DOI: 10.1063/1.1749394 ISSN:

A New Electroaffinity Scale; Together with Data on Valence States and on Valence Ionization Potentials and Electron Affinities

Robert S. Mulliken
  • Physical and Theoretical Chemistry
  • General Physics and Astronomy

A new approximate ``absolute'' scale of electronegativity, or electroaffinity, is set up. The absolute electroaffinity on this scale is equal to the average of ionization potential and electron affinity. These quantities must, however, in general, be calculated not in the ordinary way, but for suitable ``valence states'' of the positive and negative ion. Also, the electroaffinity of an atom has different values for different values of its valence; in general the electroaffinity as here calculated (in agreement with chemical facts) is larger for higher valences. Electroaffinity values have been calculated here for H, Li, B, C, N, O, F, Cl, Br, I. They show good agreement in known cases with Pauling's electronegativity scale based on thermal data, and with the dipole moment scale. The present electronegativity scale (like the others) is rather largely empirical, especially as to its quantitative validity; and it remains to be seen whether or not the latter will be more than very rough when tested for a wider range of cases. Nevertheless the new scale has a degree of theoretical background and foundation which throws some new light on the physical meaning of the concept of electronegativity (or electro-affinity). The basis of the present scale, it should be mentioned, is simpler and more certain for univalent than for polyvalent atoms.—The nature of valence states of atoms is briefly discussed. It is hoped that the tabulations of atomic valence state energies and valence state ionization potentials and electron affinities given at the end of this paper may be useful in problems of molecular structure.

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