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Anomalous polarization dependence in vibrationally resolved RIXS of H2O
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Theoretical Chemistry and Biology. KTH.
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Theoretical Chemistry and Biology.
KTH, School of Engineering Sciences in Chemistry, Biotechnology and Health (CBH), Theoretical Chemistry and Biology.
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(English)Manuscript (preprint) (Other academic)
Abstract [en]

It is well established that different electronic channels, in resonant inelastic X-ray scattering (RIXS), display different polarization dependences due to different orientations of their corresponding transition dipole moments in the molecular frame. However, this effect does not influence the vibrational progression in the Franck-Condon approximation. We have found that the transition dipole moments of core-excitation and de-excitation experience ultrafast rotation during the dissociation in intermediate core-excited state. This rotations makes the vibrational progression in RIXS spectra sensitive to the polarisation of the X-ray photons. The studied effect is exemplified for the RIXS of the water molecule through the dissociative core-excited state where the vibrational scattering anisotropy is accompanied also by violation of parity selection rules for vibrations.

National Category
Physical Sciences Atom and Molecular Physics and Optics Theoretical Chemistry
Identifiers
URN: urn:nbn:se:kth:diva-227947OAI: oai:DiVA.org:kth-227947DiVA, id: diva2:1205775
Note

QC 20180515

Available from: 2018-05-15 Created: 2018-05-15 Last updated: 2018-05-15Bibliographically approved
In thesis
1. Quantum Nuclear Dynamics in Resonant X-ray Scattering of Gas-Phase and Liquid Systems
Open this publication in new window or tab >>Quantum Nuclear Dynamics in Resonant X-ray Scattering of Gas-Phase and Liquid Systems
2018 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

This thesis focuses on the role of the nuclear degrees of freedom in X-ray induced molecular processes. An important part of it is devoted to establishing theoretical principles to model and interpret high-resolution resonant X-ray scattering experiments in gases and liquids. Our investigations address the resonant inelastic x-ray scattering (RIXS) of H2O(g), H2O(l) and CH3OH(g) and Auger emission induced by hard X-rays in CO(g). The simulations for gas-phase systems are based on a multi-mode wave packet formalism and on potential energy surfaces computed with multi-configurational approaches.

For liquid systems, we propose a classical/quantum formalism for simulating RIXS based on a combination of ab initio molecular dynamics, density functional theory calculations and quantum nuclear wave packet propagation. The developed model is able to reproduce the experimental observation of shortening of the vibrational progression in H2O(l).

We show that electronically-elastic RIXS has an intrinsic capability to map the potential energy surface and to carry out vibrational analysis of the electronic ground state in free molecules as well as liquids. For gas-phase water, we see that the landscape of different core-excited states cause the nuclear wave packet to be localized along specific directions thus allowing to reconstruct one-dimensional potential energy curves. For liquid water, we propose a model for deriving, from experiment, confidence intervals for the molecular potential energy curves along the OH bonds, which are determined by the local arrangement of the hydrogen bond network.

We also investigate the role of ultra-fast rotations induced by photoionization by hard X-rays. In this case, the ejection of a fast photoelectron results in an ultra-fast rotational motion of the molecule, which combined with the anisotropy of the Auger process causes the spectral profile to be split due to a dynamical Doppler effect.

Place, publisher, year, edition, pages
Stockholm: KTH Royal Institute of Technology, 2018. p. 88
Series
TRITA-CBH-FOU ; 2018:24
Keywords
resonant inelastic X-ray scattering, X-ray absorption, water, methanol, CO, rotational doppler effect, recoil, wave packet, non-Franck-Condon effect, ultra-fast molecular dissociation, potential energy surface, hydrogen bond, liquid
National Category
Theoretical Chemistry Physical Sciences Atom and Molecular Physics and Optics
Research subject
Theoretical Chemistry and Biology
Identifiers
urn:nbn:se:kth:diva-227962 (URN)978-91-7729-806-9 (ISBN)
Public defence
2018-06-12, FA32, AlbaNova University Center, Roslagstullsbacken 21, Stockholm, 10:00 (English)
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Note

QC 20180515

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

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