arXiv subjects

Frank Stienkemeier

Publications and source records attributed to Frank Stienkemeier.

At least 19 recordsLinked to original sources

arXiv2026

Model-free pattern separation of two-color ultrafast X-ray diffraction

Two-color X-ray imaging with Free Electron Laser pulses offers a powerful approach for probing ultrafast structural dynamics in nanoscale systems, combining (near-)atomic spatial resolution with femtosecond temporal precision. The first X-ray pulse captures the object's initial state, while the second, time-delayed pulse records its subsequent evolution. A key challenge lies in disentangling the two patterns simultaneously recorded by the same detector. We demonstrate the realization of this approach on structurally varying nanoscale particles using two X-ray pulses of different photon energies, 1 and 1.2 keV. Sub-micrometer helium nanodroplets generated in vacuum are irradiated by the two X-ray pulses separated in time by up to 750 femtoseconds. Taking advantage of the high photon-energy resolution of the imaging detector, we separate the overlapping diffraction signals by analyzing individual pixel counts and applying pattern recognition. The helium nanodroplets' spherical shape allows us to cross-validate this approach by fitting the radial scattering profiles with Mie solutions for abichromatic field. The excellent agreement between the two methods, particularly in the sparsely illuminated outer regions of the diffraction patterns where high-resolution structural information is encoded, highlights the quality of this approach and its potential for future advanced X-ray movie techniques.

physics.optics↗

arXiv2026

Size characterization of neutral rare-gas clusters based on time-resolved polarization anisotropy measurements

The size determination of neutral clusters is experimentally challenging. In particular, weakly-bound rare-gas clusters tend to fragment upon ionization, resulting in systematic errors in cluster size studies. In contrast, characterization of the temporal polarization anisotropy dephasing provides a soft detection scheme for cluster size estimation, which avoids fragmentation of the clusters. Here, we present a systematic experimental study of argon and neon clusters in the size range of 50 to 10.000 atoms using this technique. In order to extract the mean cluster sizes from the data, we present an efficient analytical model of the polarization anisotropy dephasing of an ensemble of doped clusters. The approach shows remarkable sensitivity to small changes in the mean cluster size of just a few tens of atoms and allows us to refine the widely used Hagena scaling law for the estimation of rare-gas cluster sizes.

physics.atm-clus↗

arXiv2026

Ultrafast configuration changes and anomalous diffusion of an aromatic adsorbate on rare-gas nanoparticles

Nanoparticles (NPs) exhibit tunable catalytic properties and serve as nanoreactors for controlled multimolecular chemistry. The kinetics and reactivity of such systems are critically governed by the surface binding configurations of adsorbates, their stochastic fluctuations, and the adsorbate mobility across the nanosurface. However, resolving these properties with sufficient structural, spatial, and temporal resolution remains a major experimental challenge. Here, we study phthalocyanine adsorbates on rare-gas clusters as a test case. By combining high-resolution two-dimensional electronic spectroscopy and molecular dynamics simulations, we reveal the configurational dynamics of the adsorbates and establish a direct relation between these dynamics and the nanoscale properties of the clusters. Our findings indicate sub-diffusive surface motion and trapping of the adsorbate within single surface facets. Such dynamical behavior seems unexpected considering the weak adsorbate-surface interaction and cluster temperatures close to the sublimation point. These results provide direct insight into the ultrafast binding dynamics of molecular adsorbates on nanoscale objects, which is critical for our understanding of the chemistry of such systems.

physics.chem-ph↗

arXiv2026

Dissociative Single and Double Ionization of Pyridine

Dissociative ionization processes of simple heterocyclic molecules like pyridine are relevant for an understanding of radiation damage processes in biological material that occur naturally in complex condensed environments. Pyridine can thereby be considered a simple analogue of nucleobases and related ring structures are included in many important biomolecules. We present here a detailed study of dissociative single-photon single and double ionization processes using double imaging photoelectron photoion coincidence spectroscopy, supported by quantum chemical calculations. In the case of single ionization we correlate previously described cationic states to their corresponding ionic dissociation products observed at a photon energy of 23 eV, providing additional information beyond previously reported ion appearance energies. For the case of double ionization by 36 eV photons the analysis of electron-ion-ion triple coincidences provides detailed information on the onsets of various dissociative double ionization pathways, often only different by the locations of single hydrogen atoms. The detailed understanding of dissociative single and double ionization of pyridine is a prerequisite for future studies addressing radiation damage processes of such molecules in complex environments.

