On the Origins of Spontaneous Spherical Symmetry-Breaking in Open-Shell Atoms Through Polymer Self-Consistent Field Theory

Abstract

An alternative approach to density functional theory based on self-consistent field theory for ring polymers is applied to neutral atoms hydrogen to neon in their ground states. The spontaneous emergence of atomic shell structure and spherical symmetry-breaking of the total electron density is predicted by the model using ideas of polymer excluded-volume between pairs of electrons to enforce the Pauli-exclusion principle, and an exact electron self-interaction correction. The Pauli potential is approximated and correlations are neglected, leading to comparisons with Hartree-Fock theory, which also ignores correlations. The model shows excellent agreement with Hartree-Fock theory for the atomic binding energies and density profiles of the first six elements, providing exact matches for the elements hydrogen and helium. The predicted shell structure starts to deviate significantly past the element neon and spherical symmetry-breaking is first predicted to occur at carbon instead of boron. The self-consistent field theory energy functional which describes the model is decomposed into thermodynamic components to trace the origin of spherical symmetry-breaking. It is found to arise from the electron density approaching closer to the nucleus in non-spherical distributions, which lowers the energy despite resulting in frustration between the quantum kinetic energy, electron-electron interaction, and the Pauli exclusion interaction. The symmetry-breaking effect is also found to have minimal impact on the binding energies. The pair density profiles display behaviour similar to polymer macro-phase separation, where electron pairs occupy lobe-like structures that combined together, resemble traditional electronic orbitals. It is further shown that the predicted densities satisfy known constraints and produce the same total electronic density profile that is predicted by quantum mechanics.