Chemical potential, ionization energies, and electron correlation in atoms

Publisher Website
Google Scholar
Abstract
The total energy E(Z,N) of an atomic ion with nuclear charge Ze and N electrons is expanded in a Taylor series about the neutral atom energy E(Z,Z). By truncating the Taylor expansion, the chemical potential μ of the neutral atom is expressed in terms of the nth ionization potential In = E(Z,Z−n)−E(Z, Z−n+1), the most refined formula given being to fifth order, and involving up to and including I4. As an approximate test of the validity of this expression, one can then make use of the empirical relation that In∼nI1, in which case, with the electron affinity consistently taken as small, one obtains μ∼−I1/2, consistent with Mulliken’s electronegativity. The relation of the present work to that of March and Bader, which involves the potential energy of the electron correlations, is briefly discussed.

This publication has 8 references indexed in Scilit: