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Rotationally averaged linear absorption spectra beyond the electric-dipole approximation
Linköpings universitet, Institutionen för fysik, kemi och biologi. Linköpings universitet, Tekniska fakulteten.
University of Toulouse III Paul Sabatier, France.
Linköpings universitet, Institutionen för fysik, kemi och biologi, Teoretisk kemi. Linköpings universitet, Tekniska fakulteten.
2017 (engelsk)Inngår i: Molecular Physics, ISSN 0026-8976, E-ISSN 1362-3028, Vol. 115, nr 1-2, s. 63-74Artikkel i tidsskrift (Fagfellevurdert) Published
Abstract [en]

Based on the recently developed implementation of the full semi-classical field-matter interaction operator, we present a numerically accurate yet efficient scheme to perform rotational averaging of linear absorption spectra beyond the electric-dipole approximation. This allows for a gauge-origin independent determination of UV/vis and X-ray absorption spectra for randomly oriented systems such as multilayers, liquids, and gas phase samples. The approach is illustrated by the determination of spectral intensities of electric-dipole allowed pi -amp;gt; pi* transitions and electric-dipole forbidden n -amp;gt;pi* transitions in the UV-vis region of the spectrum as well as electric-dipole forbidden 1s. 3d transitions in the X-ray region of the spectrum. The employed Lebedev quadrature scheme shows very fast convergence with respect to the number of symmetry-independent quadrature points-in all considered cases, the oscillator strengths for the randomly oriented systems are fully converged with use of only seven quadrature points. [GRAPHICS]

sted, utgiver, år, opplag, sider
TAYLOR & FRANCIS LTD , 2017. Vol. 115, nr 1-2, s. 63-74
Emneord [en]
Response theory; multipole-expansion free; rotational averaging; Lebedev quadrature; X-ray absorption
HSV kategori
Identifikatorer
URN: urn:nbn:se:liu:diva-136373DOI: 10.1080/00268976.2016.1187773ISI: 000396794700008OAI: oai:DiVA.org:liu-136373DiVA, id: diva2:1087793
Merknad

Funding Agencies|Carlsberg Foundation [CF15-0792]; Knut and Alice Wallenberg Foundation [KAW-2013.0020]; Swedish Research Council [621-2014-4646]; Swedish National Infrastructure for Computing (SNIC), National Supercomputer Centre (NSC)

Tilgjengelig fra: 2017-04-10 Laget: 2017-04-10 Sist oppdatert: 2018-03-27

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