The theoretical basis of electronegativity

Abstract

Electronegativity is one of the most enduring concepts in chemistry, which, on occasion, has been referred to as the third dimension of the periodic table. All this without a secure theoretical basis for this concept. It has now been found that the ground-state energy of the valence electron of an atom in its promotion state provides this theoretical basis. It can be calculated from first principles by simulated compression of the atom to the point where the valence electron decouples from the core and behaves like a free particle in an impenetrable sphere. This calculated energy represents the atomic Fermi level, which is the electronic chemical potential of a single atom in its valence state. All empirical statements about electronegativity are readily reconciled with this theoretical concept which, in addition, closely reflects the expected periodicity. 1997 by John Wiley & Sons, Ltd.