physics.chem-ph↗

arXiv2026

Dichography: Two-frame Ultrafast Imaging from a Single Diffraction Pattern

We experimentally demonstrate that pairs of time-delayed ultrabright and ultrashort X-ray pulses of two different colors, delivered by modern X-ray Free Electron Lasers, can provide two time-delayed snapshots of a sample. We introduce Dichography, a method that algorithmically separates the diffraction signals overlapping on the detector and independently retrieves the two images of the specimen. We employ Dichography to reconstruct two views of individual xenon-doped helium nanodroplets with 20 nm spatial resolution. The consistency of structures observed in both images at delays up to 750 fs provides evidence that, under these illumination conditions, significant structural damage only occurs at longer timescales. We further validate the method by imaging pairs of silver nanoparticles intercepted by the same light pulse. Dichography enables a new class of experiments across physics, chemistry, and materials science, making a significant step toward the original promise of X-ray free-electron lasers to capture ultrafast movies of nanomatter.

physics.optics↗

arXiv2026

Impact of interference between two infrared pulses driving high harmonic generation

Extreme ultraviolet (XUV) interferometry is technically challenging to implement. One approach to generating interference between two XUV pulses relies on driving high-harmonic generation in a gas jet with two collinearly overlapping infrared laser pulses. We investigate this scheme through a combined experimental and theoretical study, with particular emphasis on the regime of temporal overlap between the driving pulses. A special phase-modulation interferometry technique is implemented to increase the sensitivity for the comprehensive mapping of the strong-field induced high-order nonlinear response. We find that the dynamics arising from the interference of the two electric fields can be adequately described by the non-perturbative model developed by Lewenstein and co-workers.

physics.optics↗

arXiv2025

Control of molecular rotation in helium nanodroplets with an optical centrifuge

We experimentally demonstrate that the rotation of molecules embedded in helium nanodroplets can be controlled with an optical centrifuge, allowing for the study of molecular dynamics inside the strongly interacting many-body environment of superfluid helium at variable levels of rotational excitation. By doping the droplets with dimers of nitric oxide, (NO)$_2$, and measuring the degree of their centrifuge-induced alignment as a function of time, we show both the forced in-field rotation of molecules in a continuous range of frequencies, as well as the field-free resonant rotation with a long nanosecond-scale decay. The ability to control and monitor the rotational dynamics of molecular rotors inside the superfluid medium may shed new light on superfluidity and the interaction of superfluids with defects at the atomic level.

quant-ph↗

arXiv2025

Anisotropic fluorescence signals retarded dipole-dipole interactions in a thermal atomic cloud

We experimentally observe and theoretically explain anisotropic multiple quantum coherence signals in the fluorescence from dilute thermal potassium vapors, at room temperature and particle densities $\sim 10^8\ \rm{cm}^{-3}$. We identify the retarded part of the geometrically fully resolved inter-atomic, resonant dipole-dipole interaction as the crucial ingredient to theoretically reproduce all qualitative features of the experimental spectra.

quant-ph↗

arXiv2025

H2-roaming dynamics in the formation of H3+ following two-photon double ionization of ethanol and aminoethanol

Roaming reactions involving a neutral fragment of a molecule that transiently wanders around another fragment before forming a new bond are intriguing and peculiar pathways for molecular rearrangement. Such reactions can occur for example upon double ionization of small organic molecules, and have recently sparked much scientific interest. We have studied the dynamics of the H$_2$-roaming reaction leading to the formation of H$_3^+$ after two-photon double ionization of ethanol and 2-aminoethanol, using an XUV-UV pump-probe scheme. For ethanol, we find dynamics similar to previous studies employing different pump-probe schemes, indicating the independence of the observed dynamics from the method of ionization and the photon energy of the disruptive probe pulse. Surprisingly, we do not observe a kinetic isotope effect in ethanol-D$_6$, in contrast to previous experiments on methanol where such an effect was observed. This distinction indicates fundamental differences in the energetics of the reaction pathways as compared to the methanol molecule. The larger number of possible roaming pathways compared to methanol complicates the analysis considerably. In contrast to previous studies, we additionally analyze a broad range of dissociative ionization products, which feature distinct dynamics from that of H$_{3}^{+}$ and allow initial insight into the action of the disruptive UV-probe pulse.

