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How related are the ergodic properties of the over- and underdamped Langevin equations driven by fractional Gaussian noise? We here find that for massive particles performing fractional Brownian motion (FBM) inertial effects not only destroy the stylized fact of the equivalence of the ensemble-averaged mean-squared displacement (MSD) to the time-averaged MSD (TAMSD) of overdamped or massless FBM, but also dramatically alter the values of the ergodicity-breaking parameter (EB). Our theoretical results for the behavior of EB for underdamped or massive FBM for varying particle mass m, Hurst exponent H, and trace length T are in excellent agreement with the findings of stochastic computer simulations. The current results can be of interest for the experimental community employing various single-particle-tracking techniques and aiming at assessing the degree of nonergodicity for the recorded time series (studying, e.g., the behavior of EB versus lag time). To infer FBM as a realizable model of anomalous diffusion for a set single-particle-tracking data when massive particles are being tracked, the EBs from the data should be compared to EBs of massive (rather than massless) FBM.
We employ Langevin-dynamics simulations to unveil non-Brownian and non-Gaussian center-of-mass self-diffusion of massive flexible dumbbell-shaped particles in crowded two-dimensional solutions. We study the intradumbbell dynamics of the relative motion of the two constituent elastically coupled disks. Our main focus is on effects of the crowding fraction phi and of the particle structure on the diffusion characteristics. We evaluate the time-averaged mean-squared displacement (TAMSD), the displacement probability-density function (PDF), and the displacement autocorrelation function (ACF) of the dimers. For the TAMSD at highly crowded conditions of dumbbells, e.g., we observe a transition from the short-time ballistic behavior, via an intermediate subdiffusive regime, to long-time Brownian-like spreading dynamics. The crowded system of dimers exhibits two distinct diffusion regimes distinguished by the scaling exponent of the TAMSD, the dependence of the diffusivity on phi, and the features of the displacement-ACF. We attribute these regimes to a crowding-induced transition from viscous to viscoelastic diffusion upon growing phi. We also analyze the relative motion in the dimers, finding that larger phi suppress their vibrations and yield strongly non-Gaussian PDFs of rotational displacements. For the diffusion coefficients D(phi) of translational and rotational motion of the dumbbells an exponential decay with phi for weak and a power-law variation D(phi) proportional to (phi - phi(star))(2.4) for strong crowding is found. A comparison of simulation results with theoretical predictions for D(phi) is discussed and some relevant experimental systems are overviewed.
We consider the spatiotemporal states of an ensemble of nonlocally coupled nonidentical phase oscillators, which correspond to different regimes of the long-term evolution of such a system. We have obtained homogeneous, twisted, and nonhomogeneous stationary solutions to the Ott-Antonsen equations corresponding to key variants of the realized collective rotational motion of elements of the medium in question with nonzero mesoscopic characteristics determining the degree of coherence of the dynamics of neighboring particles. We have described the procedures of the search for the class of nonhomogeneous solutions as stationary points of the auxiliary point map and of determining the stability based on analysis of the eigenvalue spectrum of the composite operator. Static and breather cluster regimes have been demonstrated and described, as well as the regimes with an irregular behavior of averaged complex fields including, in particular, the local order parameter.
We consider an array of nonlocally coupled oscillators on a ring, which for equally spaced units possesses a Kuramoto-Battogtokh chimera regime and a synchronous state. We demonstrate that disorder in oscillators positions leads to a transition from the synchronous to the chimera state. For a static (quenched) disorder we find that the probability of synchrony survival depends on the number of particles, from nearly zero at small populations to one in the thermodynamic limit. Furthermore, we demonstrate how the synchrony gets destroyed for randomly (ballistically or diffusively) moving oscillators. We show that, depending on the number of oscillators, there are different scalings of the transition time with this number and the velocity of the units.
Binary III-V nitrides such as AlN, GaN and InN in the wurtzite-type structure have long been considered as potent semiconducting materials because of their optoelectronic properties, amongst others. With rising concerns over the utilization of scarce elements, a replacement of the trivalent cations by others in ternary and multinary nitrides has led to the development of different variants of nitrides and oxide nitrides crystallizing in lower-symmetry variants of wurtzite. This work presents the symmetry relationships between these structural types specific to nitrides and oxide nitrides and updates some prior work on this matter. The non-existence of compounds crystallizing in Pmc2(1), formally the highest subgroup of the wurtzite type fulfilling Pauling's rules for 1:1:2 stoichiometries, has been puzzling scientists for a while; a rationalization is given, from a crystallographic basis, of why this space group is unlikely to be adopted.
Development of functional and stable solid polymer electrolytes (SPEs) for battery applications is an important step towards both safer batteries and for the realization of lithium-based or anode-less batteries. The interface between the lithium and the solid polymer electrolyte is one of the bottlenecks, where severe degradation is expected. Here, the stability of three different SPEs - poly(ethylene oxide) (PEO), poly(epsilon-caprolactone) (PCL) and poly(trimethylene carbonate) (PTMC) - together with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) salt, is investigated after they have been exposed to lithium metal under UHV conditions. Degradation compounds, e.g. Li-O-R, LiF and LixSyOz, are identified for all SPEs using soft X-ray photoelectron spectroscopy. A competing degradation between polymer and salt is identified in the outermost surface region (<7 nm), and is dependent on the polymer host. PTMC:LiTFSI shows the most severe decomposition of both polymer and salt followed by PCL:LiTFSI and PEO:LiTFSI. In addition, the movement of lithium species through the decomposed interface shows large variation depending on the polymer electrolyte system.
Quenching mechanism of uranyl(VI) by chloride and bromide in aqueous and non-aqueous solutions
(2021)
A major hindrance in utilizing uranyl(VI) luminescence as a standard analytical tool, for example, in environmental monitoring or nuclear industries, is quenching by other ions such as halide ions, which are present in many relevant matrices of uranyl(VI) speciation. Here, we demonstrate through a combination of time-resolved laser-induced fluorescence spectroscopy, transient absorption spectroscopy, and quantum chemistry that coordinating solvent molecules play a crucial role in U(VI) halide luminescence quenching. We show that our previously suggested quenching mechanism based on an internal redox reaction of the 1:2-uranyl-halide-complex holds also true for bromide-induced quenching of uranyl(VI). By adopting specific organic solvents, we were able to suppress the separation of the oxidized halide ligand X-2(center dot-) and the formed uranyl(V) into fully solvated ions, thereby "reigniting" U(VI) luminescence. Time-dependent density functional theory calculations show that quenching occurs through the outer-sphere complex of U(VI) and halide in water, while the ligand-to-metal charge transfer is strongly reduced in acetonitrile.
How different are the results of constant-rate resetting of anomalous-diffusion processes in terms of their ensemble-averaged versus time-averaged mean-squared displacements (MSDs versus TAMSDs) and how does stochastic resetting impact nonergodicity? We examine, both analytically and by simulations, the implications of resetting on the MSD- and TAMSD-based spreading dynamics of particles executing fractional Brownian motion (FBM) with a long-time memory, heterogeneous diffusion processes (HDPs) with a power-law space-dependent diffusivity D(x) = D0|x|gamma and their "combined" process of HDP-FBM. We find, inter alia, that the resetting dynamics of originally ergodic FBM for superdiffusive Hurst exponents develops disparities in scaling and magnitudes of the MSDs and mean TAMSDs indicating weak ergodicity breaking. For subdiffusive HDPs we also quantify the nonequivalence of the MSD and TAMSD and observe a new trimodal form of the probability density function. For reset FBM, HDPs and HDP-FBM we compute analytically and verify by simulations the short-time MSD and TAMSD asymptotes and long-time plateaus reminiscent of those for processes under confinement. We show that certain characteristics of these reset processes are functionally similar despite a different stochastic nature of their nonreset variants. Importantly, we discover nonmonotonicity of the ergodicitybreaking parameter EB as a function of the resetting rate r. For all reset processes studied we unveil a pronounced resetting-induced nonergodicity with a maximum of EB at intermediate r and EB similar to(1/r )-decay at large r. Alongside the emerging MSD-versus-TAMSD disparity, this r-dependence of EB can be an experimentally testable prediction. We conclude by discussing some implications to experimental systems featuring resetting dynamics.
