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Selective gating to vibrational modes through resonant X-ray scattering
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology. (Theoretical Chemistry and Biology)ORCID iD: 0000-0003-4020-0923
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology. (Theoretical Chemistry and Biology)
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2017 (English)In: Nature Communications, ISSN 2041-1723, E-ISSN 2041-1723, Vol. 8, 14165-1-14165-7 p.Article in journal, Letter (Refereed) Published
Abstract [en]

The dynamics of fragmentation and vibration of molecular systems with a large number of coupled degrees of freedom are key aspects for understanding chemical reactivity and properties. Here we present a resonant inelastic X-ray scattering (RIXS) study to show how it is possible to break down such a complex multidimensional problem into elementary components. Local multimode nuclear wave packets created by X-ray excitation to different core-excited potential energy surfaces (PESs) will act as spatial gates to selectively probe the particular ground-state vibrational modes and, hence, the PES along these modes. We demonstrate this principle by combining ultra-high resolution RIXS measurements for gas-phase water with state-of-the-art simulations.

Place, publisher, year, edition, pages
Macmillan Publishers Ltd., 2017. Vol. 8, 14165-1-14165-7 p.
Keyword [en]
water, resonant inelastic x-ray scattering, vibrational modes, RIXS
National Category
Atom and Molecular Physics and Optics Theoretical Chemistry
Research subject
Theoretical Chemistry and Biology
Identifiers
URN: urn:nbn:se:kth:diva-187011DOI: 10.1038/ncomms14165ISI: 000392541700001Scopus ID: 2-s2.0-85009990586OAI: oai:DiVA.org:kth-187011DiVA: diva2:928528
Funder
Knut and Alice Wallenberg Foundation, KAW-2013.0020Carl Tryggers foundation , CTS 15:266Carl Tryggers foundation , CTS 14:355Swedish Research Council, C0334701Swedish Research Council, 2015-03781Swedish Research Council, 2015-03956Swedish Research Council, 2015-04510EU, Horizon 2020, 669531 EDAX
Note

QC 20170123

Available from: 2016-05-16 Created: 2016-05-16 Last updated: 2017-03-09Bibliographically approved
In thesis
1. Coupled electron-nuclear dynamics in inelastic X-ray scattering
Open this publication in new window or tab >>Coupled electron-nuclear dynamics in inelastic X-ray scattering
2016 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This Thesis is devoted to theoretical and experimental studies of resonant inelastic X-ray scattering (RIXS) of carbon monoxide and water molecules. Using state-of-the-art ab initio electronic structure calculations and a time-dependent wave packet formalism, we make a complete analysis of the experimental RIXS spectra of the two molecular systems. In the CO RIXS analysis, we are able to reproduce the RIXS experiment with an excellent accuracy. Interference between different RIXS channels corresponding to the scattering via orthogonal molecular orbitals in the core-excited state of CO is described. We show the complete breakdown of the Born-Oppenheimer approximation in the region where forbidden final Rydberg states are mixed with a valence allowed final state. Here we explain the formation of a spectral feature which was attributed to a single state in previous studies. Moreover, through an experimental-theoretical combination, we improve the minimum of the valence E’Π excited state potential, along with the coupling constant between two Rydberg states. We developed a new theoretical approach to describe triatomic molecules through the wave packet propagation formalism to study the water system, which reproduces with high accuracy the vibrational structure of the high-resolution experimental quasi-elastic RIXS spectra. We demonstrate that due to the vibrational mode coupling and anharmonicity of the ground and core-excited potential energy surfaces, different core-excited states in RIXS can be used as gates to probe different vibrational dynamics and to map the ground state potential. Isotopic substitution is investigated by theoretical simulations and important dynamical features are discussed, especially for the dissociative core-excited state, where a so-called “atomic” peak is formed. We show the strong potential of high-resolution RIXS experiments combined with high-level theoretical simulations for advanced studies of highly excited molecular states.

Place, publisher, year, edition, pages
Stockholm, Sweden: KTH Royal Institute of Technology, 2016. 87 p.
Series
TRITA-BIO-Report, ISSN 1654-2312 ; 2016:10
Keyword
X-ray spectroscopy, resonant inelastic X-ray scattering, water, carbon monoxide
National Category
Theoretical Chemistry
Research subject
Theoretical Chemistry and Biology
Identifiers
urn:nbn:se:kth:diva-186530 (URN)978-91-7595-988-7 (ISBN)
Public defence
2016-06-08, FB53, AlbaNova University Center, Roslagstullsbacken 21, Stockholm, 10:00 (English)
Opponent
Supervisors
Funder
Knut and Alice Wallenberg Foundation, KAW-2013.0020
Note

QC 20160516

Available from: 2016-05-16 Created: 2016-05-12 Last updated: 2016-05-16Bibliographically approved

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