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TDDFT and the x-ray absorption spectrum of liquid water: Finding the “best” functional
Stockholm University, Faculty of Science, Department of Physics.ORCID iD: 0000-0002-3770-9780
Stockholm University, Faculty of Science, Department of Physics.ORCID iD: 0000-0003-1133-9934
Number of Authors: 22024 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 160, no 23, article id 234105Article in journal (Refereed) Published
Abstract [en]

We investigate the performance of time-dependent density functional theory (TDDFT) for reproducing high-level reference x-ray absorption spectra of liquid water and water clusters. For this, we apply the integrated absolute difference (IAD) metric, previously used for x-ray emission spectra of liquid water [T. Fransson and L. G. M. Pettersson, J. Chem. Theory Comput. 19, 7333-7342 (2023)], in order to investigate which exchange-correlation (xc) functionals yield TDDFT spectra in best agreement to reference, as well as to investigate the suitability of IAD for x-ray absorption spectroscopy spectrum calculations. Considering highly asymmetric and symmetric six-molecule clusters, it is seen that long-range corrected xc-functionals are required to yield good agreement with the reference coupled cluster (CC) and algebraic-diagrammatic construction spectra, with 100% asymptotic Hartree-Fock exchange resulting in the lowest IADs. The xc-functionals with best agreement to reference have been adopted for larger water clusters, yielding results in line with recently published CC theory, but which still show some discrepancies in the relative intensity of the features compared to experiment.

Place, publisher, year, edition, pages
2024. Vol. 160, no 23, article id 234105
National Category
Oceanography, Hydrology and Water Resources
Identifiers
URN: urn:nbn:se:su:diva-235508DOI: 10.1063/5.0209719ISI: 001254147600005PubMedID: 38884399Scopus ID: 2-s2.0-85196406543OAI: oai:DiVA.org:su-235508DiVA, id: diva2:1913594
Available from: 2024-11-15 Created: 2024-11-15 Last updated: 2025-10-03Bibliographically approved

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Fransson, ThomasPettersson, Lars Gunnar Moody

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