Halide perovskites
(2021)
Both ground- and satellite-based airglow imaging have significantly contributed to understanding the low-latitude ionosphere, especially the morphology and dynamics of the equatorial ionization anomaly (EIA). The NASA Global-scale Observations of the Limb and Disk (GOLD) mission focuses on far-ultraviolet airglow images from a geostationary orbit at 47.5 degrees W. This region is of particular interest at low magnetic latitudes because of the high magnetic declination (i.e., about -20 degrees) and proximity of the South Atlantic magnetic anomaly. In this study, we characterize an exciting feature of the nighttime EIA using GOLD observations from October 5, 2018 to June 30, 2020. It consists of a wavelike structure of a few thousand kilometers seen as poleward and equatorward displacements of the EIA-crests. Initial analyses show that the synoptic-scale structure is symmetric about the dip equator and appears nearly stationary with time over the night. In quasi-dipole coordinates, maxima poleward displacements of the EIA-crests are seen at about +/- 12 degrees latitude and around 20 and 60 degrees longitude (i.e., in geographic longitude at the dip equator, about 53 degrees W and 14 degrees W). The wavelike structure presents typical zonal wavelengths of about 6.7 x 10(3) km and 3.3 x 10(3) km. The structure's occurrence and wavelength are highly variable on a day-to-day basis with no apparent dependence on geomagnetic activity. In addition, a cluster or quasi-periodic wave train of equatorial plasma depletions (EPDs) is often detected within the synoptic-scale structure. We further outline the difference in observing these EPDs from FUV images and in situ measurements during a GOLD and Swarm mission conjunction.
Accurate and precise characterization of cirrus cloud geometrical and optical properties is essential for better constraining their radiative footprint. A lidar-based retrieval scheme is proposed here, with its performance assessed on fine spatio-temporal observations over the Arctic site of Ny-Alesund, Svalbard. Two contributions related to cirrus geometrical (dynamic Wavelet Covariance Transform (WCT)) and optical properties (constrained Klett) are reported. The dynamic WCT rendered cirrus detection more robust, especially for thin cirrus layers that frequently remained undetected by the classical WCT method. Regarding optical characterization, we developed an iterative scheme for determining the cirrus lidar ratio (LRci) that is a crucial parameter for aerosol - cloud discrimination. Building upon the Klett-Fernald method, the LRci was constrained by an additional reference value. In established methods, such as the double-ended Klett, an aerosol-free reference value is applied. In the proposed constrained Klett, however, the reference value was approximated from cloud-free or low cloud optical depth (COD up to 0.2) profiles and proved to agree with independent Raman estimates. For optically thin cirrus, the constrained Klett inherent uncertainties reached 50% (60-74%) in terms of COD (LRci). However, for opaque cirrus COD (LRci) uncertainties were lower than 10% (15%). The detection method discrepancies (dynamic versus static WCT) had a higher impact on the optical properties of low COD layers (up to 90%) compared to optically thicker ones (less than 10%). The constrained Klett presented high agreement with two established retrievals. For an exemplary cirrus cloud, the constrained Klett estimated the COD355 (LRci355) at 0.28 +/- 0.17 (29 +/- 4 sr), the double-ended Klett at 0.27 +/- 0.15 (32 +/- 4 sr) and the Raman retrievals at 0.22 +/- 0.12 (26 +/- 11 sr). Our approach to determine the necessary reference value can also be applied in established methods and increase their accuracy. In contrast, the classical aerosol-free assumption led to 44 sr LRci overestimation in optically thin layers and 2-8 sr in thicker ones. The multiple scattering effect was corrected using Eloranta (1998) and accounted for 50-60% extinction underestimation near the cloud base and 20-30% within the cirrus layers.
Most image restoration methods in astronomy rely upon probabilistic tools that infer the best solution for a deconvolution problem. They achieve good performances when the point spread function (PSF) is spatially invariant in the image plane.
However, this condition is not always satisfied in real optical systems. We propose a new method for the restoration of images affected by static and anisotropic aberrations using Deep Neural Networks that can be directly applied to sky images.
The network is trained using simulated sky images corresponding to the T80-S Telescope optical model, a 80-cm survey imager at Cerro Tololo (Chile), which are synthesized using a Zernike polynomial representation of the optical system.
Once trained, the network can be used directly on sky images, outputting a corrected version of the image that has a constant and known PSF across its field of view. The method is to be tested on the T80-S Telescope.
We present the method and results on synthetic data.
Symmetry and its breaking crucially define the chemical properties of molecules and their functionality. Resonant inelastic X-ray scattering is a local electronic structure probe reporting on molecular symmetry and its dynamical breaking within the femtosecond scattering duration. Here, we study pyrimidine, a system from the C-2v point group, in an aqueous solution environment, using scattering though its 2a(2) resonance. Despite the absence of clean parity selection rules for decay transitions from in-plane orbitals, scattering channels including decay from the 7b(2) and 11a(1) orbitals with nitrogen lone pair character are a direct probe for molecular symmetry. Computed spectra of explicitly solvated molecules sampled from a molecular dynamics simulation are combined with the results of a quantum dynamical description of the X-ray scattering process. We observe dominant signatures of core-excited Jahn-Teller induced symmetry breaking for resonant excitation. Solvent contributions are separable by shortening of the effective scattering duration through excitation energy detuning.
Based on suggested interactions of potential tipping elements in the Earth's climate and in ecological systems, tipping cascades as possible dynamics are increasingly discussed and studied. The activation of such tipping cascades would impose a considerable risk for human societies and biosphere integrity. However, there are ambiguities in the description of tipping cascades within the literature so far. Here we illustrate how different patterns of multiple tipping dynamics emerge from a very simple coupling of two previously studied idealized tipping elements. In particular, we distinguish between a two phase cascade, a domino cascade and a joint cascade. A mitigation of an unfolding two phase cascade may be possible and common early warning indicators are sensitive to upcoming critical transitions to a certain degree. In contrast, a domino cascade may hardly be stopped once initiated and critical slowing down-based indicators fail to indicate tipping of the following element. These different potentials for intervention and anticipation across the distinct patterns of multiple tipping dynamics should be seen as a call to be more precise in future analyses of cascading dynamics arising from tipping element interactions in the Earth system.
In contrast to the common conception that the interfacial energy-level alignment is affixed once the interface is formed, we demonstrate that heterojunctions between organic semiconductors and metal-halide perovskites exhibit huge energy-level realignment during photoexcitation. Importantly, the photoinduced level shifts occur in the organic component, including the first molecular layer in direct contact with the perovskite. This is caused by charge-carrier accumulation within the organic semiconductor under illumination and the weak electronic coupling between the junction components.
The first detections of black hole-neutron star mergers (GW200105 and GW200115) by the LIGO-Virgo-Kagra Collaboration mark a significant scientific breakthrough. The physical interpretation of pre- and postmerger signals requires careful cross-examination between observational and theoretical modelling results. Here we present the first set of black hole-neutron star simulations that were obtained with the numerical-relativity code BAM. Our initial data are constructed using the public LORENE spectral library, which employs an excision of the black hole interior. BAM, in contrast, uses the moving-puncture gauge for the evolution. Therefore, we need to "stuff" the black hole interior with smooth initial data to evolve the binary system in time. This procedure introduces constraint violations such that the constraint damping properties of the evolution system are essential to increase the accuracy of the simulation and in particular to reduce spurious center-of-mass drifts. Within BAM we evolve the Z4c equations and we compare our gravitational-wave results with those of the SXS collaboration and results obtained with the SACRA code. While we find generally good agreement with the reference solutions and phase differences less than or similar to 0.5 rad at the moment of merger, the absence of a clean convergence order in our simulations does not allow for a proper error quantification. We finally present a set of different initial conditions to explore how the merger of black hole neutron star systems depends on the involved masses, spins, and equations of state.
