Simulating X-ray emission spectroscopy with algebraic diagrammatic construction schemes for the polarization propagator

• Verfasst von: Fransson, Thomas [VerfasserIn]
• Verfasst von: Dreuw, Andreas [VerfasserIn]
• Titel: Simulating X-ray emission spectroscopy with algebraic diagrammatic construction schemes for the polarization propagator
• Verf.angabe: Thomas Fransson and Andreas Dreuw
• Jahr: 2019
• Jahr des Originals: 2018
• Umfang: 11 S.
• Fussnoten: Published: November 27, 2018 ; Gesehen am 23.07.2019
• Titel Quelle: Enthalten in: Journal of chemical theory and computation
• Ort Quelle: Washington, DC, 2004
• Jahr Quelle: 2019
• Band/Heft Quelle: 15(2019), 1, Seite 546-556
• ISSN Quelle: 1549-9626
• DOI: doi:10.1021/acs.jctc.8b01046
• Datenträger: Online-Ressource
• Sprache: eng
• K10plus-PPN: 1669610977

Abstract

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.