Search

The journal of physical chemistry / A 125, 10138���10143 (2021). doi:10.1021/acs.jpca.1c06033, We performed a time-resolved spectroscopy experixment on the dissociation of oxygen molecules after the interactionwith intense extreme-ultraviolet (XUV) light from the free-electronlaser in Hamburg at Deutsches Elektronen-Synchrotron. Using anXUV-pump/XUV-probe transient-absorption geometry with asplit-and-delay unit, we observe the onset of electronic transitionsin the O$^{2+}$ cation near 50 eV photon energy, marking the end ofthe progression from a molecule to two isolated atoms. We observetwo different time scales of 290 �� 53 and 180 �� 76 fs for theemergence of different ionic transitions, indicating differentdissociation pathways taken by the departing oxygen atoms.With regard to the emerging opportunities of tuning the centralfrequencies of pump and probe pulses and of increasing the probe���pulse bandwidth, future pump���probe transient-absorptionexperiments are expected to provide a detailed view of the coupled nuclear and electronic dynamics during molecular dissociation, Published by Soc., Washington, DC

Physical review / X 11(3), 031001 (1-9) (2021). doi:10.1103/PhysRevX.11.031001, In this work, we use an extreme-ultraviolet (XUV) free-electron laser (FEL) to resonantly excite the I: 4$d_{5/2}–σ^∗$ transition of a gas-phase di-iodomethane (CH$_2$I$_2$) target. This site-specific excitation generates a 4$d$ core hole located at an iodine site, which leaves the molecule in a well-defined excited state. We subsequently measure the time-dependent absorption change of the molecule with the FEL probe spectrum centered on the same I: 4$_d$ resonance. Using ab initio calculations of absorption spectra of a transient isomerization pathway observed in earlier studies, our time-resolved measurements allow us to assign the timescales of the previously reported direct and indirect dissociation pathways. The presented method is thus sensitive to excited-state molecular geometries in a time-resolved manner, following a core-resonant site-specific trigger., Published by APS, College Park, Md.

Physical review letters 123(10), 103001 (2019). doi:10.1103/PhysRevLett.123.103001, We demonstrate time-resolved nonlinear extreme-ultraviolet absorption spectroscopy on multiply charged ions, here applied to the doubly charged neon ion, driven by a phase-locked sequence of two intense free-electron laser pulses. Absorption signatures of resonance lines due to $2p-3d$ bound–bound transitions between the spin-orbit multiplets $^3P_{0,1,2}$ and $^3D_{1,2,3}$ of the transiently produced doubly charged Ne$^{2+}$ ion are revealed, with time-dependent spectral changes over a time-delay range of (2.4±0.3) fs. Furthermore, we observe 10-meV-scale spectral shifts of these resonances owing to the ac Stark effect. We use a time-dependent quantum model to explain the observations by an enhanced coupling of the ionic quantum states with the partially coherent free-electron laser radiation when the phase-locked pump and probe pulses precisely overlap in time., Published by APS, College Park, Md.

[Proceedings] - , 2017. - doi:10.1117/12.2265708 Advances in X-ray Free-Electron Lasers Instrumentation IV, Prague, Czech Republic, 24 Apr 2017 - 27 Apr 2017; Proceedings of SPIE 10237, 1023712 (2017). doi:10.1117/12.2265708, For the soft x-ray free-electron laser FLASH II at DESY in Hamburg a new split-and-delay unit (SDU) is built for photon energies in the range of 30 eV < hν < 1500 eV with an option to expand this range to hν = 2500 eV. The SDU is based on wavefront beam splitting at grazing incidence angles. A three dimensional set-up allows for the use of two different beam paths. With grazing angles of θ = 1.3° in the fixed beam paths and θ = 1.8° in the variable beam path a good compromise between a sufficient reflectance (shallow angles) and a large possible maximum delay (steeper angles) has been chosen. The maximum possible delay is -6 ps < Δt < 18 ps. For photon energies in the range of 30 eV < hν < 800 eV the mirrors are coated with Ni providing a total transmission between T = 57 % at hν = 30 eV and still T >; 30 % at hν = 800 eV. For photon energies up to hν = 1800 eV a different beam path with platinum coated mirrors is used enabling a total transmission in the fixed beam path of T > 29 % at hν = 800 eV and T = 24 % at hν = 1800 eV, respectively. In the variable beam path the total transmission in this photon energy range is considerably lower but still sufficient with T = 13 % at hν = 800 eV and T > 6 % at hν = 1800 eV., Published by SPIE, Bellingham, Wash.

