Topologically controlled synthesis of active colloidal bipeds.

Topological growth control allows to produce a narrow distribution of outgrown colloidal rods with defined and adjustable length. We use an external magnetic field to assemble paramagnetic colloidal spheres into colloidal rods of a chosen length. The rods reside above a metamorphic hexagonal magnetic pattern. The periodic repetition of specific loops of the orientation of an applied external field renders paramagnetic colloidal particles and their assemblies into active bipeds that walk on the pattern. The metamorphic patterns allow the robust and controlled polymerization of single colloids to bipeds of a desired length. The colloids are exposed to this fixed external control loop that causes multiple simultaneous responses: Small bipeds and single colloidal particles interpret the external magnetic loop as an order to walk toward the active zone, where they assemble and polymerize. Outgrown bipeds interpret the same loop as an order to walk away from the active zone. The topological transition occurs solely for the growing biped and nothing is changed in the environment nor in the magnetic control loop. As in many biological systems the decision of a biped that reached its outgrown length to walk away from the reaction site is made internally, not externally.

Experimental Realization of Auger Decay in the Field of a Positive Elementary Charge.

Auger electron spectroscopy is an omnipresent experimental tool in many fields of fundamental research and applied science. The determination of the kinetic energies of the Auger electrons yields information about the element emitting the electron and its chemical environment at the time of emission. Here, we present an experimental approach to determine Auger spectra for emitter sites in the vicinity of a positive elementary charge based on electron-electron-electron and electron-electron-photon coincidence spectroscopy. We observe a characteristic redshift of the Auger spectrum caused by the Coulomb interaction with the charged environment. Our results are relevant for the interpretation of Auger spectra of extended systems like large molecules, clusters, liquids, and solids, in particular in high-intensity radiation fields which are nowadays routinely available, e.g., at x-ray free-electron laser facilities. The effect has been widely ignored in the literature so far, and some interpretations of Auger spectra from clusters might need to be revisited.

X-ray radiation damage cycle of solvated inorganic ions.

X-ray-induced damage is one of the key topics in radiation chemistry. Substantial damage is attributed to low-energy electrons and radicals emerging from direct inner-shell photoionization or produced by subsequent processes. We apply multi-electron coincidence spectroscopy to X-ray-irradiated aqueous solutions of inorganic ions to investigate the production of low-energy electrons (LEEs) in a predicted cascade of intermolecular charge- and energy-transfer processes, namely electron-transfer-mediated decay (ETMD) and interatomic/intermolecular Coulombic decay (ICD). An advanced coincidence technique allows us to identify several LEE-producing steps during the decay of 1s vacancies in solvated Mg2+ ions, which escaped observation in previous non-coincident experiments. We provide strong evidence for the predicted recovering of the ion's initial state. In natural environments the recovering of the ion's initial state is expected to cause inorganic ions to be radiation-damage hot spots, repeatedly producing destructive particles under continuous irradiation.

Combined Funnel, Concentrator, and Particle Valve Functional Element for Magnetophoretic Bead Transport Based on Engineered Magnetic Domain Patterns.

Controlled actuation of superparamagnetic beads (SPBs) within a microfluidic environment using tailored dynamic magnetic field landscapes (MFLs) is a potent approach for the realization of point-of-care diagnostics within Lab-on-a-chip (LOC) systems. Making use of an engineered magnetic domain pattern as the MFL source, a functional LOC-element with combined magnetophoretic "funnel", concentrator, and "valve" functions for micron-sized SPBs is presented. A parallel-stripe domain pattern design with periodically decreasing/increasing stripe lengths is fabricated in a topographically flat continuous exchange biased (EB) thin film system by ion bombardment induced magnetic patterning (IBMP). It is demonstrated that, upon application of external magnetic field pulses, a fully reversible concentration of SPBs at the domain pattern's focal point occurs. In addition, it is shown that this functionality may be used as an SPB "funnel", allowing only a maximum number of particles to pass through the focal point. Adjusting the pulse time length, the focal point can be clogged up for incoming SPBs, resembling an on/off switchable particle "valve". The observations are supported by quantitative theoretical force considerations.

