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The three-body recombination reaction, or ternary association, is a termolecular reaction leading to a molecule after a three-body encounter that plays a vital role in many relevant scenarios in chemical physics. Here, we introduce the Python 3-Body Recombination program, which is dedicated to the computation of atomic three-body recombination rate coefficients. The software is based on a classical trajectory approach in hyperspherical coordinates after mapping the three-body problem as a single particle in a higher-dimensional space. This theoretical approach is fully general and applicable to any ion-atom-atom or atom-atom-atom three-body process. The predictive power of the methodology has been tested in several different experimental scenarios, reaching a good description of every system. The code structure is presented alongside examples and tests to ensure the software's capacity. In addition, the performance of the software after parallelization is shown., (© 2024 Wiley Periodicals LLC.)

Chiral molecules, used in applications such as enantioselective photocatalysis 1 , circularly polarized light detection 2 and emission 3 and molecular switches 4,5 , exist in two geometrical configurations that are non-superimposable mirror images of each other. These so-called (R) and (S) enantiomers exhibit different physical and chemical properties when interacting with other chiral entities. Attosecond technology might enable influence over such interactions, given that it can probe and even direct electron motion within molecules on the intrinsic electronic timescale 6 and thereby control reactivity 7-9 . Electron currents in photoexcited chiral molecules have indeed been predicted to enable enantiosensitive molecular orientation 10 , but electron-driven chiral dynamics in neutral molecules have not yet been demonstrated owing to the lack of ultrashort, non-ionizing and perturbative light pulses. Here we use time-resolved photoelectron circular dichroism (TR-PECD) 11-15 with an unprecedented temporal resolution of 2.9 fs to map the coherent electronic motion initiated by ultraviolet (UV) excitation of neutral chiral molecules. We find that electronic beatings between Rydberg states lead to periodic modulations of the chiroptical response on the few-femtosecond timescale, showing a sign inversion in less than 10 fs. Calculations validate this and also confirm that the combination of the photoinduced chiral current with a circularly polarized probe pulse realizes an enantioselective filter of molecular orientations following photoionization. We anticipate that our approach will enable further investigations of ultrafast electron dynamics in chiral systems and reveal a route towards enantiosensitive charge-directed reactivity., (© 2024. The Author(s).)

Luminescence constitutes a unique source of insight into hot carrier processes in metals, including those in plasmonic nanostructures used for sensing and energy applications. However, being weak in nature, metal luminescence remains poorly understood, its microscopic origin strongly debated, and its potential for unraveling nanoscale carrier dynamics largely unexploited. Here, we reveal quantum-mechanical effects in the luminescence emanating from thin monocrystalline gold flakes. Specifically, we present experimental evidence, supported by first-principles simulations, to demonstrate its photoluminescence origin (i.e., radiative emission from electron/hole recombination) when exciting in the interband regime. Our model allows us to identify changes to the measured gold luminescence due to quantum-mechanical effects as the gold film thickness is reduced. Excitingly, such effects are observable in the luminescence signal from flakes up to 40 nm in thickness, associated with the out-of-plane discreteness of the electronic band structure near the Fermi level. We qualitatively reproduce the observations with first-principles modeling, thus establishing a unified description of luminescence in gold monocrystalline flakes and enabling its widespread application as a probe of carrier dynamics and light-matter interactions in this material. Our study paves the way for future explorations of hot carriers and charge-transfer dynamics in a multitude of material systems., (© 2024. The Author(s).)

The valley degree of freedom 1-4 of electrons in materials promises routes towards energy-efficient information storage with enticing prospects for quantum information processing 5-7 . Current challenges in utilizing valley polarization are symmetry conditions that require monolayer structures 8,9 or specific material engineering 10-13 , non-resonant optical control to avoid energy dissipation and the ability to switch valley polarization at optical speed. We demonstrate all-optical and non-resonant control over valley polarization using bulk MoS 2, a centrosymmetric material without Berry curvature at the valleys. Our universal method utilizes spin angular momentum-shaped trefoil optical control pulses 14,15 to switch the material's electronic topology and induce valley polarization by transiently breaking time and space inversion symmetry 16 through a simple phase rotation. We confirm valley polarization through the transient generation of the second harmonic of a non-collinear optical probe pulse, depending on the trefoil phase rotation. The investigation shows that direct optical control over the valley degree of freedom is not limited to monolayer structures. Indeed, such control is possible for systems with an arbitrary number of layers and for bulk materials. Non-resonant valley control is universal and, at optical speeds, unlocks the possibility of engineering efficient multimaterial valleytronic devices operating on quantum coherent timescales., (© 2024. The Author(s), under exclusive licence to Springer Nature Limited.)

