Information encoding in spherical DFT

TL;DR

This paper proves that sphericalized densities in spherical DFT encode all necessary spatial information to uniquely determine the external potential in Coulombic systems, supported by numerical examples.

Contribution

It demonstrates that sphericalized densities alone suffice to reconstruct the external potential, removing the need for atomic location knowledge in spherical DFT.

Findings

Sphericalized densities encode atomic positions for Coulombic systems.

The set of sphericalized densities uniquely determines the external potential.

Numerical examples confirm theoretical predictions for LiF and glycine.

Abstract

Spherical density functional theory (DFT) is a reformulation of the classic theorems of DFT, in which the role of the total density of a many-electron system is replaced by a set of sphericalized densities, constructed by spherically-averaging the total electron density about each atomic nucleus. In Hohenberg-Kohn DFT and its constrained-search generalization, the electron density suffices to reconstruct the spatial locations and atomic numbers of the constituent atoms, and thus the external potential. However, the original proofs of spherical DFT require knowledge of the atomic locations at which each sphericalized density originates, in addition to the set of sphericalized densities themselves. In the present work, we utilize formal results from geometric algebra -- in particular, the subfield of distance geometry -- to show that for Coulombic systems this spatial information is encoded within the ensemble of sphericalized densities themselves, and does not require independent specification. Consequently, the set of sphericalized densities uniquely determines the total external potential of the system, exactly as in Hohenberg-Kohn DFT. This theoretical result is illustrated through numerical examples for LiF and for glycine, the simplest amino acid. In addition to establishing a sound practical foundation for spherical DFT as applied to Coulombic systems, the extended theorem provides a rationale for the use of sphericalized atomic basis densities -- rather than orientation-dependent basis functions -- when designing classical or machine-learned potentials for atomistic simulation.