Electron spectra from an extensive series of sulfur compounds have been studied. A correlation has been established between the observed position of inner electron lines of sulfur and structure. The influence of structure on the electron binding energies is discussed in terms of a calculated atomic charge, based on the concepts of electronegativity and partial ionic character of bonds. The results are useful for the study of bonding and structure in sulfur chemistry, and are applied particularly to the discussion of the sulfur-oxygen bond (S=O).

Carbon 1s energies are measured by ESCA for a series of aliphatic saturated compounds, carbonyl compounds, and some aromatic compounds. For convenient use in chemical structure analysis the binding energy shifts are correlated with a charge parameter obtained from electronegativity considerations. The shifts are also analyzed in terms of group shifts from which group electronegativities are derived. A comparison is made between the shifts in solid and gaseous samples and it is shown that solid state effects are small for non-ionic compounds. The observed shifts are then compared with results of semi-empirical and ab initio molecular orbital calculations on free molecules. The theoretical calculations are simplified by use of an electrostatic potential model.

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The core lines and valence bands of LiF, BeO, BN and graphite have been studied by the ESCA technique. The energy differences between inner levels and valence bands are compared with X-ray transition energies. The changes in binding energy for the Bels level when going from metal to oxide and fluoride are compared with X-ray spectroscopic data and with a study of the disintegration constant in electron capture of 7Be in the same compounds.