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Photoelectron Spectroscopy of Molecules Beyond the Electric Dipole Approximation
Department of Theoretical Chemistry and Biology, KTH Royal Institute of Technology, Stockholm, Sweden; Department of Chemistry, Korea Advanced Institute of Science and Technology, Daejeon, Korea.
Örebro University, School of Science and Technology. Department of Physics and Astronomy, Uppsala University, Uppsala, Sweden.
Department of Theoretical Chemistry and Biology, KTH Royal Institute of Technology, Stockholm, Sweden.
2019 (English)In: Journal of Chemical Theory and Computation, ISSN 1549-9618, E-ISSN 1549-9626, Vol. 15, no 10, p. 5483-5494Article in journal (Refereed) Published
Abstract [en]

A methodology implemented to compute photoionization cross sections beyond the electric dipole approximation using Gaussian type orbitals for the initial state and plane waves for the final state is applied to molecules of various sizes. The molecular photoionization cross sections computed for valence molecular orbitals as a function of photon energy present oscillations due to the wave-like nature of both the outgoing photoelectron and of the incoming photon. These oscillations are damped by rotational and vibrational averaging or by performing a k-point summation for the solid state case. For core orbitals, the corrections introduced by going beyond the electric dipole approximation are comparable to the atomic case. For valence orbitals, nondipole corrections to the total photoinization cross sections can reach up to 20% at photon energies above 1 keV. The corrections to the differential cross sections calculated at the magic angle are larger, reaching values between 30% and 50% for all molecules included. Our findings demonstrate that photoelectron spectroscopy, especially angle-resolved, on, e.g., molecules and clusters on surfaces, using high photon energies, must be accompanied by theories that go beyond the electric dipole approximation.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2019. Vol. 15, no 10, p. 5483-5494
National Category
Theoretical Chemistry
Identifiers
URN: urn:nbn:se:oru:diva-76832DOI: 10.1021/acs.jctc.9b00470ISI: 000489678700028PubMedID: 31509709Scopus ID: 2-s2.0-85072975282OAI: oai:DiVA.org:oru-76832DiVA, id: diva2:1355556
Funder
Knut and Alice Wallenberg Foundation, KAW-2013.0020Swedish Research Council, 621-2014-4646 2017-06419eSSENCE - An eScience CollaborationAvailable from: 2019-09-30 Created: 2019-09-30 Last updated: 2019-10-25Bibliographically approved

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Eriksson, Olle

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