Simple and robust
(2021)
A spectrum of 7562 publications on Molecularly Imprinted Polymers (MIPs) has been presented in literature within the last ten years (Scopus, September 7, 2020). Around 10 % of the papers published on MIPs describe the recognition of proteins. The straightforward synthesis of MIPs is a significant advantage as compared with the preparation of enzymes or antibodies. MIPs have been synthesized from only one up to six functional monomers while proteins are made up of 20 natural amino acids. Furthermore, they can be synthesized against structures of low immunogenicity and allow multi-analyte measurements via multi-target synthesis. Electrochemical methods allow simple polymer synthesis, removal of the template and readout. Among the different sensor configurations electrochemical MIP-sensors provide the broadest spectrum of protein analytes. The sensitivity of MIP-sensors is sufficiently high for biomarkers in the sub-nanomolar region, nevertheless the cross-reactivity of highly abundant proteins in human serum is still a challenge. MIPs for proteins offer innovative tools not only for clinical and environmental analysis, but also for bioimaging, therapy and protein engineering.
Destabilization of super-rotating Taylor-Couette flows by current-free helical magnetic fields
(2021)
In an earlier paper we showed that the combination of azimuthal magnetic fields and super-rotation in Taylor-Couette flows of conducting fluids can be unstable against non-axisymmetric perturbations if the magnetic Prandtl number of the fluid is Pm not equal 1. Here we demonstrate that the addition of a weak axial field component allows axisymmetric perturbation patterns for Pm of order unity depending on the boundary conditions. The axisymmetric modes only occur for magnetic Mach numbers (of the azimuthal field) of order unity, while higher values are necessary for the non-axisymmetric modes. The typical growth time of the instability and the characteristic time scale of the axial migration of the axisymmetric mode are long compared with the rotation period, but short compared with the magnetic diffusion time. The modes travel in the positive or negative z direction along the rotation axis depending on the sign of B phi Bz. We also demonstrate that the azimuthal components of flow and field perturbations travel in phase if vertical bar B phi vertical bar >> vertical bar B-z vertical bar, independent of the form of the rotation law. Within a short-wave approximation for thin gaps it is also shown (in an appendix) that for ideal fluids the considered helical magnetorotational instability only exists for rotation laws with negative shear.
Non-linear dielectric spectroscopy (NLDS) is employed as an effective tool to study relaxation processes and phase transitions of a poly(vinylidenefluoride-trifluoroethylene-chlorofluoroethylene) (P(VDF-TrFE-CFE)) relaxor-ferroelectric (R-F) terpolymer in detail. Measurements of the non-linear dielectric permittivity epsilon 2 ' reveal peaks at 30 and 80 degrees C that cannot be identified in conventional dielectric spectroscopy. By combining the results from NLDS experiments with those from other techniques such as thermally stimulated depolarization and dielectric-hysteresis studies, it is possible to explain the processes behind the additional peaks. The former peak, which is associated with the mid-temperature transition, is found in all other vinylidene fluoride-based polymers and may help to understand the non-zero epsilon 2 ' values that are detected on the paraelectric phase of the terpolymer. The latter peak can also be observed during cooling of P(VDF-TrFE) copolymer samples at 100 degrees C and is due to conduction and space-charge polarization as a result of the accumulation of real charges at the electrode-sample interface.
We investigate a diffusion process with a time-dependent diffusion coefficient, both exponentially increasing and decreasing in time, D(t)=D-0(e +/- 2 alpha t). For this (hypothetical) nonstationary diffusion process we compute-both analytically and from extensive stochastic simulations-the behavior of the ensemble- and time-averaged mean-squared displacements (MSDs) of the particles, both in the over- and underdamped limits. Simple asymptotic relations derived for the short- and long-time behaviors are shown to be in excellent agreement with the results of simulations. The diffusive characteristics in the presence of ageing are also considered, with dramatic differences of the over- versus underdamped regime. Our results for D(t)=D-0(e +/- 2 alpha t) extend and generalize the class of diffusive systems obeying scaled Brownian motion featuring a power-law-like variation of the diffusivity with time, D(t) similar to t(alpha-1). We also examine the logarithmically increasing diffusivity, D(t)=D(0)log[t/tau(0)], as another fundamental functional dependence (in addition to the power-law and exponential) and as an example of diffusivity slowly varying in time. One of the main conclusions is that the behavior of the massive particles is predominantly ergodic, while weak ergodicity breaking is repeatedly found for the time-dependent diffusion of the massless particles at short times. The latter manifests itself in the nonequivalence of the (both nonaged and aged) MSD and the mean time-averaged MSD. The current findings are potentially applicable to a class of physical systems out of thermal equilibrium where a rapid increase or decrease of the particles' diffusivity is inherently realized. One biological system potentially featuring all three types of time-dependent diffusion (power-law-like, exponential, and logarithmic) is water diffusion in the brain tissues, as we thoroughly discuss in the end.
Writing a history of a scientific theory is always difficult because it requires to focus on some key contributors and to "reconstruct" some supposed influences. In the 1970s, a new way of performing science under the name "chaos" emerged, combining the mathematics from the nonlinear dynamical systems theory and numerical simulations. To provide a direct testimony of how contributors can be influenced by other scientists or works, we here collected some writings about the early times of a few contributors to chaos theory. The purpose is to exhibit the diversity in the paths and to bring some elements-which were never published-illustrating the atmosphere of this period. Some peculiarities of chaos theory are also discussed.
Fires are a fundamental part of the Earth System. In the last decades, they have been altering ecosystem structure, biogeochemical cycles and atmospheric composition with unprecedented rapidity. In this study, we implement a complex networks-based methodology to track individual fires over space and time. We focus on extreme fires-the 5% most intense fires-in the tropical forests of the Brazilian Legal Amazon over the period 2002-2019. We analyse the interannual variability in the number and spatial patterns of extreme forest fires in years with diverse climatic conditions and anthropogenic pressure to examine potential synergies between climate and anthropogenic drivers. We observe that major droughts, that increase forest flammability, co-occur with high extreme fire years but also that it is fundamental to consider anthropogenic activities to understand the distribution of extreme fires. Deforestation fires, fires escaping from managed lands, and other types of forest degradation and fragmentation provide the ignition sources for fires to ignite in the forests. We find that all extreme forest fires identified are located within a 0.5-km distance from forest edges, and up to 56% of them are within a 1-km distance from roads (which increases to 73% within 5 km), showing a strong correlation that defines spatial patterns of extreme fires.
Topic and aim. Synchronization in populations of coupled oscillators can be characterized with order parameters that describe collective order in ensembles. A dependence of the order parameter on the coupling constants is well-known for coupled periodic oscillators. The goal of the study is to extend this analysis to ensembles of oscillators with chaotic phases, moreover with phases possessing hyperbolic chaos. Models and methods. Two models are studied in the paper. One is an abstract discrete-time map, composed with a hyperbolic Bernoulli transformation and with Kuramoto dynamics. Another model is a system of coupled continuous-time chaotic oscillators, where each individual oscillator has a hyperbolic attractor of Smale-Williams type. Results. The discrete-time model is studied with the Ott-Antonsen ansatz, which is shown to be invariant under the application of the Bernoulli map. The analysis of the resulting map for the order parameter shows, that the asynchronouis state is always stable, but the synchronous one becomes stable above a certain coupling strength. Numerical analysis of the continuous-time model reveals a complex sequence of transitions from an asynchronous state to a completely synchronous hyperbolic chaos, with intermediate stages that include regimes with periodic in time mean field, as well as with weakly and strongly irregular mean field variations. Discussion. Results demonstrate that synchronization of systems with hyperbolic chaos of phases is possible, although a rather strong coupling is required. The approach can be applied to other systems of interacting units with hyperbolic chaotic dynamics.
