses empirical energies, predicts the Auger energies satisfactorily. The measured S 1s binding energies are 2478.5(1) eV, 2483.7(1) eV and 2490.1(1) eV, and KL2L3(1D2) Auger energies are 2098.7(1) eV, 2095.5(2) eV, 2092.6(1) eV for H2S, SO2 and SF6, respectively. The chemical shift for the 1s electron is found to be greater than for the 2s or 2p electron and in better accord with the prediction of the potential model. Data suggest the molecular relaxation energy to be small compared with the atomic relaxation energy.