ATOMIC POLARIZABILITY AND ELECTRONEGATIVITY

A close relationship between atomic polarizability and electronegativity is demonstrated. It is shown how atomic polarizability can be used in conjunction with the number of s and p valence electrons to derive electronegativities interpreted as either valence electron densities or the electrostatic force exerted on valence electrons. This leads to a new set of electronegativities for every element in the periodic table that can be easily calculated and understood. Such values are in substantially better agreement with traditional Pauling values than those derived as the average of ionization energy and electron affinity. It is further demonstrated that traditional or chemical electronegativities are more closely related to the density functional definition of hardness than to the corresponding definition of electronegativity. This approach offers promise to ongoing theoretical efforts to delineate the role of electronegativity in chemical bonding. © 1990, American Chemical Society. All rights reserved.