We introduce and study a family of lattice equations which may be viewed either as a strongly nonlinear discrete extension of the Gardner equation, or a non-convex variant of the Lotka-Volterra chain. Their deceptively simple form supports a very rich family of complex solitary patterns. Some of these patterns are also found in the quasi-continuum rendition, but the more intriguing ones, like interlaced pairs of solitary waves, or waves which may reverse their direction either spontaneously or due a collision, are an intrinsic feature of the discrete realm.
We report on the multiple response of microgels triggered by a single optical stimulus. Under irradiation, the volume of the microgels is reversibly switched by more than 20 times. The irradiation initiates two different processes: photo-isomerization of the photo-sensitive surfactant, which forms a complex with the anionic microgel, rendering it photo-responsive; and local heating due to a thermo-plasmonic effect within the structured gold layer on which the microgel is deposited. The photo-responsivity is related to the reversible accommodation/release of the photo-sensitive surfactant depending on its photo-isomerization state, while the thermo-sensitivity is intrinsically built in. We show that under exposure to green light, the thermo-plasmonic effect generates a local hot spot in the gold layer, resulting in the shrinkage of the microgel. This process competes with the simultaneous photo-induced swelling. Depending on the position of the laser spot, the spatiotemporal control of reversible particle shrinking/swelling with a predefined extent on a per-second base can be implemented.
A theory for diffusivity estimation for spatially extended activator-inhibitor dynamics modeling the evolution of intracellular signaling networks is developed in the mathematical framework of stochastic reaction-diffusion systems. In order to account for model uncertainties, we extend the results for parameter estimation for semilinear stochastic partial differential equations, as developed in Pasemann and Stannat (Electron J Stat 14(1):547-579, 2020), to the problem of joint estimation of diffusivity and parametrized reaction terms. Our theoretical findings are applied to the estimation of effective diffusivity of signaling components contributing to intracellular dynamics of the actin cytoskeleton in the model organism Dictyostelium discoideum.
Laser-based additive manufacturing methods allow the production of complex metal structures within a single manufacturing step. However, the localized heat input and the layer-wise manufacturing manner give rise to large thermal gradients. Therefore, large internal stress (IS) during the process (and consequently residual stress (RS) at the end of production) is generated within the parts. This IS or RS can either lead to distortion or cracking during fabrication or in-service part failure, respectively. With this in view, the knowledge on the magnitude and spatial distribution of RS is important to develop strategies for its mitigation. Specifically, diffraction-based methods allow the spatial resolved determination of RS in a non-destructive fashion. In this review, common diffraction-based methods to determine RS in laser-based additive manufactured parts are presented. In fact, the unique microstructures and textures associated to laser-based additive manufacturing processes pose metrological challenges. Based on the literature review, it is recommended to (a) use mechanically relaxed samples measured in several orientations as appropriate strain-free lattice spacing, instead of powder, (b) consider that an appropriate grain-interaction model to calculate diffraction-elastic constants is both material- and texture-dependent and may differ from the conventionally manufactured variant. Further metrological challenges are critically reviewed and future demands in this research field are discussed.
We investigate whether the dust content of the circum-galactic medium (CGM) depends on the location of the quasar sightline with respect to the galaxy major-axis using 13 galaxy-Mg II absorber pairs (9-81 kpc distance) from the MusE GAs FLOw and Wind (MEGAFLOW) survey at 0.4 < z < 1.4. The dust content of the CGM is obtained from [Zn/Fe] using ultraviolet and visual echelle spectrograph data. When a direct measurement of [Zn/Fe] is unavailable, we estimate the dust depletion from a method that consists in solving for the depletion from multiple singly ionized ions (e.g. Mn II, Cr II, and Zn II) since each ion depletes on dust grains at different rates. We find a positive correlation between the azimuthal angle and [Zn/Fe] with a Pearson's gamma = 0.70 +/- 0.14. The sightlines along the major axis show [Zn/Fe] < 0.5, whereas the [Zn/Fe] is > 0.8 along the minor axis. These results suggest that the CGM along the minor axis is on average more metal enriched (by approximate to 1 dex) than the gas located along the major axis of galaxies provided that dust depletion is a proxy for metallicity. This anisotropic distribution is consistent with recent results on outflow and accretion in hydro-dynamical simulations.
Various mathematical Black-Scholes-Merton-like models of option pricing employ the paradigmatic stochastic process of geometric Brownian motion (GBM). The innate property of such models and of real stock-market prices is the roughly exponential growth of prices with time [on average, in crisis-free times]. We here explore the ensemble- and time averages of a multiplicative-noise stochastic process with power-law-like time-dependent volatility, sigma(t) similar to t(alpha), named scaled GBM (SGBM). For SGBM, the mean-squared displacement (MSD) computed for an ensemble of statistically equivalent trajectories can grow faster than exponentially in time, while the time-averaged MSD (TAMSD)-based on a sliding-window averaging along a single trajectory-is always linear at short lag times Delta. The proportionality factor between these the two averages of the time series is Delta/T at short lag times, where T is the trajectory length, similarly to GBM. This discrepancy of the scaling relations and pronounced nonequivalence of the MSD and TAMSD at Delta/T << 1 is a manifestation of weak ergodicity breaking for standard GBM and for SGBM with s (t)-modulation, the main focus of our analysis. The analytical predictions for the MSD and mean TAMSD for SGBM are in quantitative agreement with the results of stochastic computer simulations.
Self-organized coherence-incoherence patterns, called chimera states, have first been reported in systems of Kuramoto oscillators. For coupled excitable units, similar patterns where coherent units are at rest are called bump states. Here, we study bumps in an array of active rotators coupled by nonlocal attraction and global repulsion. We demonstrate how they can emerge in a supercritical scenario from completely coherent Turing patterns: a single incoherent unit appears in a homoclinic bifurcation, undergoing subsequent transitions to quasiperiodic and chaotic behavior, which eventually transforms into extensive chaos with many incoherent units. We present different types of transitions and explain the formation of coherence-incoherence patterns according to the classical paradigm of short-range activation and long-range inhibition.
Hydrogels with a hierarchical structure were prepared from a new highly water-soluble crosslinker N,N,N',N'-tetramethyl-N,N'-bis(2-ethylmethacrylate)-propyl-1,3-diammonium dibromide and from the sulfobetaine monomer 2-(N-3-sulfopropyl-N,N-dimethyl ammonium)ethyl methacrylate. The free radical polymerization of the two compounds is rapid and yields near-transparent hydrogels with sizes up to 5 cm in diameter. Rheology shows a clear correlation between the monomer-to-crosslinker ratio and the storage and loss moduli of the hydrogels. Cryo-scanning electron microscopy, low-field nuclear magnetic resonance (NMR) spectroscopy, and small-angle X-ray scattering show that the gels have a hierarchical structure with features spanning the nanometer to the sub-millimeter scale. The NMR study is challenged by the marked inhomogeneity of the gels and the complex chemical structure of the sulfobetaine monomer. NMR spectroscopy shows how these complications can be addressed via a novel fitting approach that considers the mobility gradient along the side chain of methacrylate-based monomers.
Using magneto-optical Faraday and Kerr measurements, we investigate the magnetic and magnetooptical properties of a thick Bi-substituted gadolinium iron garnet film over a broad range of wavelengths (250-850 nm) and temperatures (150-300 K), including the magnetization compensation point, TM. We observe an exchange-bias-like effect in the vicinity of TM. By slightly changing the sample temperature, we can precisely tune the bias field, which reaches a magnitude 6 times higher than the coercive field. We explain this phenomenon by considering the short-range superexchange interaction and a change in the magnetic behavior when moving from the surface to the bulk of the film. This finding may lead to the development of single-film magneto-optical devices based on the exchange-bias effect.