The light-induced ultrafast switching between molecular isomers norbornadiene and quadricyclane can reversibly store and release a substantial amount of chemical energy. Prior work observed signatures of ultrafast molecular dynamics in both isomers upon ultraviolet excitation but could not follow the electronic relaxation all the way back to the ground state experimentally. Here we study the electronic relaxation of quadricyclane after exciting in the ultraviolet (201 nanometres) using time-resolved gas-phase extreme ultraviolet photoelectron spectroscopy combined with non-adiabatic molecular dynamics simulations. We identify two competing pathways by which electronically excited quadricyclane molecules relax to the electronic ground state. The fast pathway (<100 femtoseconds) is distinguished by effective coupling to valence electronic states, while the slow pathway involves initial motions across Rydberg states and takes several hundred femtoseconds. Both pathways facilitate interconversion between the two isomers, albeit on different timescales, and we predict that the branching ratio of norbornadiene/quadricyclane products immediately after returning to the electronic ground state is approximately 3:2., (© 2024. The Author(s).)

Ever since its discovery 1 , the notion of the Berry phase has permeated all branches of physics and plays an important part in a variety of quantum phenomena 2 . However, so far all its realizations have been based on a continuous evolution of the quantum state, following a cyclic path. Here we introduce and demonstrate a conceptually new manifestation of the Berry phase in light-driven crystals, in which the electronic wavefunction accumulates a geometric phase during a discrete evolution between different bands, while preserving the coherence of the process. We experimentally reveal this phase by using a strong laser field to engineer an internal interferometer, induced during less than one cycle of the driving field, which maps the phase onto the emission of higher-order harmonics. Our work provides an opportunity for the study of geometric phases, leading to a variety of observations in light-driven topological phenomena and attosecond solid-state physics., (© 2024. The Author(s).)

Single-shot coherent diffraction imaging of isolated nanosized particles has seen remarkable success in recent years, yielding in-situ measurements with ultra-high spatial and temporal resolution. The progress of high-repetition-rate sources for intense X-ray pulses has further enabled recording datasets containing millions of diffraction images, which are needed for the structure determination of specimens with greater structural variety and dynamic experiments. The size of the datasets, however, represents a monumental problem for their analysis. Here, we present an automatized approach for finding semantic similarities in coherent diffraction images without relying on human expert labeling. By introducing the concept of projection learning, we extend self-supervised contrastive learning to the context of coherent diffraction imaging and achieve a dimensionality reduction producing semantically meaningful embeddings that align with physical intuition. The method yields substantial improvements compared to previous approaches, paving the way toward real-time and large-scale analysis of coherent diffraction experiments at X-ray free-electron lasers., Competing Interests: Competing interestsThe authors declare no competing financial or non-financial interests., (© The Author(s) 2023, corrected publication 2023.)

Magnetic nanoparticles such as FePt in the L1 0 phase are the bedrock of our current data storage technology. As the grains become smaller to keep up with technological demands, the superparamagnetic limit calls for materials with higher magnetocrystalline anisotropy. This, in turn, reduces the magnetic exchange length to just a few nanometers, enabling magnetic structures to be induced within the nanoparticles. Here, we describe the existence of spin-wave solitons, dynamic localized bound states of spin-wave excitations, in FePt nanoparticles. We show with time-resolved x-ray diffraction and micromagnetic modeling that spin-wave solitons of sub-10 nm sizes form out of the demagnetized state following femtosecond laser excitation. The measured soliton spin precession frequency of 0.1 THz positions this system as a platform to develop novel miniature devices.

Structured light, which exhibits nontrivial intensity, phase, and polarization patterns in space, has key applications ranging from imaging and 3D micromanipulation to classical and quantum communication. However, to date, its application to molecular chirality has been limited by the weakness of magnetic interactions. Here we structure light's local handedness in space to introduce and realize an enantio-sensitive interferometer for efficient chiral recognition without magnetic interactions, which can be seen as an enantio-sensitive version of Young's double slit experiment. Upon interaction with isotropic chiral media, such chirality-structured light effectively creates chiral emitters of opposite handedness, located at different positions in space. We show that if the distribution of light's handedness breaks left-right symmetry, the interference of these chiral emitters leads to unidirectional bending of the emitted light, in opposite directions in media of opposite handedness, even if the number of the left-handed and right-handed emitters excited in the medium is exactly the same. Our work introduces the concepts of polarization of chirality and chirality-polarized light, exposes the immense potential of sculpting light's local chirality, and offers novel opportunities for efficient chiral discrimination, enantio-sensitive optical molecular fingerprinting and imaging on ultrafast time scales.

