Exact static linear response of excited states from ensemble density functional theory

TL;DR

This paper develops an exact static linear response theory within ensemble density functional theory to accurately evaluate excited-state response functions, incorporating weight derivatives of the Hxc functional.

Contribution

It derives a frequency-independent, exact linear response framework for excited states in ensemble DFT, including a Dyson-type equation for individual states.

Findings

Exact excited-state response functions can be obtained in a frequency-independent manner.

The theory reveals the significance of weight derivatives of the Hxc functional for excited-state corrections.

A zero-weight limit connects the theory to standard Kohn-Sham DFT, enabling practical approximations.

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.