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XABOOM: An X-ray Absorption Benchmark of Organic Molecules Based on Carbon, Nitrogen, and Oxygen 1s -> π* Transitions
Stockholm University, Faculty of Science, Department of Physics. Ruprecht-Karls University, Germany.ORCID iD: 0000-0002-3770-9780
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Number of Authors: 62021 (English)In: Journal of Chemical Theory and Computation, ISSN 1549-9618, E-ISSN 1549-9626, Vol. 17, no 3, p. 1618-1637Article in journal (Refereed) Published
Abstract [en]

The performance of several standard and popular approaches for calculating X-ray absorption spectra at the carbon, nitrogen, and oxygen K-edges of 40 primarily organic molecules up to the size of guanine has been evaluated, focusing on the low-energy and intense 1s -> pi* transitions. Using results obtained with CVS-ADC(2)-x and fc-CVS-EOM-CCSD as benchmark references, we investigate the performance of CC2, ADC(2), ADC(3/2), and commonly adopted density functional theory (DFT)-based approaches. Here, focus is on precision rather than on accuracy of transition energies and intensities-in other words, we target relative energies and intensities and the spread thereof, rather than absolute values. The use of exchange-correlation functionals tailored for time-dependent DFT calculations of core excitations leads to error spreads similar to those seen for more standard functionals, despite yielding superior absolute energies. Long-range corrected functionals are shown to perform particularly well compared to our reference data, showing error spreads in energy and intensity of 0.2-0.3 eV and similar to 10%, respectively, as compared to 0.3-0.6 eV and similar to 20% for a typical pure hybrid. In comparing intensities, state mixing can complicate matters, and techniques to avoid this issue are discussed. Furthermore, the influence of basis sets in high-level ab initio calculations is investigated, showing that reasonably accurate results are obtained with the use of 6-311++G**. We name this benchmark suite as XABOOM (X-ray absorption benchmark of organic molecules) and provide molecular structures and ground-state self-consistent field energies and spectroscopic data. We believe that it provides a good assessment of electronic structure theory methods for calculating X-ray absorption spectra and will become useful for future developments in this field.

Place, publisher, year, edition, pages
2021. Vol. 17, no 3, p. 1618-1637
Keywords [en]
Light absorption, Oxygen, Energy, Basis sets, Phase transitions, Order
National Category
Chemical Sciences Physical Sciences
Identifiers
URN: urn:nbn:se:su:diva-193367DOI: 10.1021/acs.jctc.0c01082ISI: 000629135700027PubMedID: 33544612OAI: oai:DiVA.org:su-193367DiVA, id: diva2:1557612
Available from: 2021-05-26 Created: 2021-05-26 Last updated: 2022-03-23Bibliographically approved

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Fransson, ThomasBrumboiu, Iulia E.Coriani, Sonia

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