Circularly polarized attosecond pulses are powerful tool to study chiral light-matter interaction via chiral electron dynamics. However, access to isolated circularly polarized attosecond pulses enabling straightforward interpretation of measurements, still remains a challenge. In this work, we experimentally demonstrate the generation of highly elliptically polarized high-harmonics in a two-color, bi-circular, collinear laser field. The intensity and shape of the combined few-cycle driving radiation is optimized to produce a broadband continuum with enhanced spectral chirality in the range of 15-55 eV supporting the generation of isolated attosecond pulses with duration down to 150 as. We apply spectrally resolved polarimetry to determine the full Stokes vector of different spectral components of the continuum, yielding a homogenous helicity distribution with ellipticity in the range of 0.8-0.95 and a negligible unpolarized content.

Topological insulators combine insulating properties in the bulk with scattering-free transport along edges, supporting dissipationless unidirectional energy and information flow even in the presence of defects and disorder. The feasibility of engineering quantum Hamiltonians with photonic tools, combined with the availability of entangled photons, raises the intriguing possibility of employing topologically protected entangled states in optical quantum computing and information processing. However, while two-photon states built as a product of two topologically protected single-photon states inherit full protection from their single-photon "parents", a high degree of non-separability may lead to rapid deterioration of the two-photon states after propagation through disorder. In this work, we identify physical mechanisms which contribute to the vulnerability of entangled states in topological photonic lattices. Further, we show that in order to maximize entanglement without sacrificing topological protection, the joint spectral correlation map of two-photon states must fit inside a well-defined topological window of protection.

Topological states of matter exhibit fascinating physics combined with an intrinsic stability. A key challenge is the fast creation of topological phases, which requires massive reorientation of charge or spin degrees of freedom. Here we report the picosecond emergence of an extended topological phase that comprises many magnetic skyrmions. The nucleation of this phase, followed in real time via single-shot soft X-ray scattering after infrared laser excitation, is mediated by a transient topological fluctuation state. This state is enabled by the presence of a time-reversal symmetry-breaking perpendicular magnetic field and exists for less than 300 ps. Atomistic simulations indicate that the fluctuation state largely reduces the topological energy barrier and thereby enables the observed rapid and homogeneous nucleation of the skyrmion phase. These observations provide fundamental insights into the nature of topological phase transitions, and suggest a path towards ultrafast topological switching in a wide variety of materials through intermediate fluctuating states.

Photoinduced isomerization reactions lie at the heart of many chemical processes in nature. The mechanisms of such reactions are determined by a delicate interplay of coupled electronic and nuclear dynamics occurring on the femtosecond scale, followed by the slower redistribution of energy into different vibrational degrees of freedom. Here we apply time-resolved photoelectron spectroscopy with a seeded extreme ultraviolet free-electron laser to trace the ultrafast ring opening of gas-phase thiophenone molecules following ultraviolet photoexcitation. When combined with ab initio electronic structure and molecular dynamics calculations of the excited- and ground-state molecules, the results provide insights into both the electronic and nuclear dynamics of this fundamental class of reactions. The initial ring opening and non-adiabatic coupling to the electronic ground state are shown to be driven by ballistic S-C bond extension and to be complete within 350 fs. Theory and experiment also enable visualization of the rich ground-state dynamics that involve the formation of, and interconversion between, ring-opened isomers and the cyclic structure, as well as fragmentation over much longer timescales.

We have investigated the ionization and fragmentation of a metallo-endohedral fullerene, Sc 3 N@C 80 , using ultrashort (10 fs) x-ray pulses. Following selective ionization of a Sc (1s) electron (hν = 4.55 keV), an Auger cascade leads predominantly to either a vibrationally cold multiply charged parent molecule or multifragmentation of the carbon cage following a phase transition. In contrast to previous studies, no intermediate regime of C 2 evaporation from the carbon cage is observed. A time-delayed, hard x-ray pulse (hν = 5.0 keV) was used to attempt to probe the electron transfer dynamics between the encapsulated Sc species and the carbon cage. A small but significant change in the intensity of Sc-containing fragment ions and coincidence counts for a delay of 100 fs compared to 0 fs, as well as an increase in the yield of small carbon fragment ions, may be indicative of incomplete charge transfer from the carbon cage on the sub-100 fs time scale.

