Controlling the distribution of electrons in materials is the holy grail of chemistry and material science. Practical attempts at this feat are common but are often reliant on simplistic arguments based on electronegativity. One challenge is knowing when such arguments work, and which other factors may play a role. Ultimately, electrons move to equalize chemical potentials. In this work, we outline a theory in which chemical potentials of atoms and molecules are expressed in terms of reinterpretations of common chemical concepts and some physical quantities: electronegativity, chemical hardness, and the sensitivity of electronic repulsion and core levels with respect to changes in the electron density. At the zero-temperature limit, an expression of the Fermi level emerges that helps to connect several of these quantities to a plethora of material properties, theories and phenomena predominantly explored in condensed matter physics. Our theory runs counter to Sanderson’s postulate of electronega-tivity equalization and allows a perspective in which electronegativities of bonded atoms need not be equal. As chemical potentials equalize in this framework, electronegativities equilibrate.
The manuscript has been shortened overall, literature citations have been added and the comparison with CDFT slightly expanded.