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Gradual collapse of nuclear wave functions regulated by frequency tuned X-ray scattering
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Theoretical Chemistry and Biology. Siberian Federal University.ORCID iD: 0000-0003-3754-6763
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.ORCID iD: 0000-0003-4020-0923
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2017 (English)In: Scientific Reports, ISSN 2045-2322, E-ISSN 2045-2322, Vol. 7, no 43891Article in journal (Refereed) Published
Abstract [en]

As is well established, the symmetry breaking by isotope substitution in the water molecule results in localisation of the vibrations along one of the two bonds in the ground state. In this study we find that this localisation may be broken in excited electronic states. Contrary to the ground state, the stretching vibrations of HDO are delocalised in the bound core-excited state in spite of the mass difference between hydrogen and deuterium. The reason for this effect can be traced to the narrow “canyon-like” shape of the potential of the state along the symmetric stretching mode, which dominates over the localisation mass-difference effect. In contrast, the localisation of nuclear motion to one of the HDO bonds is preserved in the dissociative core-excited state . The dynamics of the delocalisation of nuclear motion in these core-excited states is studied using resonant inelastic X-ray scattering of the vibrationally excited HDO molecule. The results shed light on the process of a wave function collapse. After core-excitation into the state of HDO the initial wave packet collapses gradually, rather than instantaneously, to a single vibrational eigenstate.

Place, publisher, year, edition, pages
London: Nature Publishing Group, 2017. Vol. 7, no 43891
Keywords [en]
Atomic and molecular interactions with photons
National Category
Natural Sciences
Research subject
Physics
Identifiers
URN: urn:nbn:se:kth:diva-204921DOI: 10.1038/srep43891ISI: 000395655000001PubMedID: 28266586Scopus ID: 2-s2.0-85014777715OAI: oai:DiVA.org:kth-204921DiVA, id: diva2:1086880
Funder
Swedish Research CouncilCarl Tryggers foundation Knut and Alice Wallenberg Foundation, 2013.0020
Note

QC 20170419

Available from: 2017-04-04 Created: 2017-04-04 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
Supervisors
Note

QC 20180516

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

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