Intermolecular reactions in and on icy films on silicate and carbonaceous grains constitute a major route for the formation of new molecular constituents in interstellar molecular clouds. In more diffuse regions and in protoplanetary discs, energetic radiation can trigger reaction routes far from thermal equilibrium. As an analog of interstellar ice-covered dust grains, highly-oriented pyrolytic graphite (HOPG) covered with D2O, NO, and H atoms is irradiated by ultrashort XUV pulses and the desorbing ionic and neutral products are analysed. The yields of several products show a nonlinear intensity dependence and thus enable the elucidation of reaction dynamics by two-pulse correlated desorption.

Structural dynamics 5(5), 054501 (2018). doi:10.1063/1.5042847, We present a general experimental concept for jitter-free pump and probe experiments at free electron lasers. By generating pump and probe pulse from one and the same X-ray pulse using an optical split-and-delay unit, we obtain a temporal resolution that is limited only by the X-ray pulse lengths. In a two-color X-ray pump and X-ray probe experiment with sub 70 fs temporal resolution, we selectively probe the response of orbital and charge degree of freedom in the prototypical functional oxide magnetite after photoexcitation. We find electronic order to be quenched on a time scale of (30 ± 30) fs and hence most likely faster than what is to be expected for any lattice dynamics. Our experimental result hints to the formation of a short lived transient state with decoupled electronic and lattice degree of freedom in magnetite. The excitation and relaxation mechanism for X-ray pumping is discussed within a simple model leading to the conclusion that within the first 10 fs the original photoexcitation decays into low-energy electronic excitations comparable to what is achieved by optical pump pulse excitation. Our findings show on which time scales dynamical decoupling of degrees of freedom in functional oxides can be expected and how to probe this selectively with soft X-ray pulses. Results can be expected to provide crucial information for theories for ultrafast behavior of materials and help to develop concepts for novel switching devices., Published by AIP Publishing LLC, Melville, NY

We investigate subpicosecond dynamics of warm dense hydrogen at the XUV free-electron laser facility (FLASH) at DESY (Hamburg). Ultrafast impulsive electron heating is initiated by a â‰300-fs short x-ray burst of 92-eV photon energy. A second pulse probes the sample via x-ray scattering at jitter-free variable time delay. We show that the initial molecular structure dissociates within (0.9±0.2) ps, allowing us to infer the energy transfer rate between electrons and ions. We evaluate Saha and Thomas-Fermi ionization models in radiation hydrodynamics simulations, predicting plasma parameters that are subsequently used to calculate the static structure factor. A conductivity model for partially ionized plasma is validated by two-temperature density-functional theory coupled to molecular dynamic simulations and agrees with the experimental data. Our results provide important insights and the needed experimental data on transport properties of dense plasmas. © 2014 American Physical Society.

We report on the dynamics of ultrafast heating in cryogenic hydrogen initiated by a ≲300 fs, 92 eV free electron laser x-ray burst. The rise of the x-ray scattering amplitude from a second x-ray pulse probes the transition from dense cryogenic molecular hydrogen to a nearly uncorrelated plasmalike structure, indicating an electron-ion equilibration time of ∼0.9 ps. The rise time agrees with radiation hydrodynamics simulations based on a conductivity model for partially ionized plasma that is validated by two-temperature density-functional theory. © 2014 American Physical Society.

