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Intramolecular soft modes and intermolecular interactions in liquid acetone
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology.
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2011 (English)In: Physical Review B. Condensed Matter and Materials Physics, ISSN 1098-0121, E-ISSN 1550-235X, Vol. 84, no 13, 132202- p.Article in journal (Refereed) Published
Abstract [en]

Resonant inelastic x-ray scattering spectra excited at the O1s(-1)pi* resonance of liquid acetone are presented. Scattering to the electronic ground state shows a resolved vibrational progression where the dominant contribution is due to the C-O stretching mode, thus demonstrating a unique sensitivity of the method to the local potential energy surface in complex molecular systems. For scattering to electronically excited states, soft vibrational modes and, to a smaller extent, intermolecular interactions give a broadening, which blurs the vibrational fine structure. It is predicted that environmental broadening is dominant in aqueous acetone.

Place, publisher, year, edition, pages
2011. Vol. 84, no 13, 132202- p.
National Category
Physical Sciences
URN: urn:nbn:se:kth:diva-48513DOI: 10.1103/PhysRevB.84.132202ISI: 000296372300001ScopusID: 2-s2.0-80155152537OAI: diva2:458741
Swedish Research Council
QC 20111123 Uppdaterat från ManuskriptAvailable from: 2011-11-23 Created: 2011-11-21 Last updated: 2011-11-23Bibliographically approved
In thesis
1. Spontaneous and stimulated X-ray Raman scattering
Open this publication in new window or tab >>Spontaneous and stimulated X-ray Raman scattering
2011 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

The present thesis is devoted to theoretical studies of resonant X-ray scattering and propagation of strong X-ray pulses. In the first part of the thesis the nuclear dynamics of different molecules is studied using resonant X-ray Raman and resonant Auger scattering techniques. We show that the shortening of the scattering duration by the detuning results in a purification of the Raman spectra from overtones and soft vibrational modes. The simulations are in a good agreement with measurements, performed at the MAX-II and the Swiss Light Source with vibrational resolution. We explain why the scattering to the ground state nicely displays the vibrational structure of liquid acetone in contrast to excited final state. Theory of resonant X-ray scattering by liquids is developed. We show that, contrary to aqueous acetone, the environmental broadening in pure liquid acetone is twice smaller than the broadening by soft vibrational modes significantly populated at room temperature. Similar to acetone, the "elastic" band of X-ray Raman spectra of molecular oxygen is strongly affected by the Thomson scattering. The Raman spectrum demonstrates spatial quantum beats caused by two interfering wave packets with different momenta as the oxygen atoms separate. It is found that the vibrational scattering anisotropy caused by the interference of the "inelastic" Thomson and resonant scattering channels in O2. A new spin selection rule is established in inelastic X-ray Raman spectra of O2. It is shown that the breakdown of the symmetry selection rule based on the parity of the core hole, as the core hole and excited electron swap parity. Multimode calculations explain the two thresholds of formation of the resonant Auger spectra of the ethene molecule by the double-edge structure of absorption spectrum caused by the out-of- and in-plane modes. We predict the rotational Doppler effect and related broadening of X-ray photoelectron and resonant Auger spectra, which has the same magnitude as its counterpart-the translational Doppler effect. The second part of the thesis explores the interaction of the medium with strong X-ray free-electron laser (XFEL) fields. We perform simulations of nonlinear propagation of femtosecond XFEL pulses in atomic vapors by solving coupled Maxwell's and density matrix equations. We show that self-seeded stimulated X-ray Raman scattering strongly influences the temporal and spectral structure of the XFEL pulse. The generation of Stokes and four-wave mixing fields starts from the seed field created during pulse propagation due to the formation of extensive ringing pattern with long spectral tail. We demonstrate a compression into the attosecond region and a slowdown of the XFEL pulse up to two orders of magnitude. In the course of pulse propagation, the Auger yield is strongly suppressed due to the competitive channel of stimulated emission. We predict a strong X-ray fluorescence from the two-core-hole states of Ne created in the course of the two-photon X-ray absorption.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2011. viii, 71 p.
Trita-BIO-Report, ISSN 1654-2312 ; 2011:8
resonant X-ray scattering, resonant Auger scattering, rotational Doppler broadening, XFEL pulse
National Category
Atom and Molecular Physics and Optics Analytical Chemistry
urn:nbn:se:kth:diva-32859 (URN)978-91-7415-925-7 (ISBN)
Public defence
2011-05-13, FA32, AlbaNova, Stockholm, 10:00 (English)
QC 20110426Available from: 2011-04-26 Created: 2011-04-21 Last updated: 2011-11-23Bibliographically approved

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