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A study of the water molecule using frequency control over nuclear dynamics in resonant X-ray scattering
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology. (Theoretical chemistry and biology)
KTH, School of Biotechnology (BIO), Theoretical Chemistry and Biology. (Theoretical Chemistry and Biology)ORCID iD: 0000-0003-4020-0923
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2017 (English)In: Physical Chemistry, Chemical Physics - PCCP, ISSN 1463-9076, E-ISSN 1463-9084, Vol. 19, no 30, p. 19573-19589Article in journal (Refereed) Published
Abstract [en]

In this combined theoretical and experimental study we report a full analysis of the resonant inelastic X-ray scattering (RIXS) spectra of H2O, D2O and HDO. We demonstrate that electronically-elastic RIXS has an inherent capability to map the potential energy surface and to perform vibrational analysis of the electronic ground state in multimode systems. We show that the control and selection of vibrational excitation can be performed by tuning the X-ray frequency across core-excited molecular bands and that this is clearly reflected in the RIXS spectra. Using high level ab initio electronic structure and quantum nuclear wave packet calculations together with high resolution RIXS measurements, we discuss in detail the mode coupling, mode localization and anharmonicity in the studied systems.

Place, publisher, year, edition, pages
Royal Society of Chemistry, 2017. Vol. 19, no 30, p. 19573-19589
Keywords [en]
RIXS, water, quantum dynamics, x-ray
National Category
Atom and Molecular Physics and Optics
Research subject
Theoretical Chemistry and Biology
Identifiers
URN: urn:nbn:se:kth:diva-187012DOI: 10.1039/C7CP01215BISI: 000407053000006PubMedID: 28352891Scopus ID: 2-s2.0-85027313711OAI: oai:DiVA.org:kth-187012DiVA, id: diva2:928542
Funder
Knut and Alice Wallenberg Foundation, KAW-2013.0020Carl Tryggers foundation , CTS 15:266Swedish Research Council
Note

QC 20160516

Available from: 2016-05-16 Created: 2016-05-16 Last updated: 2018-05-15Bibliographically 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. p. 87
Series
TRITA-BIO-Report, ISSN 1654-2312 ; 2016:10
Keywords
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
2. 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)
Opponent
Supervisors
Note

QC 20180515

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

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