Counterexamples to the Convexity of the Energy for Coulomb Particles
Abstract
We present examples where successive ionization potentials of an isolated electronic system are nonincreasing; ergo, the energy is a nonconvex function of particle number. The basic strategy, which is based on minimizing the energy of the N ± 1-electron systems by leveraging solutions to the Thomson problem, seems quite general, giving large families of systems with nonconvex behavior; we show examples for N = 5 and N = 7 charged particles. As with previous counterexamples in the literature, the key ingredient is a qualitative change in configuration upon ionization. We propose two families of molecular structures, F 4 Br 6 5 − and F 6 Br 8 7 −, that are expected to show nonconvex behavior with respect to the number of electrons.
Fields of Study & Subjects
Spectral Theory in Mathematical Physics
Atomic and Molecular Physics
Mathematical functions and polynomials
Publication details
- Journal / source
- The Journal of Physical Chemistry Letters
- Publisher
- American Chemical Society (ACS)
- Volume
- 17
- Issue
- 9
- Pages
- 2524–2529
- Publication date
- 19 February 2026
- Language
- EN