On the existence of absolute Pauling electronegativities

Abstract

From a reappreciation of the recently proposed Parr—Pearson scheme on absolute electronegativity and hardness, it follows that electron affinities can be considered as absolute Pauling electronegativities. The fundamental difference between Pauling and Mulliken electronegativities is demonstrated. A quantumchemical framework of Hückel-type is developed wherein these electron affinities act as one-electron energies (diagonal matrix elements). This novel definition of absolute Pauling electronegativities is shown to be consistent with Pauling's original bond energy equation. The validity of the deductions made implies a possible new look at chemical exchange forces in terms of intra-atomic charge-invariance effects (atom—antiatom interactions).