Ground state energy is not always convex in the number of electrons

TL;DR

This paper presents the first counterexample demonstrating that the ground state energy of electrons in an external Coulomb potential is not always convex as previously conjectured, challenging assumptions in quantum chemistry.

Contribution

It provides a specific counterexample with six nuclei and fractional charges, showing non-convexity of ground state energy as a function of electron number.

Findings

Ground state energy for 3 electrons exceeds the average of 2 and 4 electrons.

Nuclei can bind 2 or 4 electrons but not 3.

Convexity of energy may not hold for all molecules with integer charges.

Abstract

We provide the first counterexample showing that the ground state energy of electrons in an external Coulomb potential is not always a convex function of the number of electrons. This convexity has been conjectured for decades and plays an important role in quantum chemistry. Our counterexample involves six nuclei with small fractional charges placed far apart. The ground state energy of 3 electrons is shown to be higher than the average of the energies for 2 and 4 electrons. We also show that the nuclei can bind 2 or 4 electrons, but not 3. This article raises the question of whether the energy convexity really holds for all possible molecules (with nuclei of integer charge).