| 1. |
- Bennett, Kochise, et al.
(författare)
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Multidimensional resonant nonlinear spectroscopy with coherent broadband x-ray pulses
- 2016
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Ingår i: Physica Scripta. - : IOP PUBLISHING LTD. - 0031-8949 .- 1402-4896. ; T169
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Tidskriftsartikel (refereegranskat)abstract
- New x-ray free electron laser (XFEL) and high harmonic generation (HHG) light sources are capable of generating short and intense pulses that make x-ray nonlinear spectroscopy possible. Multidimensional spectroscopic techniques, which have long been used in the nuclear magnetic resonance, infrared, and optical regimes to probe the electronic structure and nuclear dynamics of molecules by sequences of short pulses with variable delays, can thus be extended to the attosecond x-ray regime. This opens up the possibility of probing core-electronic structure and couplings, the real-time tracking of impulsively created valence-electronic wavepackets and electronic coherences, and monitoring ultrafast processes such as nonadiabatic electron-nuclear dynamics near conical-intersection crossings. We survey various possible types of multidimensional x-ray spectroscopy techniques and demonstrate the novel information they can provide about molecules.
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| 2. |
- Chergui, Majed, et al.
(författare)
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Progress and prospects in nonlinear extreme-ultraviolet and X-ray optics and spectroscopy
- 2023
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Ingår i: Nature reviews physics. - 2522-5820. ; :5, s. 578-596
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Forskningsöversikt (refereegranskat)abstract
- Free-electron lasers and high-harmonic-generation table-top systems are new sources of extreme-ultraviolet to hard X-ray photons, providing ultrashort pulses that are intense, coherent and tunable. They are enabling a broad range of nonlinear optical and spectroscopic methods at short wavelengths, similar to those developed in the terahertz to ultraviolet regimes over the past 60 years. The extreme-ultraviolet to X-ray wavelengths access core transitions that can provide element and orbital selectivity, structural resolution down to the sub-nanometre scale and, for some methods, high momentum transfers across typical Brillouin zones; the possibilities for polarization control and sub-femtosecond time resolution are opening up new frontiers in research. In this Roadmap, we review the emergence of this field over the past 10 years or so, covering methods such as sum or difference frequency generation and second-harmonic generation, two-photon absorption, stimulated emission or Raman spectroscopy and transient grating spectroscopy. We then discuss the unique opportunities provided by these techniques for probing elementary dynamics in a wide variety of systems. X-ray free-electron lasers and high-harmonic-generation sources of extreme-ultraviolet (EUV) to hard X-ray photons deliver intense ultrashort pulses and enable the extension of nonlinear methods to much shorter wavelengths.EUV to X-ray wavelengths access core transitions that can provide element and orbital selectivity. These wavelengths also achieve sub-nanometre structural resolution and high momentum transfer, with femtosecond and attosecond time resolution.Nonlinear EUV/X-ray methods that have emerged include sum or difference frequency generation, parametric down-conversion, second-harmonic generation, two-photon absorption, stimulated emission or Raman spectroscopy and transient grating spectroscopy.Nonlinear EUV/X-ray science is developing hand-in-hand with instrumentation, to improve pulse features and enhance accessibility with the use of table-top systems or compact accelerators.These techniques offer unique opportunities for probing dynamical events in a wide variety of systems, including surface and interface processes, chirality, nanoscale transport and multidimensional core-level spectroscopy. New sources of extreme-ultraviolet to hard X-ray photons have enabled a wide range of short-wavelength nonlinear optical and spectroscopic methods over the past decade, and, for the future, offer unique opportunities to probe elementary dynamics in various systems.
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| 3. |
- Cho, Daeheum, et al.
(författare)
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Imaging of transition charge densities involving carbon core excitations by all X-ray sum-frequency generation
- 2019
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Ingår i: Philosophical Transactions. Series A. - : The Royal Society. - 1364-503X .- 1471-2962. ; 377:2145
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Tidskriftsartikel (refereegranskat)abstract
- X-ray diffraction signals from the time-evolving molecular charge density induced by selective core excitation of chemically inequivalent carbon atoms are calculated. A narrowband X-ray pulse selectively excites the carbon K-edge of the –CH3 or –CH2F groups in fluoroethane (CH3–CH2F). Each excitation creates a distinct core coherence which depends on the character of the electronic transition. Direct propagation of the reduced single-electron density matrix, using real-time time-dependent density functional theory, provides the time-evolving charge density following interactions with external fields. The interplay between partially filled valence molecular orbitals upon core excitation induces characteristic femtosecond charge migration which depends on the core–valence coherence, and is monitored by the sum-frequency generation diffraction signal.
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| 4. |
- Hua, Weijie, et al.
(författare)
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Study of double core hole excitations in molecules by X-ray double-quantum-coherence signals : a multi-configuration simulation
- 2016
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Ingår i: Chemical Science. - : Royal Society of Chemistry. - 2041-6520 .- 2041-6539. ; 7:9, s. 5922-5933
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Tidskriftsartikel (refereegranskat)abstract
- The multi-configurational self-consistent field method is employed to simulate the two-dimensional all-X-ray double-quantum-coherence (XDQC) spectroscopy, a four-wave mixing signal that provides direct signatures of double core hole (DCH) states. The valence electronic structure is probed by capturing the correlation between the single (SCH) and double core hole states. The state-averaged restricted-activespace self-consistent field (SA-RASSCF) approach is used which can treat the valence, SCH, and DCH states at the same theoretical level, and applies to all types of DCHs (located on one or two atoms, K-edge or L-edge), with both accuracy and efficiency. Orbital relaxation introduced by the core hole(s) and the static electron correlation is properly accounted for. The XDQC process can take place via different intermediate DCH state channels by tuning the pulse frequencies. We simulate the XDQC signals for the three isomers of aminophenol at 8 pulse frequency configurations, covering all DCH pathways involving the N1s and O1s core hole (N1sN1s, O1sO1s and N1sO1s), which reveal different patterns of valence excitations.
