an-experimental-protocol-for-femtosecond-niruv-xuv-pump-probe

An Experimental Protocol for Femtosecond NIR/UV - XUV Pump-Probe Experiments with Free-Electron Lasers

This protocol describes key steps in performing and analyzing femtosecond pump-probe experiments that combine a femtosecond optical laser with a ...

Deutsches Elektronen-Synchrotron DESY

European XFEL GmbH

Studies of charge transfer are often hampered by difficulties in determining the charge localization at a given time. Here, we used ultrashort x-ray free-electron laser pulses to image charge rearrangement dynamics within gas-phase iodomethane molecules during dissociation induced by a synchronized near-infrared (NIR) laser pulse. Inner-shell photoionization creates positive charge, which is initially localized on the iodine atom. We map the electron transfer between the methyl and iodine fragments as a function of their interatomic separation set by the NIR-x-ray delay. We observe signatures of electron transfer for distances up to 20 angstroms and show that a realistic estimate of its effective spatial range can be obtained from a classical over-the-barrier model. The presented technique is applicable for spatiotemporal imaging of charge transfer dynamics in a wide range of molecular systems. 

Imaging charge transfer in iodomethane upon x-ray photoabsorption.

Helium nanodroplets are considered ideal model systems to explore quantum hydrodynamics in self-contained, isolated superfluids. However, exploring the dynamic properties of individual droplets is experimentally challenging. In this work, we used single-shot femtosecond x-ray coherent diffractive imaging to investigate the rotation of single, isolated superfluid helium-4 droplets containing ~10(8) to 10(11) atoms. The formation of quantum vortex lattices inside the droplets is confirmed by observing characteristic Bragg patterns from xenon clusters trapped in the vortex cores. The vortex densities are up to five orders of magnitude larger than those observed in bulk liquid helium. The droplets exhibit large centrifugal deformations but retain axially symmetric shapes at angular velocities well beyond the stability range of viscous classical droplets.

Helium superfluidity. Shapes and vorticities of superfluid helium nanodroplets.

This paper gives an account of our progress towards performing femtosecond time-resolved photoelectron diffraction on gas-phase molecules in a pump-probe setup combining optical lasers and an X-ray free-electron laser. We present results of two experiments aimed at measuring photoelectron angular distributions of laser-aligned 1-ethynyl-4-fluorobenzene (C(8)H(5)F) and dissociating, laser-aligned 1,4-dibromobenzene (C(6)H(4)Br(2)) molecules and discuss them in the larger context of photoelectron diffraction on gas-phase molecules. We also show how the strong nanosecond laser pulse used for adiabatically laser-aligning the molecules influences the measured electron and ion spectra and angular distributions, and discuss how this may affect the outcome of future time-resolved photoelectron diffraction experiments.

Imaging molecular structure through femtosecond photoelectron diffraction on aligned and oriented gas-phase molecules.

Ultrafast electron transfer in dissociating iodomethane and fluoromethane molecules was studied at the Linac Coherent Light Source free-electron laser using an ultraviolet-pump, X-ray-probe scheme. The results for both molecules are discussed with respect to the nature of their UV excitation and different chemical properties. Signatures of long-distance intramolecular charge transfer are observed for both species, and a quantitative analysis of its distance dependence in iodomethane is carried out for charge states up to I(21+). The reconstructed critical distances for electron transfer are in good agreement with a classical over-the-barrier model and with an earlier experiment employing a near-infrared pump pulse. 

Charge transfer in dissociating iodomethane and fluoromethane molecules ionized by intense femtosecond X-ray pulses.

Laser-induced adiabatic alignment and mixed-field orientation of 2,6-difluoroiodobenzene (CHFI) molecules are probed by Coulomb explosion imaging following either near-infrared strong-field ionization or extreme-ultraviolet multi-photon inner-shell ionization using free-electron laser pulses. The resulting photoelectrons and fragment ions are captured by a double-sided velocity map imaging spectrometer and projected onto two position-sensitive detectors. The ion side of the spectrometer is equipped with a pixel imaging mass spectrometry camera, a time-stamping pixelated detector that can record the hit positions and arrival times of up to four ions per pixel per acquisition cycle. Thus, the time-of-flight trace and ion momentum distributions for all fragments can be recorded simultaneously. We show that we can obtain a high degree of one-and three-dimensional alignment and mixed-field orientation and compare the Coulomb explosion process induced at both wavelengths.

Alignment, orientation, and Coulomb explosion of difluoroiodobenzene studied with the pixel imaging mass spectrometry (PImMS) camera.

We explore time-resolved Coulomb explosion induced by intense, extreme ultraviolet (XUV) femtosecond pulses from a free-electron laser as a method to image photo-induced molecular dynamics in two molecules, iodomethane and 2,6-difluoroiodobenzene. At an excitation wavelength of 267 nm, the dominant reaction pathway in both molecules is neutral dissociation via cleavage of the carbon-iodine bond. This allows investigating the influence of the molecular environment on the absorption of an intense, femtosecond XUV pulse and the subsequent Coulomb explosion process. We find that the XUV probe pulse induces local inner-shell ionization of atomic iodine in dissociating iodomethane, in contrast to non-selective ionization of all photofragments in difluoroiodobenzene. The results reveal evidence of electron transfer from methyl and phenyl moieties to a multiply charged iodine ion. In addition, indications for ultrafast charge rearrangement on the phenyl radical are found, suggesting that time-resolved Coulomb explosion imaging is sensitive to the localization of charge in extended molecules.