Refraction is a well-known optical phenomenon that alters the direction of light waves propagating through matter. Microscopes, lenses and prisms based on refraction are indispensable tools for controlling light beams at visible, infrared, ultraviolet and X-ray wavelengths 1 . In the past few decades, a range of extreme-ultraviolet and soft-X-ray sources has been developed in laboratory environments 2-4 and at large-scale facilities 5,6 . But the strong absorption of extreme-ultraviolet radiation in matter hinders the development of refractive lenses and prisms in this spectral region, for which reflective mirrors and diffractive Fresnel zone plates 7 are instead used for focusing. Here we demonstrate control over the refraction of extreme-ultraviolet radiation by using a gas jet with a density gradient across the profile of the extreme-ultraviolet beam. We produce a gas-phase prism that leads to a frequency-dependent deflection of the beam. The strong deflection near to atomic resonances is further used to develop a deformable refractive lens for extreme-ultraviolet radiation, with low absorption and a focal length that can be tuned by varying the gas pressure. Our results open up a route towards the transfer of refraction-based techniques, which are well established in other spectral regions, to the extreme-ultraviolet domain.

Spintronics is a research field that aims to understand and control spins on the nanoscale and should enable next-generation data storage and manipulation. One technological and scientific key challenge is to stabilize small spin textures and to move them efficiently with high velocities. For a long time, research focused on ferromagnetic materials, but ferromagnets show fundamental limits for speed and size. Here, we circumvent these limits using compensated ferrimagnets. Using ferrimagnetic Pt/Gd 44 Co 56 /TaO x films with a sizeable Dzyaloshinskii-Moriya interaction, we realize a current-driven domain wall motion with a speed of 1.3 km s -1 near the angular momentum compensation temperature (T A ) and room-temperature-stable skyrmions with minimum diameters close to 10 nm near the magnetic compensation temperature (T M ). Both the size and dynamics of the ferrimagnet are in excellent agreement with a simplified effective ferromagnet theory. Our work shows that high-speed, high-density spintronics devices based on current-driven spin textures can be realized using materials in which T A and T M are close together.

Free-electron lasers (FELs) in the extreme ultraviolet (XUV) and X-ray regime opened up the possibility for experiments at high power densities, in particular allowing for fluence-dependent absorption and scattering experiments to reveal non-linear light-matter interactions at ever shorter wavelengths. Findings of such non-linear effects are met with tremendous interest, but prove difficult to understand and model due to the inherent shot-to-shot fluctuations in photon intensity and the often structured, non-Gaussian spatial intensity profile of a focused FEL beam. Presently, the focused beam is characterized and optimized separately from the actual experiment. Here, we present the simultaneous measurement of XUV diffraction signals from solid samples in tandem with the corresponding single-shot spatial fluence distribution on the actual sample. Our in situ characterization scheme enables direct monitoring of the sample illumination, providing a basis to optimize and quantitatively understand FEL experiments.

A new device for polarization control at the free electron laser facility FLASH1 at DESY has been commissioned for user operation. The polarizer is based on phase retardation upon reflection off metallic mirrors. Its performance is characterized in three independent measurements and confirms the theoretical predictions of efficient and broadband generation of circularly polarized radiation in the extreme ultraviolet spectral range from 35 eV to 90 eV. The degree of circular polarization reaches up to 90% while maintaining high total transmission values exceeding 30%. The simple design of the device allows straightforward alignment for user operation and rapid switching between left and right circularly polarized radiation.

The temporal evolution of the exchange-split Δ(2)-like Σ valence bands of the 4f-ferromagnet gadolinium after femtosecond laser excitation has been studied using angle-resolved photoelectron spectroscopy based on high-order harmonic generation. The ultrafast drop of the exchange splitting reflects the magnetic response seen in femtosecond magnetic dichroism experiments. However, while the minority valence band reacts immediately, the response of the majority counterpart is delayed by 1 picosecond and is only half as fast. These findings demonstrate that laser excitation drives the valence band structure out of magnetic equilibrium.

We report on the generation and laser acceleration of bunches of energetic deuterons with a small energy spread at about 2 MeV. This quasimonoenergetic peak within the ion energy spectrum was observed when heavy-water microdroplets were irradiated with ultrashort laser pulses of about 40 fs duration and high (10(-8)) temporal contrast, at an intensity of 10(19) W/cm(2). The results can be explained by a simple physical model related to spatial separation of two ion species within a finite-volume target. The production of quasimonoenergetic ions is a long-standing goal in laser-particle acceleration; it could have diverse applications such as in medicine or in the development of future compact ion accelerators.

Exchange splitting and dynamics of image-potential states in front of a 3 monolayer iron film on Cu(100) have been studied with time-, energy-, and spin-resolved bichromatic two-photon photoemission. For the first image-potential state n=1 we observe an exchange splitting of 56 +/- 10 meV and spin-dependent lifetimes of 16 +/- 2 fs for majority-spin and of 11 +/- 2 fs for minority-spin electrons, respectively. The time-resolved studies of both the population and the linewidth of image-potential states manifest that at the magnetic surface not only inelastic but also quasielastic scattering processes are spin dependent.