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Setting the stage for theoretical x-ray spectra of the H2S molecule with multi-configurational quantum chemical calculations of the energy landscape
Stockholm University, Faculty of Science, Department of Physics.
Stockholm University, Faculty of Science, Department of Physics.ORCID iD: 0000-0002-7023-2486
Number of Authors: 42020 (English)In: Journal of Chemical Physics, ISSN 0021-9606, E-ISSN 1089-7690, Vol. 152, no 9, article id 094305Article in journal (Refereed) Published
Abstract [en]

In the H2S molecule, the interplay between different core levels can be investigated in great detail in relation to x-ray spectroscopy, which requires a theory for interpretation. Hence, valence and core excitations into the two antibonding molecular orbitals of the H2S molecule have been calculated within a multi-configurational wave function framework. Scanning along the S-H stretching coordinates, we derive potential energy surfaces and transition dipole moments involving the ground state and core and valence excited states. Both valence excitations and the S1s(-1) and S2p(-1) core excitations show pairs of dissociative and bound electronic states. These pairs of states are nearly degenerate in H2S at the ground state geometry. The close degeneracy together with conical intersections makes H2S an interesting target for x-ray spectroscopy involving ultra-fast dissociation influenced by non-adiabatic transitions and interference. For future investigations with x-ray absorption spectroscopy (XAS) and resonant inelastic x-ray scattering (RIXS), it is valuable to compare H2S with the water molecule, which exhibits state-selective gating to different vibrational modes [R. C. Couto et al., Nat. Commun. 8, 14165 (2017)] in its well-separated O1s(-1) core excited states. The dense manifolds of the S2p(-1) core excited states will complicate the analysis of K-alpha edge RIXS, but dynamical effects could be evaluated through detuning and by comparing with L edge XAS. In L edge RIXS, the dynamical effects will be more pronounced due to the longer lifetime of the S2p(-1) core excited states compared to the S1s(-1) core excited states.

Place, publisher, year, edition, pages
2020. Vol. 152, no 9, article id 094305
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Chemical Sciences Physical Sciences
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URN: urn:nbn:se:su:diva-181191DOI: 10.1063/1.5145139ISI: 000519569400002PubMedID: 33480721Scopus ID: 2-s2.0-85081237174OAI: oai:DiVA.org:su-181191DiVA, id: diva2:1427777
Available from: 2020-05-01 Created: 2020-05-01 Last updated: 2022-11-10Bibliographically approved

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Lundberg, MarcusOdelius, Michael

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