Photodissociation of aligned CHI and CHFI molecules probed with time-resolved Coulomb explosion imaging by site-selective extreme ultraviolet ionization.

The application of a novel fast optical-imaging camera, TimepixCam, to molecular photoionization experiments using the velocity-map imaging technique at a free-electron laser is described. TimepixCam is a 256 × 256 pixel CMOS camera that is able to detect and time-stamp ion hits with 20 ns timing resolution, thus making it possible to record ion momentum images for all fragment ions simultaneously and avoiding the need to gate the detector on a single fragment. This allows the recording of significantly more data within a given amount of beam time and is particularly useful for pump-probe experiments, where drifts, for example, in the timing and pulse energy of the free-electron laser, severely limit the comparability of pump-probe scans for different fragments taken consecutively. In principle, this also allows ion-ion covariance or coincidence techniques to be applied to determine angular correlations between fragments.

Time-resolved ion imaging at free-electron lasers using TimepixCam.

A photofragmentation study of gas-phase indole (C8H7N) upon single-photon ionization at a photon energy of 420 eV is presented. Indole was primarily inner-shell ionized at its nitrogen and carbon 1s orbitals. Electrons and ions were measured in coincidence by means of velocity map imaging. The angular relationship between ionic fragments is discussed along with the possibility to use the angle-resolved coincidence detection to perform experiments on molecules that are strongly oriented in their recoil-frame. The coincident measurement of electrons and ions revealed fragmentation-pathway-dependent electron spectra, linking the structural fragmentation dynamics to different electronic excitations. Evidence for photoelectron-impact self-ionization was observed.

Photophysics of indole upon X-ray absorption.

We have investigated the photoionization and photofragmentation yields of gas-phase multiply protonated melittin cations for photon energies at the K-shell absorption edges of carbon, nitrogen, and oxygen. Two similar experimental approaches were employed. In both experiments, mass selected [melittin+qH] (q=2-4) ions were accumulated in radiofrequency ion traps. The trap content was exposed to intense beams of monochromatic soft X-ray photons from synchrotron beamlines and photoproducts were analyzed by means of time-of-flight mass spectrometry. Mass spectra were recorded for fixed photon energies, and partial ion yield spectra were recorded as a function of photon energy. The combination of mass spectrometry and soft X-ray spectroscopy allows for a direct correlation of protein electronic structure with various photoionization channels. Non-dissociative single and double ionization are used as a reference. The contribution of both channels to various backbone scission channels is quantified and related to activation energies and protonation sites. Soft X-ray absorption mass spectrometry combines fast energy deposition with single and double ionization and could complement established activation techniques. Graphical Abstract ᅟ.

Near-Edge Soft X-ray Absorption Mass Spectrometry of Protonated Melittin.

Extreme ultraviolet (XUV) and X-ray free-electron lasers enable new scientific opportunities. Their ultra-intense coherent femtosecond pulses give unprecedented access to the structure of undepositable nanoscale objects and to transient states of highly excited matter. In order to probe the ultrafast complex light-induced dynamics on the relevant time scales, the multi-purpose end-station CAMP at the free-electron laser FLASH has been complemented by the novel multilayer-mirror-based split-and-delay unit DESC (DElay Stage for CAMP) for time-resolved experiments. XUV double-pulses with delays adjustable from zero femtoseconds up to 650 picoseconds are generated by reflecting under near-normal incidence, exceeding the time range accessible with existing XUV split-and-delay units. Procedures to establish temporal and spatial overlap of the two pulses in CAMP are presented, with emphasis on the optimization of the spatial overlap at long time-delays via time-dependent features, for example in ion spectra of atomic clusters.

XUV double-pulses with femtosecond to 650 ps separation from a multilayer-mirror-based split-and-delay unit at FLASH.

The non-monochromatic beamline BL1 at the FLASH free-electron laser facility at DESY was upgraded with new transport and focusing optics, and a new permanent end-station, CAMP, was installed. This multi-purpose instrument is optimized for electron- and ion-spectroscopy, imaging and pump-probe experiments at free-electron lasers. It can be equipped with various electron- and ion-spectrometers, along with large-area single-photon-counting pnCCD X-ray detectors, thus enabling a wide range of experiments from atomic, molecular, and cluster physics to material and energy science, chemistry and biology. Here, an overview of the layout, the beam transport and focusing capabilities, and the experimental possibilities of this new end-station are presented, as well as results from its commissioning.

CAMP@FLASH: an end-station for imaging, electron- and ion-spectroscopy, and pump-probe experiments at the FLASH free-electron laser.

An accurate description of the interaction of intense hard X-ray pulses with heavy atoms, which is crucial for many applications of free-electron lasers, represents a hitherto unresolved challenge for theory because of the enormous number of electronic configurations and relativistic effects, which need to be taken into account. Here we report results on multiple ionization of xenon atoms by ultra-intense (about 10 W/cm) femtosecond X-ray pulses at photon energies from 5.5 to 8.3 keV and present a theoretical model capable of reproducing the experimental data in the entire energy range. Our analysis shows that the interplay of resonant and relativistic effects results in strongly structured charge state distributions, which reflect resonant positions of relativistically shifted electronic levels of highly charged ions created during the X-ray pulse. The theoretical approach described here provides a basis for accurate modeling of radiation damage in hard X-ray imaging experiments on targets with high-Z constituents.

Rebecca Boll

Deutsches Elektronen-Synchrotron DESY

An Experimental Protocol for Femtosecond NIR/UV - XUV Pump-Probe Experiments with Free-Electron Lasers