For the European x-ray free electron laser (XFEL) a split-and-delay unit based on geometrical wavefront beam splitting and multilayer mirrors is built which covers the range of photon energies from 5 keV up to 20 keV. Maximum delays between $\mathrm{\ensuremath{\Delta}}\ensuremath{\tau}=\ifmmode\pm\else\textpm\fi{}2.5\text{ }\text{ }\mathrm{ps}$ at $h\ensuremath{\nu}=20\text{ }\mathrm{keV}$ and up to $\mathrm{\ensuremath{\Delta}}\ensuremath{\tau}=\ifmmode\pm\else\textpm\fi{}23\text{ }\text{ }\mathrm{ps}$ at $h\ensuremath{\nu}=5\text{ }\text{ }\mathrm{keV}$ will be possible. Time-dependent wave-optics simulations have been performed by means of Synchrotron Radiation Workshop software for XFEL pulses at $h\ensuremath{\nu}=5\text{ }\text{ }\mathrm{keV}$. The XFEL radiation was simulated using results of time-dependent simulations applying the self-amplified spontaneous emission code FAST. Main features of the optical layout, including diffraction on the beam splitter edge and optics imperfections measured with a nanometer optic component measuring machine slope measuring profiler, were taken into account. The impact of these effects on the characterization of the temporal properties of XFEL pulses is analyzed. An approach based on fast Fourier transformation allows for the evaluation of the temporal coherence despite large wavefront distortions caused by the optics imperfections. In this way, the fringes resulting from time-dependent two-beam interference can be filtered and evaluated yielding a coherence time of ${\ensuremath{\tau}}_{c}=0.187\text{ }\text{ }\mathrm{fs}$ (HWHM) for real, nonperfect mirrors, while for ideal mirrors a coherence time of ${\ensuremath{\tau}}_{c}=0.191\text{ }\text{ }\mathrm{fs}$ (HWHM) is expected.

To provide two jitter‐free soft x‐ray pulses for femtosecond x‐ray pump and probe experiments a split and delay unit (autocorrelator) has been constructed for the VUV—FEL in Hamburg (FLASH). Here we report experiments applying this autocorrelator to examine the average temporal properties of FEL pulses delivered from FLASH at 24 nm (51.8 eV). In a linear autocorrelation experiment the spatio‐temporal coherence properties are measured for both the first and the third harmonic of the FEL pulses. Furthermore, we report on the first evaluation of the pulse length from the time‐resolved observation of doubly charged helium ions produced by direct two‐photon double ionization at 24 nm. In summary the determination of the longitudinal pulse parameter of FLASH at 24 nm to 6 fs and 29±5 fs for the coherence time and the pulse length (FWHM) respectively proofs the autocorrelator as a valuable tool for time resolved two pulse X‐ray experiments.

Physical review / A 80(2), 4 (2009). doi:10.1103/PhysRevA.80.025402, The pulse duration of soft x-ray free-electron laser (FEL) radiation is directly measured by time-resolved observation of doubly charged helium ions at 51.8 eV. A wave front splitting autocorrelator produces two correlated FEL pulses with a resolution of better than a femtosecond. In the interesting intensity range from 10$_{13}$ to 10$_{16]$ W/cm$_2$ direct and sequential double ionization contribute to the ion yield which has significant influence on the correlation width, being a general feature at high photon energies. Here, a duration of τL=(29±5) fs is derived for the soft x-ray pulses at FLASH., Published by APS, College Park, Md.

The expansion and disintegration dynamics of xenon clusters initiated by the ionization with femtosecond soft x-ray extreme ultraviolet (XUV) pulses were studied with pump–probe spectroscopy using the autocorrelator setup of the Free-Electron LASer in Hamburg (FLASH) facility. The ionization by the first XUV pulse of 92 eV photon energy (8 × 10 12 Wc m −2 ) leads to the generation of a large number of quasi-free electrons trapped by the space charge of the cluster ions. A temporally delayed, more intense probe (4 × 10 13 Wc m −2 ) pulse substantially increases a population of nanoplasma electrons providing a way of probing plasma states in the expanding cluster by tracing the average charge of fragment ions. The results of the study reveal a timescale for cluster expansion and disintegration, which depends essentially on the initial cluster size. The average charge state of fragment ions, and thus the cluster plasma changes significantly on a timescale of 1–3 ps. (Some figures may appear in colour only in the online journal)