physics.chem-ph↗

arXiv2024

Strong-field quantum control in the extreme ultraviolet using pulse shaping

Tailored light-matter interactions in the strong coupling regime enable the manipulation and control of quantum systems with up to unit efficiency, with applications ranging from quantum information to photochemistry. While strong light-matter interactions are readily induced at the valence electron level using long-wavelength radiation, comparable phenomena have been only recently observed with short wavelengths, accessing highly-excited multi-electron and inner-shell electron states. However, the quantum control of strong-field processes at short wavelengths has not been possible, so far, due to the lack of pulse shaping technologies in the extreme ultraviolet (XUV) and X-ray domain. Here, exploiting pulse shaping of the seeded free-electron laser (FEL) FERMI, we demonstrate the strong-field quantum control of ultrafast Rabi dynamics in helium atoms with high fidelity. Our approach unravels a strong dressing of the ionization continuum, otherwise elusive to experimental observables. The latter is exploited to achieve control of the total ionization rate, with prospective applications in many XUV and soft X-ray experiments. Leveraging recent advances in intense few-femtosecond to attosecond XUV to soft X-ray light sources, our results open an avenue to the efficient manipulation and selective control of core electron processes and electron correlation phenomena in real time.

physics.atom-ph↗

arXiv2024

Non-adiabatic electronic relaxation of tetracene from its brightest singlet excited state

The ultrafast relaxation dynamics of tetracene following UV excitation to a bright singlet state S6 has been studied with time-resolved photoelectron spectroscopy. With the help of high-level ab-initio multireference perturbation theory calculations, we assign photoelectron signals to intermediate dark electronic states S3, S4 and S5 as well as a to a low-lying electronic state S2. The energetic structure of these dark states has not been determined experimentally previously. The time-dependent photoelectron yields assigned to the states S6, S5 and S4 have been analyzed and reveal the depopulation of S6 within 50 fs, while S5 and S4 are populated with delays of about 50 and 80 fs. The dynamics of the lower-lying states S3 and S2 seem to agree with a delayed population coinciding with the depopulation of the higher-lying states S4-S6, but could not be elucidated in full detail due to the low signal levels of the corresponding two-photon ionization probe processes.

physics.chem-ph↗

arXiv2024

Method of Kinetic Energy Reconstruction from Time-of-Flight Mass Spectra

We present a method for the reconstruction of ion kinetic energy distributions from ion time-of-flight mass spectra through ion trajectory simulations. In particular, this method is applicable to complicated spectrometer geometries with largely anisotropic ion collection efficiencies. A calibration procedure using a single ion mass peak allows the accurate determination of parameters related to the spectrometer calibration, experimental alignment and instrument response function, which improves the agreement between simulations and experiment. The calibrated simulation is used to generate a set of basis functions for the time-of-flight spectra, which are then used to transform from time-of-flight to kinetic-energy spectra. We demonstrate this reconstruction method on a recent pump-probe experiment by Asmussen et al. (J. D. Asmussen et al., Phys. Chem. Chem. Phys., 23, 15138, (2021)) on helium nanodroplets and retrieve time-resolved kinetic-energy-release spectra for the ions from ion time-of-flight spectra.

physics.atm-clus↗

arXiv2023

Two-dimensional electronic spectroscopy of an ultracold gas

Femtosecond coherent multidimensional spectroscopy is demonstrated for an ultracold gas. For this, a setup for phase modulation spectroscopy is used to probe the $3^2\mathrm{S}_{1/2} - 2^2\mathrm{P}_{1/2, 3/2}$ transition in an 800 $μ$K-cold sample of $^7$Li atoms confined in a magneto-optical trap. The observation of a double quantum coherence response, a signature of interparticle interactions, paves the way for detailed investigations of few- and many-body effects in ultracold atomic and molecular gases using this technique. The experiment combines a frequency resolution of 3 GHz with a potential time resolution of 200 fs, which allows for high-resolution studies of ultracold atoms and molecules both in the frequency and in the time domain.

