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Coupled electron-nuclear dynamics in resonant 1 sigma -> 2 pi x-ray Raman scattering of CO molecules
Royal Inst Technol, Sch Biotechnol, Theoret Chem & Biol, SE-10691 Stockholm, Sweden.;Univ Fed Goias, Inst Quim, Campus Samambaia,CP 131, BR-74001970 Goiania, Go, Brazil..
Lab Nacl Luz Sincrotron, BR-10000 Campinas, SP, Brazil.;Univ Paris 06, Univ Paris 04, UMR7614, Lab Chim Phys Mat & Rayonnement, F-75005 Paris, France..
Synchrotron SOLEIL, Boite Postale 48, F-91192 Gif Sur Yvette, France..
Synchrotron SOLEIL, Boite Postale 48, F-91192 Gif Sur Yvette, France..
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2016 (English)In: PHYSICAL REVIEW A, ISSN 2469-9926, Vol. 93, no 3, 032510Article in journal (Refereed) PublishedText
Abstract [en]

We present a detailed experimental-theoretical analysis of O K-edge resonant 1 sigma-2 pi inelastic x-ray scattering (RIXS) from carbon monoxide with unprecedented energy resolution. We employ high-level ab initio calculations to compute the potential energy curves of the states involved in the RIXS process and simulate the measured RIXS spectra using the wave-packet-propagation formalism, including Coulomb coupling in the final-state manifold. The theoretical analysis allows us to explain all the key features of the experimental spectra, including some that were not seen before. First, we clearly show the interference effect between different RIXS channels corresponding to the transition via orthogonal (1)Pi(x) and (1)Pi(y) core-excited states of CO. Second, the RIXS region of 13 eV energy loss presents a triple structure, revealed only by the high-resolution measurement. In previous studies, this region was attributed solely to a valence state. Here we show a strong Coulomb mixing of the Rydberg and valence final states, which opens the forbidden RIXS channels to the "dark" final Rydberg states and drastically changes the RIXS profile. Third, using a combination of high-resolution experiment and high-level theory, we improve the vertical bar 4 sigma(-1)2 pi(1)> final-state potential-energy curve by fitting its bottom part with the experiment. Also, the coupling constants between Rydberg and valence states were refined via comparison with the experiment. Our results illustrate the large potential of the RIXS technique for advanced studies of highly excited states of neutral molecules.

Place, publisher, year, edition, pages
2016. Vol. 93, no 3, 032510
National Category
Atom and Molecular Physics and Optics
URN: urn:nbn:se:uu:diva-286660DOI: 10.1103/PhysRevA.93.032510ISI: 000372399100006OAI: oai:DiVA.org:uu-286660DiVA: diva2:923659
Swedish Research CouncilKnut and Alice Wallenberg Foundation
Available from: 2016-04-27 Created: 2016-04-21 Last updated: 2016-04-27Bibliographically approved

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Ekholm, VictorRubensson, Jan-Erik
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