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First principles correction scheme for linear-response time-dependent density functional theory calculations of core electronic states

Augustin Bussy1*, Jürg Hutter1*

1 Department of Chemistry, University of Zurich, CH-8057 Zürich, Switzerland

* Corresponding authors emails:,
DOI10.24435/materialscloud:1e-b4 [version v1]

Publication date: Jun 01, 2021

How to cite this record

Augustin Bussy, Jürg Hutter, First principles correction scheme for linear-response time-dependent density functional theory calculations of core electronic states, Materials Cloud Archive 2021.82 (2021), doi: 10.24435/materialscloud:1e-b4.


Linear-response time-dependent density functional theory (LR-TDDFT) for core level spectroscopy using standard local functionals suffers from self-interaction error and a lack of orbital relaxation upon creation of the core hole. As a result, LR-TDDFT calculated X-ray absorption near edge structure (XANES) spectra need to be shifted along the energy axis to match experimental data. We propose a correction scheme based on many body perturbation theory to calculate the shift from first principles. The ionization potential of the core donor state is first computed and then substituted for the corresponding Kohn--Sham orbital energy, thus emulating Koopmans' condition. Both self-interaction error and orbital relaxation are taken into account. The method exploits the localized nature of core states for efficiency and integrates seamlessly in our previous implementation of core level LR-TDDFT, yielding corrected spectra in a single calculation. We benchmark the correction scheme on molecules at the K- and L-edges as well as for core binding energies and report accuracies comparable to higher order methods. We also demonstrate applicability in large and extended systems and discuss efficient approximations.

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External references

Preprint (Paper in which the method is described and the data discussed)


MARVEL/DD4 TDDFT XAS first principles

Version history:

2021.120 (version v2) Jul 28, 2021 DOI10.24435/materialscloud:r8-tj
2021.82 (version v1) [This version] Jun 01, 2021 DOI10.24435/materialscloud:1e-b4