A mapping is made between fermion exchange and excluded volume in the quantum-classical isomorphism using polymer self-consistent field theory. Apart from exchange, quantum particles are known to be exactly representable in classical statistical mechanics as ring polymers, with contours that are parametrized by the inverse thermal energy, often called the imaginary time. Evidence in support of a previously used approximation for fermion exchange in ring polymer self-consistent field theory is given, specifically, that the use of all-contour interactions in the mean field picture instead of equal imaginary time interactions is justified based on the symmetry of ring polymers. It is also shown that the removal of forbidden thermal trajectories, both those that violate excluded volume directly and those that represent topologically inaccessible microstates, is equivalent to antisymmetric exchange. The electron density of the beryllium atom is calculated with ring polymer self-consistent field theory ignoring classical correlations, and very good agreement is found with Hartree-Fock theory which also neglects Coulomb correlations. The total binding energies agree to within less than $6\%$, which, while still far from chemical accuracy, is remarkable given that the field theory equations are derived from first principles with zero free parameters. The discrepancy between self-consistent field theory and Hartree-Fock theory is attributed to classical Coulomb self-interactions which are included in Hartree-Fock theory but not in self-consistent field theory. A potential method to improve the agreement by more accurately representing electron-electron self-interactions in self-consistent field theory is discussed, as are the implications for quantum foundations of the quantum-classical mapping between fermion exchange and thermal trajectory excluded volume.

• Received 15 February 2024
• Accepted 29 April 2024

DOI:https://doi.org/10.1103/PhysRevA.109.052819