Simultaneous and independent topological control of identical microparticles in non-periodic energy landscapes.

Topological protection ensures stability of information and particle transport against perturbations. We explore experimentally and computationally the topologically protected transport of magnetic colloids above spatially inhomogeneous magnetic patterns, revealing that transport complexity can be encoded in both the driving loop and the pattern. Complex patterns support intricate transport modes when the microparticles are subjected to simple time-periodic loops of a uniform magnetic field. We design a pattern featuring a topological defect that functions as an attractor or a repeller of microparticles, as well as a pattern that directs microparticles along a prescribed complex trajectory. Using simple patterns and complex loops, we simultaneously and independently control the motion of several identical microparticles differing only in their positions above the pattern. Combining complex patterns and complex loops we transport microparticles from unknown locations to predefined positions and then force them to follow arbitrarily complex trajectories concurrently. Our findings pave the way for new avenues in transport control and dynamic self-assembly in colloidal science.

Three-dimensional close-to-substrate trajectories of magnetic microparticles in dynamically changing magnetic field landscapes.

The transport of magnetic particles (MPs) by dynamic magnetic field landscapes (MFLs) using magnetically patterned substrates is promising for the development of Lab-on-a-chip (LOC) systems. The inherent close-to-substrate MP motion is sensitive to changing particle-substrate interactions. Thus, the detection of a modified particle-substrate separation distance caused by surface binding of an analyte is expected to be a promising probe in analytics and diagnostics. Here, we present an essential prerequisite for such an application, namely the label-free quantitative experimental determination of the three-dimensional trajectories of superparamagnetic particles (SPPs) transported by a dynamically changing MFL. The evaluation of defocused SPP images from optical bright-field microscopy revealed a "hopping"-like motion of the magnetic particles, previously predicted by theory, additionally allowing a quantification of maximum jump heights. As our findings pave the way towards precise determination of particle-substrate separations, they bear deep implications for future LOC detection schemes using only optical microscopy.

Magnetic patterning of Co/Ni layered systems by plasma oxidation.

We studied the structural, chemical, and magnetic properties of Ti/Au/Co/Ni layered systems subjected to plasma oxidation. The process results in the formation of NiO at the expense of metallic Ni, as clearly evidenced by X-ray photoelectron spectroscopy, while not affecting the surface roughness and grain size of the Co/Ni bilayers. Since the decrease of the thickness of the Ni layer and the formation of NiO increase the perpendicular magnetic anisotropy, oxidation may be locally applied for magnetic patterning. Using this approach, we created 2D heterostructures characterized by different combinations of magnetic properties in areas modified by plasma oxidation and in the regions protected from oxidation. As plasma oxidation is an easy to use, low cost, and commonly utilized technique in industrial applications, it may constitute an improvement over other magnetic patterning methods.

Artificial intelligence for online characterization of ultrashort X-ray free-electron laser pulses.

X-ray free-electron lasers (XFELs) as the world's brightest light sources provide ultrashort X-ray pulses with a duration typically in the order of femtoseconds. Recently, they have approached and entered the attosecond regime, which holds new promises for single-molecule imaging and studying nonlinear and ultrafast phenomena such as localized electron dynamics. The technological evolution of XFELs toward well-controllable light sources for precise metrology of ultrafast processes has been, however, hampered by the diagnostic capabilities for characterizing X-ray pulses at the attosecond frontier. In this regard, the spectroscopic technique of photoelectron angular streaking has successfully proven how to non-destructively retrieve the exact time-energy structure of XFEL pulses on a single-shot basis. By using artificial intelligence techniques, in particular convolutional neural networks, we here show how this technique can be leveraged from its proof-of-principle stage toward routine diagnostics even at high-repetition-rate XFELs, thus enhancing and refining their scientific accessibility in all related disciplines.

A new route for enantio-sensitive structure determination by photoelectron scattering on molecules in the gas phase.

