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Applications to metal K pre-edges of transitionmetal dimers illustrate the approximate origin independence for the intensities in the length representation
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Theoretical Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Theoretical Chemistry.
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Theoretical Chemistry.ORCID iD: 0000-0001-7567-8295
Uppsala University, Disciplinary Domain of Science and Technology, Chemistry, Department of Chemistry - Ångström, Theoretical Chemistry.ORCID iD: 0000-0002-1312-1202
2017 (English)In: Molecular Physics, ISSN 0026-8976, E-ISSN 1362-3028, Vol. 115, no 1-2, 174-189 p.Article in journal (Refereed) Published
Abstract [en]

X-ray absorption spectroscopy (XAS) in the metal K pre-edge is a standard probe of electronic and geometric structure of transition metal complexes. Simulating the K pre-edge spectra requires contributions beyond the electric dipole, but if that term is non-zero, the second-order terms, e. g. electric quadrupoles, are no longer origin-independent. In the velocity representation, complete origin independence can be achieved by including all terms to the same order in the oscillator strength. Here, we implement that approach in the length representation and use it for restricted active space (RAS) simulations of metal K pre-edges of iron monomers and dimers. Complete origin independence is not achieved and the size of the remaining errors depends on the electric dipole oscillator strength and its ratio in length and velocity representations. The error in the origin independence is in the ANO basis sets two orders of magnitude smaller than the value of the individual contributions. For systemswith strong electric dipole contributions, the errors are not significant within 3 angstrom from a metal centre, far enough to handlemany multi-metal systems. Furthermore, we discuss the convergence of the multipole expansion, the possibility to assign spectral contributions, and the origin of negative absorption intensities. [GRAPHICS]

Place, publisher, year, edition, pages
TAYLOR & FRANCIS LTD , 2017. Vol. 115, no 1-2, 174-189 p.
Keyword [en]
Multiconfigurational wavefunction, oscillator strengths, quadrupole intensities, properties, X-ray spectroscopy
National Category
Physical Chemistry
Identifiers
URN: urn:nbn:se:uu:diva-319774DOI: 10.1080/00268976.2016.1225993ISI: 000396794700015OAI: oai:DiVA.org:uu-319774DiVA: diva2:1088315
Funder
Knut and Alice Wallenberg Foundation, KAW-2013.0020Swedish Research Council, 2012-3910 2012-3924
Available from: 2017-04-12 Created: 2017-04-12 Last updated: 2017-04-12Bibliographically approved

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