Closed-cycle noble gas recycling system for high-repetition rate high-harmonic generation.

We present a compact closed-loop recycling system for noble and inert gases. It has been developed for an extreme-ultraviolet (XUV) frequency comb based on high-harmonic generation at 100 MHz repetition rate. The system collects gas injected at several bars of backing pressure through a micrometer-sized nozzle into the laser-interaction region with a differential pumping system comprising turbomolecular pumps, and subsequently compresses the gas to a pressure of up to 200 bar. By drastically reducing the waste of expensive gases such as xenon and krypton, it enables the long operation times needed for spectroscopic measurements, as well as for continuous operation of the XUV frequency comb.

Isotope effects in dynamics of water isotopologues induced by core ionization at an x-ray free-electron laser.

Dynamical response of water exposed to x-rays is of utmost importance in a wealth of science areas. We exposed isolated water isotopologues to short x-ray pulses from a free-electron laser and detected momenta of all produced ions in coincidence. By combining experimental results and theoretical modeling, we identify significant structural dynamics with characteristic isotope effects in H2O2+, D2O2+, and HDO2+, such as asymmetric bond elongation and bond-angle opening, leading to two-body or three-body fragmentation on a timescale of a few femtoseconds. A method to disentangle the sequences of events taking place upon the consecutive absorption of two x-ray photons is described. The obtained deep look into structural properties and dynamics of dissociating water isotopologues provides essential insights into the underlying mechanisms.

Ultrastable, high-repetition-rate attosecond beamline for time-resolved XUV-IR coincidence spectroscopy.

The implementation of attosecond photoelectron-photoion coincidence spectroscopy for the investigation of atomic and molecular dynamics calls for a high-repetition-rate driving source combined with experimental setups characterized by excellent stability for data acquisition over time intervals ranging from a few hours up to a few days. This requirement is crucial for the investigation of processes characterized by low cross sections and for the characterization of fully differential photoelectron(s) and photoion(s) angular and energy distributions. We demonstrate that the implementation of industrial-grade lasers, combined with a careful design of the delay line implemented in the pump-probe setup, allows one to reach ultrastable experimental conditions leading to an error in the estimation of the time delays of only 12 as over an acquisition time of 6.5 h. This result opens up new possibilities for the investigation of attosecond dynamics in simple quantum systems.

Photoelectron tomography with an intra-cavity velocity-map imaging spectrometer at 100 MHz repetition rate.

We present a compact velocity-map imaging (VMI) spectrometer for photoelectron imaging at 100 MHz repetition rate. Ultrashort pulses from a near-infrared frequency comb laser are amplified in a polarization-insensitive passive femtosecond enhancement cavity. In the focus, multi-photon ionization (MPI) of gas-phase atoms is studied tomographically by rotating the laser polarization. We demonstrate the functioning of the VMI spectrometer by reconstructing photoelectron angular momentum distributions from xenon MPI. Our intra-cavity VMI setup collects electron energy spectra at high rates, with the advantage of transferring the coherence of the cavity-stabilized femtosecond pulses to the electrons. In addition, the setup will allow studies of strong-field effects in nanometric tips.

A new benchmark of soft X-ray transition energies of Ne , CO 2 , and SF 6 : paving a pathway towards ppm accuracy.

Abstract: A key requirement for the correct interpretation of high-resolution X-ray spectra is that transition energies are known with high accuracy and precision. We investigate the K-shell features of Ne , CO 2 , and SF 6 gases, by measuring their photo ion-yield spectra at the BESSY II synchrotron facility simultaneously with the 1s-np fluorescence emission of He-like ions produced in the Polar-X EBIT. Accurate ab initio calculations of transitions in these ions provide the basis of the calibration. While the CO 2 result agrees well with previous measurements, the SF 6 spectrum appears shifted by ∼ 0.5 eV, about twice the uncertainty of the earlier results. Our result for Ne shows a large departure from earlier results, but may suffer from larger systematic effects than our other measurements. The molecular spectra agree well with our results of time-dependent density functional theory. We find that the statistical uncertainty allows calibrations in the desired range of 1-10 meV, however, systematic contributions still limit the uncertainty to ∼ 40-100 meV, mainly due to the temporal stability of the monochromator energy scale. Combining our absolute calibration technique with a relative energy calibration technique such as photoelectron energy spectroscopy will be necessary to realize its full potential of achieving uncertainties as low as 1-10 meV.