physics.atom-ph↗

arXiv2022

Pulse overlap ambiguities in multiple quantum coherence spectroscopy

Coherent two-dimensional electronic spectroscopy probes ultrafast dynamics using femtosecond pulses. In case the timescale of the studied dynamics become comparable to the pulse duration, pulse overlap effects may compromise the experimental data. Here, we perform one-dimensional coherence scans and study pulse overlap effects in clean two-level systems. We find parasitic multiple-quantum coherence signals as a consequence of the arbitrary time ordering during the temporal pulse overlap. Surprisingly, the signal lifetimes exceed the temporal pulse overlap by a factor of 1.8. These findings have important implications for the interpretation of higher-order coherent two-dimensional and related spectroscopy experiments.

physics.chem-ph↗

arXiv2022

Diffraction imaging of light induced dynamics in xenon-doped helium nanodroplets

We have explored the light induced dynamics in superfluid helium nanodroplets with wide-angle scattering in a pump-probe measurement scheme. The droplets are doped with xenon atoms to facilitate the ignition of a nanoplasma through irradiation with near-infrared laser pulses. After a variable time delay of up to 800 ps, we image the subsequent dynamics using intense extreme ultraviolet pulses from the FERMI free-electron laser. The recorded scattering images exhibit complex intensity fluctuations that are categorized based on their characteristic features. Systematic simulations of wide-angle diffraction patterns are performed, which can qualitatively explain the observed features by employing model shapes with both randomly distributed as well as structured, symmetric distortions. This points to a connection between the dynamics and the positions of the dopants in the droplets. In particular, the structured fluctuations might be governed by an underlying array of quantized vortices in the superfluid droplet as has been observed in previous small-angle diffraction experiments. Our results provide a basis for further investigations of dopant-droplet interactions and associated heating mechanisms.

physics.atm-clus↗

arXiv2022

High-resolution two-dimensional electronic spectroscopy reveals homogeneous line profiles in isolated nanoparticles

Doped clusters in the gas phase provide nanoconfined model systems for the study of system-bath interactions. To gain insight into interaction mechanisms between chromophores and their environment, the ensemble inhomogeneity has to be lifted and the homogeneous line profile must be accessed. However, such measurements are very challenging at the low particle densities and low signal levels in cluster beam experiments. Here, we dope cryogenic rare-gas clusters with phthalocyanine molecules and apply action-detected two-dimensional electronic spectroscopy to gain insight into the local molecule-cluster environment for solid and superfluid cluster species. The high-resolution homogeneous linewidth analysis provides a benchmark for the theoretical modelling of binding configurations and shows a promising route for high-resolution molecular two-dimensional spectroscopy.

physics.chem-ph↗

arXiv2022

Extreme ultraviolet wave packet interferometry of the autoionizing HeNe dimer

Femtosecond extreme ultraviolet wave packet interferometry (XUV-WPI) was applied to study resonant inter-atomic Coulombic decay (ICD) in the HeNe dimer. The high demands on phase stability and sensitivity for vibronic XUV-WPI of molecular-beam targets are met using an XUV phase-cycling scheme. The detected quantum interferences exhibit vibronic dephasing and rephasing signatures along with an ultrafast decoherence assigned to the ICD process. A Fourier analysis reveals the molecular absorption spectrum with high resolution. The demonstrated experiment shows a promising route for the real-time analysis of ultrafast ICD processes with both high temporal and spectral resolution.

physics.atm-clus↗

arXiv2022

Spin-state-controlled chemi-ionization reactions between metastable helium atoms and ground-state lithium atoms

We demonstrate the control of $^4$He(2$^3$S$_1$)-$^7$Li(2$^2$S$_{1/2}$) chemi-ionization reactions by all-optical electron-spin-state preparation of both atomic species prior to the collision process. Our results demonstrate that chemi-ionization is strongly suppressed (enhanced) for non-spin-conserving (spin-conserving) collisions at thermal energies. These findings are in good agreement with a model based on spin angular momentum coupling of the prepared atomic states to the quasi-molecular states. Small deviations from the model indicate the contribution of the $^4Σ^+$ channel to the reaction rate which is in violation of spin conservation.

physics.atom-ph↗