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Calibrating TDDFT Calculations of the X-ray Emission Spectrum of Liquid Water: The Effects of Hartree-Fock Exchange
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: 22023 (English)In: Journal of Chemical Theory and Computation, ISSN 1549-9618, E-ISSN 1549-9626, Vol. 19, no 20, p. 7333-7342Article in journal (Refereed) Published
Abstract [en]

The structure and dynamics of liquid water continue to be debated, with insight provided by, among others, X-ray emission spectroscopy (XES), which shows a split in the high-energy 1b1 feature. This split is yet to be reproduced by theory, and it remains unclear if these difficulties are related to inaccuracies in dynamics simulations, spectrum calculations, or both. We investigate the performance of different methods for calculating XES of liquid water, focusing on the ability of time-dependent density functional theory (TDDFT) to reproduce reference spectra obtained by high-level coupled cluster and algebraic-diagrammatic construction scheme calculations. A metric for evaluating the agreement between theoretical spectra termed the integrated absolute difference (IAD), which considers the integral of shifted difference spectra, is introduced and used to investigate the performance of different exchange-correlation functionals. We find that computed spectra of symmetric and asymmetric model water structures are strongly and differently influenced by the amount of Hartree-Fock exchange, with best agreement to reference spectra for similar to 40-50%. Lower percentages tend to yield high density of contributing states, resulting in too broad features. The method introduced here is useful also for other spectrum calculations, in particular where the performance for ensembles of structures are evaluated.

Place, publisher, year, edition, pages
2023. Vol. 19, no 20, p. 7333-7342
Keywords [en]
Chemical calculations, Cluster chemistry, Energy, Time dependant density functional theory, Water
National Category
Theoretical Chemistry Atom and Molecular Physics and Optics
Identifiers
URN: urn:nbn:se:su:diva-223185DOI: 10.1021/acs.jctc.3c00728ISI: 001077682700001PubMedID: 37787584Scopus ID: 2-s2.0-85175356674OAI: oai:DiVA.org:su-223185DiVA, id: diva2:1807193
Available from: 2023-10-25 Created: 2023-10-25 Last updated: 2024-10-16Bibliographically approved

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Fransson, ThomasPettersson, Lars G. M.

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