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Ultrafast dissociation features in RIXS spectra of the water molecule
Stockholm university. (Fysikum)ORCID iD: 0000-0002-4603-2097
Siberian Federal University. (Teoretisk kemi och biologi, Theoretical Chemistry and Biology)ORCID iD: 0000-0002-4792-9525
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology. Siberian Federal University.ORCID iD: 0000-0003-3754-6763
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.ORCID iD: 0000-0001-9696-2498
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2018 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084Article in journal (Refereed) Published
Abstract [en]

In this combined theoretical and experimental study we report on an analysis of the resonant inelastic X-ray scattering spectra (RIXS) of gas phase water via the lowest dissociative core-excited state |1sO-14a11〉. We focus on the spectral feature near the dissociation limit of the electronic ground state. We show that the narrow atomic-like peak consists of the overlapping contribution from the RIXS channels back to the ground state and to the first valence excited state |1b1-14a11〉 of the molecule. The spectral feature has signatures of ultrafast dissociation (UFD) in the core-excited state, as we show by means of ab initio calculations and time-dependent nuclear wave packet simulations. We show that the electronically elastic RIXS channel gives substantial contribution to the atomic-like resonance due to the strong bond length dependence of the magnitude and orientation of the transition dipole moment. By studying the RIXS for an excitation energy scan over the core-excited state resonance, we can understand and single out the molecular and atomic-like contributions in the decay to the lowest valence-excited state. Our study is complemented by a theoretical discussion of RIXS in the case of the isotope substituted water (HDO and D2O) where the nuclear dynamics is significantly affected by the heavier fragments' mass.

Place, publisher, year, edition, pages
2018.
Keywords [en]
resonant inelastic X-ray scattering, water molecule, Ultrafast dissociation, valence excited state, core-excited state
National Category
Atom and Molecular Physics and Optics
Research subject
Chemistry; Physics
Identifiers
URN: urn:nbn:se:kth:diva-227942DOI: 10.1039/C8CP01807COAI: oai:DiVA.org:kth-227942DiVA, id: diva2:1205806
Note

QC 20180516

Available from: 2018-05-15 Created: 2018-05-15 Last updated: 2018-05-16Bibliographically approved
In thesis
1. Multimode resonant X-ray scattering of free molecules
Open this publication in new window or tab >>Multimode resonant X-ray scattering of free molecules
2018 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis is focused on the role that nuclear dynamics plays in the formation of X-ray absorption (XAS) and resonant inelastic X-ray scattering (RIXS) spectra of multimode free molecules. A combined approach based on ab initio electronic structure methods and quantum nuclear wave packet dynamics is applied to two systems -- water and methanol in the gas phase. An IR-pump – X-ray-probe spectroscopy of vibrationally excited water and its isotope substitutions is employed to explore different vibrational progressions of the final electronic state due to a spatial filtration of the vibrations in the core-excited state and selection rules. It was demonstrated the possibility to use RIXS as a tool to study X-ray absorption from a selected vibrational level of the ground state. IR-pump – X-ray-probe spectroscopy applied to the HDO molecule sheds light on the old classical problem of wave function collapse: we demonstrate numerically the gradual collapse of the initially localised vibrational wave function in the HDO molecule. It is also explained the dynamical nature of the splitting of the 1b1 peak in the RIXS spectrum of H2O, HDO and D2O molecules. This splitting is referred to close-lying molecular and atomic-like peaks. In order to study the methanol molecule a special theoretical tool for studies of multimode molecules has been developed. This approach combines the advantages of the quantum wave packet technique for simulations of the dynamics in dissociative states with the efficiency of the Franck-Condon method for computing transitions between bound states. It is shown that the multimode nuclear dynamics plays an important role in XAS and RIXS spectra of methanol. The XAS and RIXS spectra formation was explained taking into account different dynamics in different core-excited potential energy surfaces, as well as the entanglement of vibrational modes by anharmonicity and by the life-time vibrational interference.

Place, publisher, year, edition, pages
Stockholm, Sweden: KTH Royal Institute of Technology, 2018. p. 73
Series
TRITA-CBH-FOU ; 2018:23
Keywords
X-ray absorption spectroscopy, core-excited state, nuclear dynamic, wave-packet, resonant inelastic X-ray scattering, Franck-Condon, water, methanol, water isotopomer, pump-probe, quantum chemistry, ultrafast dissociation
National Category
Atom and Molecular Physics and Optics
Research subject
Chemistry; Physics
Identifiers
urn:nbn:se:kth:diva-227971 (URN)978-91-7729-800-7 (ISBN)
Public defence
2018-06-11, FA32, Roslagstullsbacken 21, Stockholm, 10:00 (English)
Opponent
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Note

QC 20180516

Available from: 2018-05-16 Created: 2018-05-15 Last updated: 2018-05-16Bibliographically approved

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Publisher's full texthttp://dx.doi.org/10.1039/C8CP01807C

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