Attosecond photoionisation time delays reveal the anisotropy of the molecular potential in the recoil frame.

Photoionisation time delays carry structural and dynamical information on the target system, including electronic correlation effects in atoms and molecules and electron transport properties at interfaces. In molecules, the electrostatic potential experienced by an outgoing electron depends on the emission direction, which should thus lead to anisotropic time delays. To isolate this effect, information on the orientation of the molecule at the photoionisation instant is required. Here we show how attosecond time delays reflect the anisotropic molecular potential landscape in CF4 molecules. The variations in the measured delays can be directly related to the different heights of the potential barriers that the outgoing electrons see in the vicinity of shape resonances. Our results indicate the possibility to investigate the spatial characteristics of the molecular potential by mapping attosecond photoionisation time delays in the recoil-frame.

Erratum: Publisher's Note: "Laser-induced electron diffraction of the ultrafast umbrella motion in ammonia" [Struct. Dyn. 8, 014301 (2021)].

[This corrects the article DOI: 10.1063/4.0000046.].

An ultralow-noise superconducting radio-frequency ion trap for frequency metrology with highly charged ions.

We present a novel ultrastable superconducting radio-frequency (RF) ion trap realized as a combination of an RF cavity and a linear Paul trap. Its RF quadrupole mode at 34.52 MHz reaches a quality factor of Q ≈ 2.3 × 105 at a temperature of 4.1 K and is used to radially confine ions in an ultralow-noise pseudopotential. This concept is expected to strongly suppress motional heating rates and related frequency shifts that limit the ultimate accuracy achieved in advanced ion traps for frequency metrology. Running with its low-vibration cryogenic cooling system, electron-beam ion trap, and deceleration beamline supplying highly charged ions (HCIs), the superconducting trap offers ideal conditions for optical frequency metrology with ionic species. We report its proof-of-principle operation as a quadrupole-mass filter with HCIs and trapping of Doppler-cooled 9Be+ Coulomb crystals.

Laser-induced electron diffraction of the ultrafast umbrella motion in ammonia.

Visualizing molecular transformations in real-time requires a structural retrieval method with Ångström spatial and femtosecond temporal atomic resolution. Imaging of hydrogen-containing molecules additionally requires an imaging method sensitive to the atomic positions of hydrogen nuclei, with most methods possessing relatively low sensitivity to hydrogen scattering. Laser-induced electron diffraction (LIED) is a table-top technique that can image ultrafast structural changes of gas-phase polyatomic molecules with sub-Ångström and femtosecond spatiotemporal resolution together with relatively high sensitivity to hydrogen scattering. Here, we image the umbrella motion of an isolated ammonia molecule (NH3) following its strong-field ionization. Upon ionization of a neutral ammonia molecule, the ammonia cation (NH3 +) undergoes an ultrafast geometrical transformation from a pyramidal ( Φ HNH = 107 ° ) to planar ( Φ HNH = 120 ° ) structure in approximately 8 femtoseconds. Using LIED, we retrieve a near-planar ( Φ HNH = 117 ± 5 ° ) field-dressed NH3 + molecular structure 7.8 - 9.8 femtoseconds after ionization. Our measured field-dressed NH3 + structure is in excellent agreement with our calculated equilibrium field-dressed structure using quantum chemical ab initio calculations.

Molecular structure retrieval directly from laboratory-frame photoelectron spectra in laser-induced electron diffraction.

Ubiquitous to most molecular scattering methods is the challenge to retrieve bond distance and angle from the scattering signals since this requires convergence of pattern matching algorithms or fitting methods. This problem is typically exacerbated when imaging larger molecules or for dynamic systems with little a priori knowledge. Here, we employ laser-induced electron diffraction (LIED) which is a powerful means to determine the precise atomic configuration of an isolated gas-phase molecule with picometre spatial and attosecond temporal precision. We introduce a simple molecular retrieval method, which is based only on the identification of critical points in the oscillating molecular interference scattering signal that is extracted directly from the laboratory-frame photoelectron spectrum. The method is compared with a Fourier-based retrieval method, and we show that both methods correctly retrieve the asymmetrically stretched and bent field-dressed configuration of the asymmetric top molecule carbonyl sulfide (OCS), which is confirmed by our quantum-classical calculations.

XUV frequency comb production with an astigmatism-compensated enhancement cavity.