This paper is concerned with correlation functions of stochastic systems with memory, a prominent example being a molecule or colloid moving through a complex (e.g. viscoelastic) fluid environment. Analytical investigations of such systems based on non-Markovian stochastic equations are notoriously difficult. A common approximation is that of a single-exponential memory, corresponding to the introduction of one auxiliary variable coupled to the Markovian dynamics of the main variable. As a generalization, we here investigate a class of 'toy' models with altogether three degrees of freedom, giving rise to more complex forms of memory. Specifically, we consider, mainly on an analytical basis, the under- and overdamped motion of a colloidal particle coupled linearly to two auxiliary variables, where the coupling between variables can be either reciprocal or non-reciprocal. Projecting out the auxiliary variables, we obtain non-Markovian Langevin equations with friction kernels and colored noise, whose structure is similar to that of a generalized Langevin equation. For the present systems, however, the non-Markovian equations may violate the fluctuation-dissipation relation as well as detailed balance, indicating that the systems are out of equilibrium. We then study systematically the connection between the coupling topology of the underlying Markovian system and various autocorrelation functions. We demonstrate that already two auxiliary variables can generate surprisingly complex (e.g. non-monotonic or oscillatory) memory and correlation functions. Finally, we show that a minimal overdamped model with two auxiliary variables and suitable non-reciprocal coupling yields correlation functions resembling those describing hydrodynamic backflow in an optical trap.
Additive manufacturing (AM) of metals and in particular laser powder bed fusion (LPBF) enables a degree of freedom in design unparalleled by conventional subtractive methods. To ensure that the designed precision is matched by the produced LPBF parts, a full understanding of the interaction between the laser and the feedstock powder is needed. It has been shown that the laser also melts subjacent layers of material underneath. This effect plays a key role when designing small cavities or overhanging structures, because, in these cases, the material underneath is feed-stock powder. In this study, we quantify the extension of the melt pool during laser illumination of powder layers and the defect spatial distribution in a cylindrical specimen. During the LPBF process, several layers were intentionally not exposed to the laser beam at various locations, while the build process was monitored by thermography and optical tomography. The cylinder was finally scanned by X-ray computed tomography (XCT). To correlate the positions of the unmolten layers in the part, a staircase was manufactured around the cylinder for easier registration. The results show that healing among layers occurs if a scan strategy is applied, where the orientation of the hatches is changed for each subsequent layer. They also show that small pores and surface roughness of solidified material below a thick layer of unmolten material (>200 mu m) serve as seeding points for larger voids. The orientation of the first two layers fully exposed after a thick layer of unmolten powder shapes the orientation of these voids, created by a lack of fusion.
The stable operation of a turbulent combustor is not completely silent; instead, there is a background of small amplitude aperiodic acoustic fluctuations known as combustion noise. Pressure fluctuations during this state of combustion noise are multifractal due to the presence of multiple temporal scales that contribute to its dynamics. However, existing models are unable to capture the multifractality in the pressure fluctuations. We conjecture an underlying fractional dynamics for the thermoacoustic system and obtain a fractional-order model for pressure fluctuations. The data from this model has remarkable visual similarity to the experimental data and also has a wide multifractal spectrum during the state of combustion noise. Quantitative similarity with the experimental data in terms of the Hurst exponent and the multifractal spectrum is observed during the state of combustion noise. This model is also able to produce pressure fluctuations that are qualitatively similar to the experimental data acquired during intermittency and thermoacoustic instability. Furthermore, we argue that the fractional dynamics vanish as we approach the state of thermoacoustic instability.
In their comment on our paper (Caesar et al 2020 Environ. Res. Lett. 15 024003), Chen and Tung (hereafter C&T) argue that our analysis, showing that over the last decades Atlantic meridional overturning circulation (AMOC) strength and global mean surface temperature (GMST) were positively correlated, is incorrect. Their claim is mainly based on two arguments, neither of which is justified: first, C&T claim that our analysis is based on 'established evidence' that was only true for preindustrial conditions-this is not the case. Using data from the modern period (1947-2012), we show that the established understanding (i.e. deep-water formation in the North Atlantic cools the deep ocean and warms the surface) is correct, but our analysis is not based on this fact. Secondly, C&T claim that our results are based on a statistical analysis of only one cycle of data which was furthermore incorrectly detrended. This, too, is not true. Our conclusion that a weaker AMOC delays the current surface warming rather than enhances it, is based on several independent lines of evidence. The data we show to support this covers more than one cycle and the detrending (which was performed to avoid spurious correlations due to a common trend) does not affect our conclusion: the correlation between AMOC strength and GMST is positive. We do not claim that this is strong evidence that the two time series are in phase, but rather that this means that the two time series are not anti-correlated.
Recent experiments on laser-dissociation of aligned homonuclear diatomic molecules show an asymmetric forward-backward (spatial) electron-localization along the laser polarization axis. Most theoretical models attribute this asymmetry to interference effects between gerade and ungerade vibronic states. Presumably due to alignment, these models neglect molecular rotations and hence infer an asymmetric (post-dissociation) charge distribution over the two identical nuclei. In this paper, we question the equivalence that is made between spatial electron-localization, observed in experiments, and atomic electron-localization, alluded by these theoretical models. We show that (seeming) agreement between these models and experiments is due to an unfortunate omission of nuclear permutation symmetry, i.e., quantum statistics. Enforcement of the latter requires mandatory inclusion of the molecular rotational degree of freedom, even for perfectly aligned molecules. Unlike previous interpretations, we ascribe spatial electron-localization to the laser creation of a rovibronic wavepacket that involves field-free molecular eigenstates with opposite space-inversion symmetry i.e., even and odd parity. Space-inversion symmetry breaking would then lead to an asymmetric distribution of the (space-fixed) electronic density over the forward and backward hemisphere. However, owing to the simultaneous coexistence of two indistinguishable molecular orientational isomers, our analytical and computational results show that the post-dissociation electronic density along a specified space-fixed axis is equally shared between the two identical nuclei-a result that is in perfect accordance with the principle of the indistinguishability of identical particles. Published under an exclusive license by AIP Publishing.
The DNA interaction with cis-isomers of photosensitive azobenzene-containing surfactants was studied by both experimental methods and computer simulation. It was shown that before the organization of micelles, such surfactants in the cis-conformation form associates of only a single type with a disordered orientation of molecules. In contrast, for trans-isomers, there exist two types of associates with head-to-head or head-to-tail orientations of molecules in dependence on salt concentration in a solution. The comparison of cis- and trans-isomer binding to DNA and the influence of salt concentration on the formation of their complexes with DNA were studied. It was shown that cis-isomers interact with phosphate groups of DNA and that their molecules were also located along the minor groove of DNA.
We analyze historical data of stock-market prices for multiple financial indices using the concept of delay-time averaging for the financial time series (FTS). The region of validity of our recent theoretical predictions [Cherstvy A G et al 2017 New J. Phys. 19 063045] for the standard and delayed time-averaged mean-squared 'displacements' (TAMSDs) of the historical FTS is extended to all lag times. As the first novel element, we perform extensive computer simulations of the stochastic differential equation describing geometric Brownian motion (GBM) which demonstrate a quantitative agreement with the analytical long-term price-evolution predictions in terms of the delayed TAMSD (for all stock-market indices in crisis-free times). Secondly, we present a robust procedure of determination of the model parameters of GBM via fitting the features of the price-evolution dynamics in the FTS for stocks and cryptocurrencies. The employed concept of single-trajectory-based time averaging can serve as a predictive tool (proxy) for a mathematically based assessment and rationalization of probabilistic trends in the evolution of stock-market prices.
We report a comparison of two photonic techniques for single-molecule sensing: fluorescence nanoscopy and optoplasmonic sensing. As the test system, oligonucleotides with and without fluorescent labels are transiently hybridized to complementary "docking" strands attached to gold nanorods. Comparing the measured single-molecule kinetics helps to examine the influence of the fluorescent labels as well as factors arising from different sensing geometries. Our results demonstrate that DNA dissociation is not significantly altered by the fluorescent labels and that DNA association is affected by geometric factors in the two techniques. These findings open the door to exploiting plasmonic sensing and fluorescence nanoscopy in a complementary fashion, which will aid in building more powerful sensors and uncovering the intricate effects that influence the behavior of single molecules.