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| 5. |
- Kimberg, Victor, 1973-
(författare)
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Pulse Propagation in Nonlinear Media and Photonic Crystals
- 2006
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- The present thesis is devoted to theoretical studies of pulse propagation of light through linear and nonlinear media, and of light-induced nuclear dynamics. The first part of the thesis addresses propagation of light pulses in linear periodical media - photonic crystals. The main accent was put on studies of the angular properties of two qualitatively different types of photonic crystals: holographic photonic crystals, and impurity band based photonic crystals. The anisotropy of band structure, group velocity and pulse delay with respect to the light polarization are analyzed. In the second part of the thesis a strict theory of nonlinear propagation of a few strong interacting light beams is presented. The key idea of this approach is a self-consistent solution of the nonlinear wave equation and the density matrix equations of the material. This technique is applied to studies of dynamics of cavityless lasing generated by ultra-fast multi-photon excitation. It is shown that interaction of co- and counter-propagating pulses of amplified spontaneous emission (ASE) affects the dynamics and efficiency of nonlinear conversion. Our dynamical theory allows to explain the asymmetric spectral properties of the forward and backward ASE pulses, which were observed in recent experiment with different dye molecules. It is shown that the ASE spectral profile changes drastically when the pump intensity approaches the threshold level. The effect of the temporal self-pulsation of ASE is studied in detail. The third part of the thesis is devoted to light-induced nuclear dynamics. Time- and frequency-resolved X-ray spectroscopy of molecules driven by strong and coherent infrared (IR) pulses shows that the phase of the IR field strongly influences the trajectory of the nuclear wave packet, and hence, the X-ray spectrum. Such a dependence arises due to the interference of one (X-ray) and two-photon (X-ray + IR) excitation channels. The phase of the light influences the dynamics also when the Rabi frequency approaches the vibrational frequency, breaking down the rotating-wave approximation. The probe X-ray spectra are also sensitive to the delay time, the duration, and the shape of the pulses. The evolution of the nuclear wave packets in the dissociative core-excited state affects the dynamics of resonant Auger scattering from fixed-in-space molecules. One of the important dynamical effects is the atomic-like resonance which experiences electronic Doppler shift. We predict that the scattering of the Auger electrons by nearby atoms leads to new Doppler shifted resonances. These extra resonances show sharp maxima in the bond directions, which makes them very promising as probes for local molecular structure using energy and angular resolved electron-ion coincidence techniques. Our theory provides prediction of several new effects, but also results that are in good agreement with the available experimental data.
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| 6. |
- Kowalewski, Markus, 1980-, et al.
(författare)
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Monitoring nonadiabatic dynamics in molecules by ultrafast X-Ray diffraction
- 2019
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Ingår i: EPJ Web of Conferences. - : EDP Sciences. - 2100-014X. ; 205
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Tidskriftsartikel (refereegranskat)abstract
- We theoretically examine time-resolved diffraction from molecules which undergo non-adiabatic dynamics and identify contributions from inelastic scattering that indicate the presence of an avoided crossing and the corresponding nuclear configuration.
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| 7. |
- Ljungberg, Mathias P., 1977-
(författare)
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Theoretical modeling of x-ray and vibrational spectroscopies applied to liquid water and surface adsorbates
- 2010
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Doktorsavhandling (övrigt vetenskapligt/konstnärligt)abstract
- This thesis presents results of theoretical modeling of x-ray and vibrational spectroscopies applied to liquid water and to CO adsorbed on a Ni(100) surface. The Reverse Monte Carlo method is used to search for water structures that reproduce diffraction, IR/Raman and x-ray absorption by fitting them to experimental data and imposed constraints. Some of the structures are created to have a large fraction of broken hydrogen bonds because recent x-ray absorption and emission studies have been seen to support the existence of such structures. In the fitting procedure a fast way of computing the IR/Raman spectrum for an isolated OH stretch is used, where the frequency is represented by the electric field projected in the direction of the stretch coordinate. This method is critically evaluated by comparing it to quantum chemical cluster calculations. Furthermore, the x-ray emission spectrum of water is investigated, the modeling of which is complicated by the necessity of including vibrational effects in the spectrum calculations due to a dissociative intermediate state. Based on the Kramers-Heisenberg formula a new semi-classical method is developed to include vibrational effects in x-ray emission calculations. The method is seen to work very well for a one-dimensional test system. Moreover, x-ray absorption and emission are implemented in a periodic Density Functional Theory code which is applied to ice and to the surface adsorbate system CO on Ni(100).
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| 9. |
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| 10. |
- Osipov, Vladimir Al., et al.
(författare)
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Multiscale wavelet decomposition of time-resolved X-ray diffraction signals in cyclohexadiene
- 2018
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Ingår i: Proceedings of the National Academy of Sciences of the United States of America. - : Proceedings of the National Academy of Sciences. - 0027-8424 .- 1091-6490. ; 115:41, s. 10269-10274
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Tidskriftsartikel (refereegranskat)abstract
- We demonstrate how the wavelet transform, which is a powerful tool for compression, filtering, and scaling analysis of signals, may be used to separate large- and short-scale electron density features in X-ray diffraction patterns. Wavelets can isolate the electron density associated with delocalized bonds from the much stronger background of highly localized core electrons. The wavelet-processed signals clearly reveal the bond formation and breaking in the early steps of the photoinduced pericyclic ring opening reaction of 1,3-cyclohexadiene, which are not resolved in the bare signal.
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