We have developed an extreme ultraviolet (XUV) frequency comb for performing ultra-high precision spectroscopy on the many XUV transitions found in highly charged ions (HCI). Femtosecond pulses from a 100 MHz phase-stabilized near-infrared frequency comb are amplified and then fed into a femtosecond enhancement cavity (fsEC) inside an ultra-high vacuum chamber. The low-dispersion fsEC coherently superposes several hundred incident pulses and, with a single cylindrical optical element, fully compensates astigmatism at the w0 = 15 µm waist cavity focus. With a gas jet installed there, intensities reaching ∼ 1014 W/cm2 generate coherent high harmonics with a comb spectrum at 100 MHz rate. We couple out of the fsEC harmonics from the 7th up to the 35th (42 eV; 30 nm) to be used in upcoming experiments on HCI frequency metrology.

TrapREMI: A reaction microscope inside an electrostatic ion beam trap.

A new experimental setup has been developed to investigate the reactions of molecular ions and charged clusters with a variety of projectile beams. An Electrostatic Ion Beam Trap (EIBT) stores fast ions at keV energies in an oscillatory motion. By crossing it with a projectile beam, e.g., an IR laser, molecular reactions can be induced. We implemented a Reaction Microscope (REMI) in the field-free region of the EIBT to perform coincidence spectroscopy on the resulting reaction products. In contrast to prior experiments, this unique combination of techniques allows us to measure the 3D momentum-vectors of ions, electrons, and neutrals as reaction products in coincidence. At the same time, the EIBT allows for advanced target preparation techniques, e.g., relaxation of hot molecules during storage times of up to seconds, autoresonance cooling, and recycling of target species, which are difficult to prepare. Otherwise, the TrapREMI setup can be connected to a variety of projectile sources, e.g., atomic gas jets, large-scale radiation facilities, and ultrashort laser pulses, which enable even time-resolved studies. Here, we describe the setup and a first photodissociation experiment on H2 +, which demonstrates the ion-neutral coincidence detection in the TrapREMI.

Reaction microscope for investigating ionization dynamics of weakly bound alkali dimers.

We report on the implementation of a far-off-resonant, optical dipole force trap in a reaction microscope combined with a magneto-optical trap. Kinematically complete multi-photon ionization experiments were performed on optically trapped 6Li atoms and photo-associated 6Li2 molecules in their highest vibrational state. The apparatus allows us to distinguish different ionization mechanisms related to the presence of the IR field of the optical dipole trap that can occur during ionization of 6Li and 6Li2 in strong fields. In a series of proof-of-principle experiments, we detect weakly bound dimers via three-photon ionization with femtosecond pulses (τ = 30 fs) at a central wavelength of 780 nm and measure directly the momenta of the photoelectrons in coincidence with recoil ions.

100 MHz frequency comb for low-intensity multi-photon studies: intra-cavity velocity-map imaging of xenon.

We raise the power from a commercial 10 W frequency comb inside an enhancement cavity and perform multi-photon ionization of gas-phase atoms at 100 MHz for the first time, to the best of our knowledge. An intra-cavity velocity-map-imaging setup collects electron-energy spectra of xenon at rates several orders of magnitude higher than those of conventional laser systems. Consequently, we can use much lower intensities ${\sim}{{10}^{12}} \;{\rm W}/{{\rm cm}^2} $∼1012W/cm2 without increasing acquisition times above just a few seconds. The high rate and coherence of the stabilized femtosecond pulses are known to be transferred to the actively stabilized cavity and will allow studying purely perturbative multi-photon effects, paving the road towards a new field of precision tests in nonlinear physics.

Electron transfer mediated decay of alkali dimers attached to He nanodroplets.

Alkali metal dimers attached to the surface of helium nanodroplets are found to be efficiently doubly ionized by electron transfer mediated decay (ETMD) when photoionizing the helium droplets. This process is evidenced by detecting in coincidence two energetic ions created by Coulomb explosion and one low-kinetic energy electron. The kinetic energy spectra of ions and electrons are reproduced by simple model calculations based on diatomic potential energy curves, and are in agreement with ab initio calculations for the He-Na2 and He-KRb systems. This work demonstrates that ETMD is an important decay channel in heterogeneous nanosystems exposed to ionizing radiation.

High-Precision Determination of Oxygen K_{α} Transition Energy Excludes Incongruent Motion of Interstellar Oxygen.