X-Ray as well as electron diffraction are powerful tools for structure determination of molecules. Studies on randomly oriented molecules in the gas phase address cases in which molecular crystals cannot be generated or the interaction-free molecular structure is to be addressed. Such studies usually yield partial geometrical information, such as interatomic distances. Here, we present a complementary approach, which allows obtaining insight into the structure, handedness, and even detailed geometrical features of molecules in the gas phase. Our approach combines Coulomb explosion imaging, the information that is encoded in the molecular-frame diffraction pattern of core-shell photoelectrons and ab initio computations. Using a loop-like analysis scheme, we are able to deduce specific molecular coordinates with sensitivity even to the handedness of chiral molecules and the positions of individual atoms, e.g., protons.

Optical and Spin Properties of NV Center Ensembles in Diamond Nano-Pillars.

Nitrogen-vacancy (NV) color centers in diamond are excellent quantum sensors possessing high sensitivity and nano-scale spatial resolution. Their integration in photonic structures is often desired, since it leads to an increased photon emission and also allows the realization of solid-state quantum technology architectures. Here, we report the fabrication of diamond nano-pillars with diameters up to 1000 nm by electron beam lithography and inductively coupled plasma reactive ion etching in nitrogen-rich diamonds (type Ib) with [100] and [111] crystal orientations. The NV centers were created by keV-He ion bombardment and subsequent annealing, and we estimate an average number of NVs per pillar to be 4300 ± 300 and 520 ± 120 for the [100] and [111] samples, respectively. Lifetime measurements of the NVs' excited state showed two time constants with average values of τ1 ≈ 2 ns and τ2 ≈ 8 ns, which are shorter as compared to a single color center in a bulk crystal (τ ≈ 10 ns). This is probably due to a coupling between the NVs as well as due to interaction with bombardment-induced defects and substitutional nitrogen (P1 centers). Optically detected magnetic resonance measurements revealed a contrast of about 5% and average coherence and relaxation times of T2 [100] = 420 ± 40 ns, T2 [111] = 560 ± 50 ns, and T1 [100] = 162 ± 11 µs, T1 [111] = 174 ± 24 µs. These pillars could find an application for scanning probe magnetic field imaging.

A localized view on molecular dissociation via electron-ion partial covariance.

Inner-shell photoelectron spectroscopy provides an element-specific probe of molecular structure, as core-electron binding energies are sensitive to the chemical environment. Short-wavelength femtosecond light sources, such as Free-Electron Lasers (FELs), even enable time-resolved site-specific investigations of molecular photochemistry. Here, we study the ultraviolet photodissociation of the prototypical chiral molecule 1-iodo-2-methylbutane, probed by extreme-ultraviolet (XUV) pulses from the Free-electron LASer in Hamburg (FLASH) through the ultrafast evolution of the iodine 4d binding energy. Methodologically, we employ electron-ion partial covariance imaging as a technique to isolate otherwise elusive features in a two-dimensional photoelectron spectrum arising from different photofragmentation pathways. The experimental and theoretical results for the time-resolved electron spectra of the 4d3/2 and 4d5/2 atomic and molecular levels that are disentangled by this method provide a key step towards studying structural and chemical changes from a specific spectator site.

Translatory and rotatory motion of exchange-bias capped Janus particles controlled by dynamic magnetic field landscapes.

Magnetic Janus particles (MJPs), fabricated by covering a non-magnetic spherical particle with a hemispherical magnetic in-plane exchange-bias layer system cap, display an onion magnetization state for comparably large diameters of a few microns. In this work, the motion characteristics of these MJPs will be investigated when they are steered by a magnetic field landscape over prototypical parallel-stripe domains, dynamically varied by superposed external magnetic field pulse sequences, in an aqueous medium. We demonstrate, that due to the engineered magnetization state in the hemispherical cap, a comparably fast, directed particle transport and particle rotation can be induced. Additionally, by modifying the frequency of the applied pulse sequence and the strengths of the individual field components, we observe a possible separation between a combined or an individual occurrence of these two types of motion. Our findings bear importance for lab-on-a-chip systems, where particle immobilization on a surface via analyte bridges shall be used for low concentration analyte detection and a particle rotation over a defined position of a substrate may dramatically increase the immobilization (and therefore analyte detection) probability.

