Nonempirical Time-Dependent Density Functional Theory Framework for Nonlocal Exchange--Correlation Potentials
Abstract
Advanced, orbital-dependent exchange--correlation (XC) functionals can significantly improve the description of electronic structural properties, but they substantially worsen spectral properties that are computed within standard linear-response time-dependent density functional theory frameworks. This is not a failure of the underlying Kohn-Sham states, but due to a formal inconsistency in the treatment of the dynamic density response when the non-locality of the XC potential is not taken into account consistently on the level of the full off-diagonal density matrix. To avoid these complexities, we present a non-empirical additive correction Δftextnormalxc(q,ω) to the dynamic XC kernel that re-enforces the exact f-sum rule of the non-local KS Hamiltonian within TDDFT. Comparing our new results against a representative set of accurate experimental measurements (ambient aluminum, silicon and carbon, as well as heated and compressed aluminum) reveals a dramatic improvement in all cases without any additional computational cost. The corresponding extension to the open-source GPAW code is made freely available online. We further investigate the implications of non-local pseudopotentials and show that the non-locality has an important, physically motivated effect that is indispensable to capture the correct plasmon dispersion in lieu of full all-electron simulations. In addition to being important for the estimation of a plethora of dynamic and spectral properties, our work constitutes an important step towards a universal XC functional that can be used to estimate all kinds of observables with high accuracy. Finally, we outline the potential utility of our framework for the development of advanced non-local XC functionals, and suggest a new way to rigorously verify non-local pseudopotentials against experimental measurements of collective excitations.
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BibTeX
@misc{moldabekov2026nonempirical,
title = {{Nonempirical Time-Dependent Density Functional Theory Framework for Nonlocal Exchange--Correlation Potentials}},
author = {Zhandos A. Moldabekov and Michele Pavanello and Thomas D. Gawne and Jan Vorberger and Tobias Dornheim},
howpublished = {arXiv},
year = {2026},
month = sep,
doi = {10.48550/arxiv.2609.18584},
eprint = {2609.18584},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2609.18584},
}
RIS
TY - UNPB
TI - Nonempirical Time-Dependent Density Functional Theory Framework for Nonlocal Exchange--Correlation Potentials
AU - Zhandos A. Moldabekov
AU - Michele Pavanello
AU - Thomas D. Gawne
AU - Jan Vorberger
AU - Tobias Dornheim
PY - 2026
DA - 2026/09/16
PB - arXiv
DO - 10.48550/arxiv.2609.18584
UR - https://arxiv.org/abs/2609.18584
AB - Advanced, orbital-dependent exchange--correlation (XC) functionals can significantly improve the description of electronic structural properties, but they substantially worsen spectral properties that are computed within standard linear-response time-dependent density functional theory frameworks. This is not a failure of the underlying Kohn-Sham states, but due to a formal inconsistency in the treatment of the dynamic density response when the non-locality of the XC potential is not taken into account consistently on the level of the full off-diagonal density matrix. To avoid these complexities, we present a non-empirical additive correction Δf_textnormalxc(q,ω) to the dynamic XC kernel that re-enforces the exact f-sum rule of the non-local KS Hamiltonian within TDDFT. Comparing our new results against a representative set of accurate experimental measurements (ambient aluminum, silicon and carbon, as well as heated and compressed aluminum) reveals a dramatic improvement in all cases without any additional computational cost. The corresponding extension to the open-source GPAW code is made freely available online. We further investigate the implications of non-local pseudopotentials and show that the non-locality has an important, physically motivated effect that is indispensable to capture the correct plasmon dispersion in lieu of full all-electron simulations. In addition to being important for the estimation of a plethora of dynamic and spectral properties, our work constitutes an important step towards a universal XC functional that can be used to estimate all kinds of observables with high accuracy. Finally, we outline the potential utility of our framework for the development of advanced non-local XC functionals, and suggest a new way to rigorously verify non-local pseudopotentials against experimental measurements of collective excitations.
ER -