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Simulating X-ray Emission Spectroscopy with Algebraic Diagrammatic Construction Schemes for the Polarization Propagator
Stockholms universitet, Naturvetenskapliga fakulteten, Fysikum. Ruprecht−Karls University, Germany.ORCID-id: 0000-0002-3770-9780
Rekke forfattare: 22019 (engelsk)Inngår i: Journal of Chemical Theory and Computation, ISSN 1549-9618, E-ISSN 1549-9626, Vol. 15, nr 1, s. 546-556Artikkel i tidsskrift (Fagfellevurdert) Published
Abstract [en]

The calculation of X-ray emission spectra has been addressed with the algebraic diagrammatic construction (ADC) scheme, using a core-ionized wave function as the reference state. With this, the valence-to-core transitions are found as the first eigenstates with negative eigenvalues. The performance of the ADC hierarchical methods ADC(2), ADC(2)-x, and ADC(3/2) has been investigated on 17 transition of second row elements (C, N, O, F, and Ne), and 5 transitions of third-row elements (S and Cl). We report ADC(2) results within 0.20 +/- 0.36 eV of experimental values with an appropriate choice of basis set and when accounting for relativistic effects, with a slight tendency toward underestimating emission energies. By comparison, ADC(2)-x yields a similar spread in relative energies, but a consistent overestimation of approximately 1.5 eV. Going to ADC(3/2), we now observe an underestimation of emission energies and a larger error spread. By comparison, calculations of X-ray absorption spectra have been reported to favor the ADC(2)-x method, with ADC(2) showing the largest error when comparing to experimental values. The difference in ADC performance trends between these core spectroscopies are attributed to the different electron rearrangement effects in X-ray absorption and emission processes.

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2019. Vol. 15, nr 1, s. 546-556
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URN: urn:nbn:se:su:diva-165703DOI: 10.1021/acs.jctc.8b01046ISI: 000455558200048PubMedID: 30481466Scopus ID: 2-s2.0-85059611825OAI: oai:DiVA.org:su-165703DiVA, id: diva2:1285575
Tilgjengelig fra: 2019-02-04 Laget: 2019-02-04 Sist oppdatert: 2022-11-03bibliografisk kontrollert

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