Abstract
Following a recent work [E. Fromager, J. Phys. Chem. A 2025, 129 (4), 1143−1155] on the ensemble density functional theory (DFT) of excited electronic energy levels, we derive, in this paper, the ensuing static linear response theory, thus allowing for an in-principle exact evaluation of excited-state density–density linear response functions in a completely frequency-independent setting. Once individual-state components of the inverse ensemble linear response function have been introduced, a working Dyson-type equation naturally emerges for each state, individually. By considering the zero-weight limit of the theory, which infinitesimally deviates from standard Kohn–Sham DFT, exact excited-state corrections to ground-state linear response DFT can be identified. They involve the first-order weight derivatives of the ensemble Hartree–exchange–correlation (Hxc) potential and kernel, thus confirming the importance in ensemble DFT of both weight and density-functional derivatives of the ensemble Hxc energy functional.
Reference
Exact Static Linear Response of Excited States from Ensemble Density Functional Theory
Lucien Dupuy & Emmanuel Fromager
The Journal of Physical Chemistry A, First published september 17, 2025 – DOI : https://doi.org/10.1021/acs.jpca.5c04552
Contacts
Lucien Dupuy & Emmanuel Fromager, team LCQS, Institut de Chimie de Strasbourg, UMR 7177.
