The x-ray photoelectron spectrum of atomic sodium

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Abstract
The Na(1s) binding energy in atomic sodium has been determined by x‐ray photoelectron spectroscopy to be 1079.1(±0.1) eV. The spectrum exhibits a satellite 8.4 eV to the high binding energy side of the primary peak with a relative intensity of 19(±1) %. It is assigned to a 3s→4s excitation accompanying ionization. Ab initio ’’ΔSCF’’ calculations are in good agreement with experiment for both the separation and intensity of the satellite. The unusually large intensity of the shakeup peak compared to those found in the inert gases is discussed. Theoretical Na(1s) binding energies in the series Na, Na2, and Na3, suggest that ∼90% of the binding energy shift between the free atom and the metal (5.1 eV) is due to the extraatomic relaxation in the metal.