Transport Efficiency of Biofunctionalized Magnetic Particles Tailored by Surfactant Concentration.

Controlled transport of surface-functionalized magnetic beads in a liquid medium is a central requirement for the handling of captured biomolecular targets in microfluidic lab-on-chip biosensors. Here, the influence of the physiological liquid medium on the transport characteristics of functionalized magnetic particles and on the functionality of the coupled protein is studied. These aspects are theoretically modeled and experimentally investigated for prototype superparamagnetic beads, surface-functionalized with green fluorescent protein immersed in buffer solution with different concentrations of a surfactant. The model reports on the tunability of the steady-state particle substrate separation distance to prevent their surface sticking via the choice of surfactant concentration. Experimental and theoretical average velocities are discussed for a ratchet-like particle motion induced by a dynamic external field superposed on a static locally varying magnetic field landscape. The developed model and experiment may serve as a basis for quantitative forecasts on the functionality of magnetic particle transport-based lab-on-chip devices.

Subsystem domination influence on magnetization reversal in designed magnetic patterns in ferrimagnetic Tb/Co multilayers.

Recent results showed that the ferrimagnetic compensation point and other characteristic features of Tb/Co ferrimagnetic multilayers can be tailored by He+ ion bombardment. With appropriate choices of the He+ ion dose, we prepared two types of lattices composed of squares with either Tb or Co domination. The magnetization reversal of the first lattice is similar to that seen in ferromagnetic heterostructures consisting of areas with different switching fields. However, in the second lattice, the creation of domains without accompanying domain walls is possible. These domain patterns are particularly stable because they simultaneously lower the demagnetizing energy and the energy associated with the presence of domain walls (exchange and anisotropy). For both lattices, studies of magnetization reversal show that this process takes place by the propagation of the domain walls. If they are not present at the onset, the reversal starts from the nucleation of reversed domains and it is followed by domain wall propagation. The magnetization reversal process does not depend significantly on the relative sign of the effective magnetization in areas separated by domain walls.

Gauge invariant and gauge dependent aspects of topological walking colloidal bipeds.

Paramagnetic colloidal spheres assemble to colloidal bipeds of various length in an external magnetic field. When the bipeds reside above a magnetic pattern and we modulate the direction of the external magnetic field, the rods perform topologically distinct classes of protected motion above the pattern. The topological protection allows each class to be robust against small continuous deformations of the driving loop of the external field. We observe motion of the rod from a passive central sliding and rolling motion for short bipeds toward a walking motion with both ends of the rod alternately touching down on the pattern for long bipeds. The change of character of the motion occurs in form of discrete topological transitions. The topological protection makes walking a form of motion robust against the breaking of the non symmorphic symmetry. In patterns with non symmorphic symmetry walking is reversible. In symmorphic patterns lacking a glide plane the walking can be irreversible or reversible involving or not involving ratchet jumps. Using different gauges allows us to unravel the active and passive aspects of the topological walks.

Site-specific interrogation of an ionic chiral fragment during photolysis using an X-ray free-electron laser.

Short-wavelength free-electron lasers with their ultrashort pulses at high intensities have originated new approaches for tracking molecular dynamics from the vista of specific sites. X-ray pump X-ray probe schemes even allow to address individual atomic constituents with a 'trigger'-event that preludes the subsequent molecular dynamics while being able to selectively probe the evolving structure with a time-delayed second X-ray pulse. Here, we use a linearly polarized X-ray photon to trigger the photolysis of a prototypical chiral molecule, namely trifluoromethyloxirane (C3H3F3O), at the fluorine K-edge at around 700 eV. The created fluorine-containing fragments are then probed by a second, circularly polarized X-ray pulse of higher photon energy in order to investigate the chemically shifted inner-shell electrons of the ionic mother-fragment for their stereochemical sensitivity. We experimentally demonstrate and theoretically support how two-color X-ray pump X-ray probe experiments with polarization control enable XFELs as tools for chiral recognition.