Master equations are a vital tool to model heat flow through nanoscale thermodynamic systems. Most practical devices are made up of interacting subsystems and are often modelled using either local master equations (LMEs) or global master equations (GMEs). While the limiting cases in which either the LME or the GME breaks down are well understood, there exists a 'grey area' in which both equations capture steady-state heat currents reliably but predict very different transient heat flows. In such cases, which one should we trust? Here we show that, when it comes to dynamics, the local approach can be more reliable than the global one for weakly interacting open quantum systems. This is due to the fact that the secular approximation, which underpins the GME, can destroy key dynamical features. To illustrate this, we consider a minimal transport setup and show that its LME displays exceptional points (EPs). These singularities have been observed in a superconducting-circuit realisation of the model [1]. However, in stark contrast to experimental evidence, no EPs appear within the global approach. We then show that the EPs are a feature built into the Redfield equation, which is more accurate than the LME and the GME. Finally, we show that the local approach emerges as the weak-interaction limit of the Redfield equation, and that it entirely avoids the secular approximation.
Spherical particles from shape-memory polymers (SMP) can be stretched to ellipsoids with high aspect ratio (AR) and temporarily stabilized. They can switch back to low AR upon thermal stimulation. Here, the creation of an alternative shape-switching capability of particles from low to high AR is introduced, where a SMP matrix from polyvinyl alcohol (PVA) is used to create crosslinked high AR particles and to program the embedded micrometer-sized particles from a second SMP (oligo(epsilon-caprolactone) micronetworks, MN) with a low switching temperature T-sw. This programming proceeds through shape-recovery of the PVA matrix, from which the MN are harvested by PVA matrix dissolution. The use of a dissolvable SMP matrix may be a general strategy to efficiently create systems with complex moving capabilities.
The electron-phonon scattering is one of the main microscopic mechanisms responsible for the spin-flip in the transient state of ultrafast demagnetization. Here, we present an experimental determination of the temperature-dependent electron-phonon scattering rate in Gd. Using a static x-ray emission spectroscopy method, where the reduction of the decay peak intensities when increasing the temperature is quantified, we measure independently the electron-phonon scattering rate for the 5d and the 4f electrons. We deduce the temperature dependence of scattering for the 5d electrons, while no effect on the phonon population is observed for the 4f electrons. Our results suggest that the ultrafast magnetization dynamics in Gd is triggered by the spin-flip in the 5d electrons. We also evidence the existence of a temperature threshold, above which spin-flip scattering of the 5d electrons takes place. We deduce that during the transient state of ultrafast demagnetization, the exchange energy between 5d electrons has to be overcome before the microscopic electron-phonon scattering process can occur.
The stratosphere is one of the main potential sources for subseasonal to seasonal predictability in midlatitudes in winter. The ability of an atmospheric model to realistically simulate the stratospheric dynamics is essential in order to move forward in the field of seasonal predictions in midlatitudes. Earlier studies with the ICOsahedral Nonhydrostatic atmospheric model (ICON) point out that stratospheric westerlies in ICON are underestimated. This is the first extensive study on the evaluation of Northern Hemisphere stratospheric winter circulation with ICON in numerical weather prediction (NWP) mode. Seasonal experiments with the default setup are able to reproduce the basic climatology of the stratospheric polar vortex. However, westerlies are too weak and major stratospheric warmings too frequent in ICON. Both a reduction of the nonorographic, and a reduction of the orographic gravity wave and wake drag lead to a strengthening of the stratospheric vortex and a bias reduction, in particular in January. However, the effect of the nonorographic gravity wave drag scheme on the stratosphere is stronger. Stratosphere-troposphere coupling is intensified and more realistic due to a reduced gravity wave drag. Furthermore, an adjustment of the subgrid-scale orographic drag parameterization leads to a significant error reduction in the mean sea level pressure. As a result of these findings, we present our current suggested improved setup for seasonal experiments with ICON-NWP. <br /> Plain Language Summary Although seasonal forecasts for midlatitudes have the potential to be highly beneficial to the public sector, they are still characterized by a large amount of uncertainty. Exact simulations of the circulation in the stratosphere can help to improve tropospheric predictability on seasonal time scales. For this reason, we investigate how well the new German atmospheric model is able to simulate the stratospheric circulation. The model reproduces the basic behavior of the Northern Hemisphere stratospheric polar vortex, but the westerly circulation in winter is underestimated. The stratospheric circulation is influenced by gravity waves that exert drag on the flow. These processes are only partly physically represented in the model, but are very important and are hence parameterized. By adjusting the parameterizations for the gravity wave drag, the stratospheric polar vortex is strengthened, thereby yielding a more realistic stratospheric circulation. In addition, the altered parameterizations improve the simulated surface pressure pattern. Based upon this, we present our current suggested improved model setup for seasonal experiments.
A symmetry-breaking mechanism is investigated that creates bistability between fully and partially synchronized states in oscillator networks. Two populations of oscillators with unimodal frequency distribution and different amplitudes, in the presence of weak global coupling, are shown to simplify to a modular network with asymmetrical coupling. With increasing the coupling strength, a synchronization transition is observed with an isolated fully synchronized state. The results are interpreted theoretically in the thermodynamic limit and confirmed in experiments with chemical oscillators.
We consider a system of two spins under a scanning tunneling microscope bias and derive its master equation. We find that the tunneling elements to the electronic contacts (tip and substrate) generate an exchange interaction between the spins as well as a Dzyaloshinskii-Moriya interaction in the presence of spin-orbit coupling. The tunnel current spectrum then shows additional lines compared to conventional spin-resonance experiments. When the spins have degenerate Larmor frequencies and equal tunneling amplitudes (without spin orbit), there is a dark state with a vanishing decay rate. The coupling to the electronic environment generates significant spin-spin entanglement via the dark state, even if the initial state is nonentangled.
How different microscopic mechanisms of ultrafast spin dynamics coexist and interplay is not only relevant for the development of spintronics but also for the thorough description of physical systems out-of-equilibrium. In pure crystalline ferromagnets, one of the main microscopic mechanism of spin relaxation is the electron-phonon (el-ph) driven spin-flip, or Elliott-Yafet, scattering. Unexpectedly, recent experiments with ferro- and ferrimagnetic alloys have shown different dynamics for the different sublattices. These distinct sublattice dynamics are contradictory to the Elliott-Yafet scenario. In order to rationalize this discrepancy, it has been proposed that the intra- and intersublattice exchange interaction energies must be considered in the microscopic demagnetization mechanism, too. Here, using a temperature-dependent x-ray emission spectroscopy (XES) method, we address experimentally the element specific el-ph angular momentum transfer rates, responsible for the spin-flips in the respective (sub)lattices of Fe20Ni80, Fe50Ni50 and pure nickel single crystals. We establish how the deduced rate evolution with the temperature is linked to the exchange coupling constants reported for different alloy stoichiometries and how sublattice exchange energies threshold the related el-ph spin-flip channels. Thus, these results evidence that the Elliott-Yafet spin-flip scattering, thresholded by sublattice exchange energies, is the relevant microscopic process to describe sublattice dynamics in alloys and elemental magnetic systems.
We study the first passage dynamics for a diffusing particle experiencing a spatially varying diffusion coefficient while driven by correlated additive Gaussian white noise and multiplicative coloured non-Gaussian noise. We consider three functional forms for position dependence of the diffusion coefficient: power-law, exponential, and logarithmic. The coloured non-Gaussian noise is distributed according to Tsallis' q-distribution. Tracks of the non-Markovian systems are numerically simulated by using the fourth-order Runge-Kutta algorithm and the first passage times (FPTs) are recorded. The FPT density is determined along with the mean FPT (MFPT). Effects of the noise intensity and self-correlation of the multiplicative noise, the intensity of the additive noise, the cross-correlation strength, and the non-extensivity parameter on the MFPT are discussed.
