Abstract
Fromager and Lasorne [Electron. Struct. 6 025002 (2024)] have recently derived an in-principle exact Kohn–Sham density functional theory (KS-DFT) of electrons and nuclei, where the nuclear density and the (so-called conditional) electronic density are mapped onto a fictitious electronically non-interacting KS molecule. In this work, we apply the exact factorization formalism to the molecular KS wavefunction, thus leading to disentangled (but coupled) marginal and conditional KS equations. We show that, while being equivalent to the original theory, these equations open new perspectives in the practical extension of regular (electronic) KS-DFT beyond the Born Oppenheimer approximation. The importance and treatment of correlations induced in this context by second-order geometrical derivatives is also discussed.
Reference
Exactly Factorized Molecular Kohn–Sham Density Functional Theory
Lucien Dupuy, Benjamin Lasorne, and Emmanuel Fromager
Computational Chemistry, First published :13 July 2026 -DOI : https://doi.org/10.1002/jcc.70459
Contact
Emmanuel Fromager, team LCQS, Institut de Chimie de Strasbourg, UMR 7177.
