Energy is not a convex function of particle number for r-k interparticle potentials with k > log34.

ABSTRACT

The energy of a many-particle system is not convex with respect to particle number for r-k interparticle repulsion potentials if k > log34 ≈ 1.262. With such potentials, some finite electronic systems have ionization potentials that are less than the electron affinity they have negative band gap (chemical hardness). Although the energy may be a convex function of the number of electrons (for which k = 1), it suggests that finding an analytic proof of convexity will be very difficult. The bound on k is postulated to be tight. An apparent signature of non-convex behavior is that the Dyson orbital corresponding to the lowest-energy mode of electron attachment has a vanishingly small amplitude.