State-of-the-art organic solar cells exhibit power conversion efficiencies of 18% and above. These devices benefit from the suppression of free charge recombination with regard to the Langevin limit of charge encounter in a homogeneous medium. It is recognized that the main cause of suppressed free charge recombination is the reformation and resplitting of charge-transfer (CT) states at the interface between donor and acceptor domains. Here, we use kinetic Monte Carlo simulations to understand the interplay between free charge motion and recombination in an energetically disordered phase-separated donor-acceptor blend. We identify conditions for encounter-dominated and resplitting-dominated recombination. In the former regime, recombination is proportional to mobility for all parameters tested and only slightly reduced with respect to the Langevin limit. In contrast, mobility is not the decisive parameter that determines the nongeminate recombination coefficient, k(2), in the latter case, where k2 is a sole function of the morphology, CT and charge-separated (CS) energetics, and CT-state decay properties. Our simulations also show that free charge encounter in the phase-separated disordered blend is determined by the average mobility of all carriers, while CT reformation and resplitting involves mostly states near the transport energy. Therefore, charge encounter is more affected by increased disorder than the resplitting of the CT state. As a consequence, for a given mobility, larger energetic disorder, in combination with a higher hopping rate, is preferred. These findings have implications for the understanding of suppressed recombination in solar cells with nonfullerene acceptors, which are known to exhibit lower energetic disorder than that of fullerenes.
Sustainable electricity systems need renewable and dispatchable energy sources. Solar energy is an abundant source of renewable energy globally which is, though, by nature only available during the day, and especially in clear weather conditions. We compare three technology configurations able to provide dispatchable solar power at times without sunshine: Photovoltaics (PV) combined with battery (BESS) or thermal energy storage (TES) and concentrating solar power (CSP) with TES. Modeling different periods without sunshine, we find that PV+BESS is competitive for shorter storage durations while CSP+TES gains economic advantages for longer storage periods (also over PV+TES). The corresponding tipping points lie at 2-3 hours (current cost), and 4-10 hours if expectations on future cost developments are taken into consideration. PV+TES becomes only more competitive than CSP+TES with immense additional cost reductions of PV. Hence, there remain distinct niches for two technologies: PV+BESS for short storage durations and CSP+TES for longer ones.
We derive modified reflection coefficients for electromagnetic waves in the THz and far infrared range. The idea is based on hydrodynamic boundary conditions for metallic conduction electrons. The temperature-dependent part of the Casimir pressure between metal plates is evaluated. The results should shed light on the "thermal anomaly," where measurements deviate from the standard fluctuation electrodynamics for conducting metals.
A characterization of the essential spectrum of Schrodinger operators on infinite graphs is derived involving the concept of R-limits. This concept, which was introduced previously for operators on N and Z(d) as "right-limits," captures the behaviour of the operator at infinity. For graphs with sub-exponential growth rate, we show that each point in sigma(ss)(H) corresponds to a bounded generalized eigenfunction of a corresponding R-limit of H. If, additionally, the graph is of uniform sub-exponential growth, also the converse inclusion holds.
Proximity to heavy sp-elements is considered promising for reaching a band gap in graphene that could host quantum spin Hall states. The recent report of an induced spin-orbit gap of 0.2 eV in Pb-intercalated graphene detectable by spin-resolved photoemission has spurred renewed interest in such systems (Klimovskikh et al 2017 ACS Nano 11, 368). In the case of Bi intercalation an even larger band gap of 0.4 eV has been observed but was assigned to the influence of a dislocation network (Warmuth et al 2016 Phys. Rev. B 93, 165 437). Here, we study Bi intercalation under graphene on Ir(111) and report a nearly ideal graphene dispersion without band replicas and no indication of hybridization with the substrate. The band gap is small (0.19 eV) and can be tuned by +/- 25 meV through the Bi coverage. The Bi atomic density is higher than in the recent report. By spin-resolved photoemission we exclude induced spin-orbit interaction as origin of the gap. Quantitative agreement of a photoemission intensity analysis with the measured band gap suggests sublattice symmetry breaking as one of the possible band gap opening mechanisms. We test several Bi structures by density functional theory. Our results indicate the possibility that Bi intercalates in the phase of bismuthene forming a graphene-bismuthene van der Waals heterostructure.
Remote synchronization implies that oscillators interacting not directly but via an additional unit (hub) adjust their frequencies and exhibit frequency locking while the hub remains asynchronous. In this paper, we analyze the mechanisms of remote synchrony in a small network of three coupled Stuart-Landau oscillators using recent results on higher-order phase reduction. We analytically demonstrate the role of two factors promoting remote synchrony. These factors are the nonisochronicity of oscillators and the coupling terms appearing in the secondorder phase approximation. We show a good correspondence between our theory and numerical results for small and moderate coupling strengths.
Generalized (non-Markovian) diffusion equations with different memory kernels and subordination schemes based on random time change in the Brownian diffusion process are popular mathematical tools for description of a variety of non-Fickian diffusion processes in physics, biology, and earth sciences. Some of such processes (notably, the fluid limits of continuous time random walks) allow for either kind of description, but other ones do not. In the present work we discuss the conditions under which a generalized diffusion equation does correspond to a subordination scheme, and the conditions under which a subordination scheme does possess the corresponding generalized diffusion equation. Moreover, we discuss examples of random processes for which only one, or both kinds of description are applicable.
Steric hindrance of hydration and hydrogen bond enhancement by localized charges have been identified as key factors for the massive chemical differences between the hydroxypyridine/pyridone isomers in aqueous solution. While all isomers occur mainly in the hydroxypyridine form in the gas phase, they differ by more than 3 orders of magnitude both in their acidity and tautomeric equilibrium constants upon hydration. By monitoring the electronic and solvation structures as a function of the protonation state and the O- substitution position on the pyridine ring, the amplification of the isomeric differences in aqueous solution has been investigated. Near-edge X-ray absorption fine structure (NEXAFS) measurements at the N K-edge served as the probe of the chemical state. The combination of molecular dynamics simulations, complete active space self-consistent field (CASSCF), and time-dependent density functional theory (TD-DFT) spectral calculations contributes to unraveling the principles of tautomerism and acidity in multiple biochemical systems based on tautomerism.
Laser based powder bed fusion additive manufacturing offers the flexibility to incorporate standard and user-defined scan strategies in a layer or in between the layers for the customized fabrication of metallic components. In the present study, four different scan strategies and their impact on the development of microstructure, texture, and residual stresses in laser powder bed fusion additive manufacturing of a nickel-based superalloy Inconel 718 was investigated. Light microscopy, scanning electron microscopy combined with electron back-scatter diffraction, and neutron diffraction were used as the characterization tools. Strong textures with epitaxially grown columnar grains were observed along the build direction for the two individual scan strategies. Patterns depicting the respective scan strategies were visible in the build plane, which dictated the microstructure development in the other planes. An alternating strategy combining the individual strategies in the successive layers and a 67 degrees rotational strategy weakened the texture by forming finer micro-structural features. Von Mises equivalent stress plots revealed lower stress values and gradients, which translates as lower distortions for the alternating and rotational strategies. Overall results confirmed the scope for manipulating the microstructure, texture, and residual stresses during laser powder bed fusion additive manufacturing by effectively controlling the scan strategies.
Characterising stochastic motion in heterogeneous media driven by coloured non-Gaussian noise
(2021)
We study the stochastic motion of a test particle in a heterogeneous medium in terms of a position dependent diffusion coefficient mimicking measured deterministic diffusivity gradients in biological cells or the inherent heterogeneity of geophysical systems. Compared to previous studies we here investigate the effect of the interplay of anomalous diffusion effected by position dependent diffusion coefficients and coloured non-Gaussian noise. The latter is chosen to be distributed according to Tsallis' q-distribution, representing a popular example for a non-extensive statistic. We obtain the ensemble and time averaged mean squared displacements for this generalised process and establish its non-ergodic properties as well as analyse the non-Gaussian nature of the associated displacement distribution. We consider both non-stratified and stratified environments.
We provide an overview of the tools and techniques of resurgence theory used in the Borel-ecalle resummation method, which we then apply to the massless Wess-Zumino model. Starting from already known results on the anomalous dimension of the Wess-Zumino model, we solve its renormalisation group equation for the two-point function in a space of formal series. We show that this solution is 1-Gevrey and that its Borel transform is resurgent. The Schwinger-Dyson equation of the model is then used to prove an asymptotic exponential bound for the Borel transformed two-point function on a star-shaped domain of a suitable ramified complex plane. This proves that the two-point function of the Wess-Zumino model is Borel-ecalle summable.
