Electronegativities of Pauling and Mulliken in Density Functional Theory

Electronegativity is a fundamental concept in chemistry that allows one to infer important aspects about the interactions between chemical species. In the present work we make use of the framework provided by the density functional theory of chemical reactivity, to discuss in a unified way the approaches to the concept of electronegativity developed by Pauling and by Mulliken. Our analysis starts by making use of the identification of the electronegativity of Mulliken with the chemical potential of density functional theory, and continues to show that the ionic correction proposed by Pauling can be derived, with certain approximations, from the quadratic smooth interpolation of the energy as a function of the number of electrons in terms of the chemical potentials and the hardnesses of the interacting species, from which one can infer the close qualitative relationship between Pauling's electronegativity and the electrophilicity concept.