Interatomic and Intermolecular Coulombic Decay.

Interatomic or intermolecular Coulombic decay (ICD) is a nonlocal electronic decay mechanism occurring in weakly bound matter. In an ICD process, energy released by electronic relaxation of an excited atom or molecule leads to ionization of a neighboring one via Coulombic electron interactions. ICD has been predicted theoretically in the mid nineties of the last century, and its existence has been confirmed experimentally approximately ten years later. Since then, a number of fundamental and applied aspects have been studied in this quickly growing field of research. This review provides an introduction to ICD and draws the connection to related energy transfer and ionization processes. The theoretical approaches for the description of ICD as well as the experimental techniques developed and employed for its investigation are described. The existing body of literature on experimental and theoretical studies of ICD processes in different atomic and molecular systems is reviewed.

Simultaneous polydirectional transport of colloidal bipeds.

Detailed control over the motion of colloidal particles is relevant in many applications in colloidal science such as lab-on-a-chip devices. Here, we use an external magnetic field to assemble paramagnetic colloidal spheres into colloidal rods of several lengths. The rods reside above a square magnetic pattern and are transported via modulation of the direction of the external magnetic field. The rods behave like bipeds walking above the pattern. Depending on their length, the bipeds perform topologically distinct classes of protected walks. We design parallel polydirectional modulation loops of the external field that command up to six classes of bipeds to walk on distinct predesigned paths. Using such loops, we induce the collision of reactant bipeds, their polymerization addition reaction to larger bipeds, the separation of product bipeds from the educts, the sorting of different product bipeds, and also the parallel writing of a word consisting of several letters. Our ideas and methodology might be transferred to other systems for which topological protection is at work.

Magnetic Structure of Ion-Beam Imprinted Stripe Domains Determined by Neutron Scattering.

We present a detailed analysis of the in-plane magnetic vector configuration in head-to-head/tail-to-tail stripe domain patterns of nominal 5 µm width. The patterns have been created by He-ion bombardment induced magnetic patterning of a CoFe/IrMn3 exchange bias thin-film system. Quantitative information about the chemical and magnetic structure is obtained from polarized neutron reflectometry (PNR) and off-specular scattering (OSS). The technique provides information on the magnetic vector orientation and magnitude along the lateral coordinate of the sample, as well as the chemical and magnetic layer structure as a function of depth. Additional sensitivity to magnetic features is obtained through a neutron wave field resonance, which is fully accounted for in the presented analysis. The scattering reveals a domain width imbalance of 5.3 to 3.7 µm of virgin and bombarded stripes, respectively. Further, we report that the magnetization in the bombarded stripe significantly deviates from the head-to-head arrangement. A domain wall of 0.6 µm with homogeneous magnetization direction is found to separate the two neighboring domains. The results contain detailed information on length scales and magnetization vectors provided by PNR and OSS in absolute units. We illustrate the complementarity of the technique to microscopy techniques for obtaining a quantitative description of imprinted magnetic domain patterns and illustrate its applicability to different sample systems.

Magnetic Domains without Domain Walls: A Unique Effect of He

We show that it is possible to engineer magnetic multidomain configurations without domain walls in a prototypical rare-earth-transition-metal ferrimagnet using keV He^{+} ion bombardment. We additionally show that these patterns display a particularly stable magnetic configuration due to a deep minimum in the energy of the system caused by flux closure and a corresponding reduction of the magnetostatic energy without an increase in energy by exchange and anisotropy terms across the walls. This occurs because light-ion bombardment affects an element's relative contribution to the properties of the ferrimagnet differently. Therefore, it is possible to control the relative contribution from each magnetic subsystem. The selection of material and the use of light-ion bombardment allow us to engineer domain patterns in continuous magnetic films, which open a way to fabricate them in a much smaller scale than currently possible. Our Letter emphasizes that the right criterion to determine the presence or absence of a domain wall is whether there is a rotation of the spin for each sublattice and that changes of the direction of effective magnetization alone do not constitute an appropriate criterion.