We demonstrate a widely applicable technique to absolutely calibrate the energy scale of x-ray spectra with experimentally well-known and accurately calculable transitions of highly charged ions, allowing us to measure the K-shell Rydberg spectrum of molecular O_{2} with 8 meV uncertainty. We reveal a systematic ∼450 meV shift from previous literature values, and settle an extraordinary discrepancy between astrophysical and laboratory measurements of neutral atomic oxygen, the latter being calibrated against the aforementioned O_{2} literature values. Because of the widespread use of such, now deprecated, references, our method impacts on many branches of x-ray absorption spectroscopy. Moreover, it potentially reduces absolute uncertainties there to below the meV level.

Detection of the 5p - 4f orbital crossing and its optical clock transition in Pr9.

Recent theoretical works have proposed atomic clocks based on narrow optical transitions in highly charged ions. The most interesting candidates for searches of physics beyond the Standard Model are those which occur at rare orbital crossings where the shell structure of the periodic table is reordered. There are only three such crossings expected to be accessible in highly charged ions, and hitherto none have been observed as both experiment and theory have proven difficult. In this work we observe an orbital crossing in a system chosen to be tractable from both sides: Pr[Formula: see text]. We present electron beam ion trap measurements of its spectra, including the inter-configuration lines that reveal the sought-after crossing. With state-of-the-art calculations we show that the proposed nHz-wide clock line has a very high sensitivity to variation of the fine-structure constant, [Formula: see text], and violation of local Lorentz invariance; and has extremely low sensitivity to external perturbations.

Charge Exchange Dominates Long-Range Interatomic Coulombic Decay of Excited Metal-Doped Helium Nanodroplets.

Atoms and molecules attached to rare-gas clusters are ionized by an interatomic autoionization process traditionally termed "Penning ionization" when the host cluster is resonantly excited. Here we analyze this process in the light of the interatomic Coulombic decay (ICD) mechanism, which usually contains a contribution from charge exchange at a short interatomic distance and one from virtual photon transfer at a large interatomic distance. For helium (He) nanodroplets doped with alkali metal atoms (Li, Rb), we show that long-range and short-range contributions to the interatomic autoionization can be clearly distinguished by detecting electrons and ions in coincidence. Surprisingly, ab initio calculations show that even for alkali metal atoms floating in dimples at a large distance from the nanodroplet surface, autoionization is largely dominated by charge-exchange ICD. Furthermore, the measured electron spectra manifest the ultrafast internal relaxation of the droplet mainly into the 1s2s1S state and partially into the metastable 1s2s3S state.

Closed-cycle, low-vibration 4 K cryostat for ion traps and other applications.

In vacuo cryogenic environments are ideal for applications requiring both low temperatures and extremely low particle densities. This enables reaching long storage and coherence times, for example, in ion traps, essential requirements for experiments with highly charged ions, quantum computation, and optical clocks. We have developed a novel cryostat continuously refrigerated with a pulse-tube cryocooler and providing the lowest vibration level reported for such a closed-cycle system with 1 W cooling power for a <5 K experiment. A decoupling system suppresses vibrations from the cryocooler by three orders of magnitude down to a level of 10 nm peak amplitudes in the horizontal plane. Heat loads of about 40 W (at 45 K) and 1 W (at 4 K) are transferred from an experimental chamber, mounted on an optical table, to the cryocooler through a vacuum-insulated massive 120 kg inertial copper pendulum. The 1.4 m long pendulum allows installation of the cryocooler in a separate, acoustically isolated machine room. At the experimental chamber, we measured the residual vibrations using an interferometric setup. The positioning of the 4 K elements is reproduced to better than a few micrometer after a full thermal cycle to room temperature. Extreme high vacuum on the 10-15 mbar level is achieved. In collaboration with the Max-Planck-Institut für Kernphysik, such a setup is now in operation at the Physikalisch-Technische Bundesanstalt for a next-generation optical clock experiment using highly charged ions.

Inelastic scattering of photoelectrons from He nanodroplets.

We present a detailed study of inelastic energy-loss collisions of photoelectrons emitted from He nanodroplets by tunable extreme ultraviolet (XUV) radiation. Using coincidence imaging detection of electrons and ions, we probe the lowest He droplet excited states up to the electron impact ionization threshold. We find significant signal contributions from photoelectrons emitted from free He atoms accompanying the He nanodroplet beam. Furthermore, signal contributions from photoionization and electron impact excitation/ionization occurring in pairs of nearest-neighbor atoms in the He droplets are detected. This work highlights the importance of inelastic electron scattering in the interaction of nanoparticles with XUV radiation.