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Infrared-pump–x-ray-probe spectroscopy of vibrationally excited molecules
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.
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.ORCID iD: 0000-0003-4020-0923
Stockholm university.
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2017 (English)In: Physical Review A, ISSN 2469-9926, Vol. 95, no 4, article id 042502Article in journal (Refereed) Published
Abstract [en]

We develop a theory of infrared (IR)-pump–x-ray-probe spectroscopy for molecular studies. We illustrate advantages of the proposed scheme by means of numerical simulations employing a vibrational wave packet technique applied to x-ray absorption and resonant inelastic x-ray scattering (RIXS) spectra of the water molecule vibrationally excited by a preceding IR field. The promotion of the vibrationally excited molecule to the dissociative 1a−114a1 and bound 1a−112b2 core-excited states with qualitatively different shapes of the potential energy surfaces creates nuclear wave packets localized along and between the OH bonds, respectively. The projection of these wave packets on the final vibrational states, governed by selection and propensity rules, results in spatial selectivity of RIXS sensitive to the initial vibrationally excited state, which makes it possible to probe selectively the ground state properties along different modes. In addition, we propose to use RIXS as a tool to study x-ray absorption from a selected vibrational level of the ground state when the spectral resolution is sufficiently high to resolve vibrational overtones. The proposed technique has potential applications for advanced mapping of multidimensional potential energy surfaces of ground and core-excited molecular states, for symmetry-resolved spectroscopy, and for steering chemical reactions.

Place, publisher, year, edition, pages
2017. Vol. 95, no 4, article id 042502
National Category
Atom and Molecular Physics and Optics
Research subject
Physics
Identifiers
URN: urn:nbn:se:kth:diva-207761DOI: 10.1103/PhysRevA.95.042502ISI: 000399378800004Scopus ID: 2-s2.0-85017294332OAI: oai:DiVA.org:kth-207761DiVA, id: diva2:1098032
Funder
Knut and Alice Wallenberg Foundation, KAW-2013.0020Carl Tryggers foundation Swedish Research Council
Note

QC 20170602

Available from: 2017-05-23 Created: 2017-05-23 Last updated: 2018-05-15Bibliographically 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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