High-resolution observations of polar crown and high-latitude filaments are scarce. We present a unique sample of such filaments observed in high-resolution H alpha narrow-band filtergrams and broad-band images, which were obtained with a new fast camera system at the Vacuum Tower Telescope (VTT), Tenerife, Spain. The Chromospheric Telescope (ChroTel) provided full-disk context observations in H alpha, CaiiK, and Hei 10830 angstrom. The Helioseismic and Magnetic Imager (HMI) and the Atmospheric Imaging Assembly (AIA) on board the Solar Dynamics Observatory (SDO) provided line-of-sight magnetograms and ultraviolet (UV) 1700 angstrom filtergrams, respectively. We study filigree in the vicinity of polar crown and high-latitude filaments and relate their locations to magnetic concentrations at the filaments' footpoints. Bright points are a well studied phenomenon in the photosphere at low latitudes, but they were not yet studied in the quiet network close to the poles. We examine size, area, and eccentricity of bright points and find that their morphology is very similar to their counterparts at lower latitudes, but their sizes and areas are larger. Bright points at the footpoints of polar crown filaments are preferentially located at stronger magnetic flux concentrations, which are related to bright regions at the border of supergranules as observed in UV filtergrams. Examining the evolution of bright points on three consecutive days reveals that their amount increases while the filament decays, which indicates they impact the equilibrium of the cool plasma contained in filaments.
I study deterministic dynamics of chiral active particles in two dimensions. Particles are considered as discs interacting with elastic repulsive forces. An ensemble of particles, started from random initial conditions, demonstrates chaotic collisions resulting in their normal diffusion. This chaos is transient, as rather abruptly a synchronous collisionless state establishes. The life time of chaos grows exponentially with the number of particles. External forcing (periodic or chaotic) is shown to facilitate the synchronization transition.
'Complex systems are information processors' is a statement that is frequently made. Here we argue for the distinction between information processing-in the sense of encoding and transmitting a symbolic representation-and the formation of correlations (pattern formation/self-organisation). The study of both uses tools from information theory, but the purpose is very different in each case: explaining the mechanisms and understanding the purpose or function in the first case, versus data analysis and correlation extraction in the latter. We give examples of both and discuss some open questions. The distinction helps focus research efforts on the relevant questions in each case.
Data-driven prediction and physics-agnostic machine-learning methods have attracted increased interest in recent years achieving forecast horizons going well beyond those to be expected for chaotic dynamical systems. In a separate strand of research data-assimilation has been successfully used to optimally combine forecast models and their inherent uncertainty with incoming noisy observations. The key idea in our work here is to achieve increased forecast capabilities by judiciously combining machine-learning algorithms and data assimilation. We combine the physics-agnostic data -driven approach of random feature maps as a forecast model within an ensemble Kalman filter data assimilation procedure. The machine-learning model is learned sequentially by incorporating incoming noisy observations. We show that the obtained forecast model has remarkably good forecast skill while being computationally cheap once trained. Going beyond the task of forecasting, we show that our method can be used to generate reliable ensembles for probabilistic forecasting as well as to learn effective model closure in multi-scale systems. (C) 2021 Elsevier B.V. All rights reserved.
Bifurcations in rotating spherical shell convection under the influence of differential rotation
(2021)
The bifurcations of thermal convection in a rotating spherical shell heated from the inner sphere and driven by the buoyancy of a central gravity field are studied numerically. This model of spherical Rayleigh-Benard convection describes large-scale convection in planets and in the outer zones of celestial bodies. In this work, the influence of an additionally imposed differential rotation of the inner sphere with respect to the outer one on the heat transfer and, more generally, on the whole bifurcation structure is investigated. In addition to numerical simulations, path-following techniques are applied in order to compute both stable and unstable solution branches. The dynamics and the heat transfer are essentially determined by a global bifurcation, which we have identified as a homoclinic bifurcation that consists of a collision of a stable modulated rotating with an unstable rotating wave.
With the advent of big data and data lakes, data are often integrated from multiple sources. Such integrated data are often of poor quality, due to inconsistencies, errors, and so forth. One way to check the quality of data is to infer functional dependencies (fds). However, in many modern applications it might be necessary to extract properties and relationships that are not captured through fds, due to the necessity to admit exceptions, or to consider similarity rather than equality of data values. Relaxed fds (rfds) have been introduced to meet these needs, but their discovery from data adds further complexity to an already complex problem, also due to the necessity of specifying similarity and validity thresholds. We propose Domino, a new discovery algorithm for rfds that exploits the concept of dominance in order to derive similarity thresholds of attribute values while inferring rfds. An experimental evaluation on real datasets demonstrates the discovery performance and the effectiveness of the proposed algorithm.
We performed numerical simulations with the Kuramoto model and experiments with oscillatory nickel electrodissolution to explore the dynamical features of the transients from random initial conditions to a fully synchronized (one-cluster) state. The numerical simulations revealed that certain networks (e.g., globally coupled or dense Erdos-Renyi random networks) showed relatively simple behavior with monotonic increase of the Kuramoto order parameter from the random initial condition to the fully synchronized state and that the transient times exhibited a unimodal distribution. However, some modular networks with bridge elements were identified which exhibited non-monotonic variation of the order parameter with local maximum and/or minimum. In these networks, the histogram of the transients times became bimodal and the mean transient time scaled well with inverse of the magnitude of the second largest eigenvalue of the network Laplacian matrix. The non-monotonic transients increase the relative standard deviations from about 0.3 to 0.5, i.e., the transient times became more diverse. The non-monotonic transients are related to generation of phase patterns where the modules are synchronized but approximately anti-phase to each other. The predictions of the numerical simulations were demonstrated in a population of coupled oscillatory electrochemical reactions in global, modular, and irregular tree networks. The findings clarify the role of network structure in generation of complex transients that can, for example, play a role in intermittent desynchronization of the circadian clock due to external cues or in deep brain stimulations where long transients are required after a desynchronization stimulus.
Moving spiral wave chimeras
(2021)
We consider a two-dimensional array of heterogeneous nonlocally coupled phase oscillators on a flat torus and study the bound states of two counter-rotating spiral chimeras, shortly two-core spiral chimeras, observed in this system. In contrast to other known spiral chimeras with motionless incoherent cores, the two-core spiral chimeras typically show a drift motion. Due to this drift, their incoherent cores become spatially modulated and develop specific fingerprint patterns of varying synchrony levels. In the continuum limit of infinitely many oscillators, the two-core spiral chimeras can be studied using the Ott-Antonsen equation. Numerical analysis of this equation allows us to reveal the stability region of different spiral chimeras, which we group into three main classes-symmetric, asymmetric, and meandering spiral chimeras.
Human migration is often studied using gravity models. These models, however, have known limitations, including analytic inconsistencies and a dependence on empirical data to calibrate multiple parameters for the region of interest. Overcoming these limitations, the radiation model has been proposed as an alternative, universal approach to predicting different forms of human mobility, but has not been adopted for studying migration. Here we show, using data on within-country migration from the USA and Mexico, that the radiation model systematically underpredicts long-range moves, while the traditional gravity model performs well for large distances. The universal opportunity model, an extension of the radiation model, shows an improved fit of long-range moves compared to the original radiation model, but at the cost of introducing two additional parameters. We propose a more parsimonious extension of the radiation model that introduces a single parameter. We demonstrate that it fits the data over the full distance spectrum and also-unlike the universal opportunity model-preserves the analytical property of the original radiation model of being equivalent to a gravity model in the limit of a uniform population distribution.
We use quantum chemical cluster models together with constrained density STM Ph CI functional theory (DFT) and ab initio molecular dynamics (AIMD) for open system to simulate tip and rationalize nonlocal scanning tunneling microscope (STM) manipulation experiments for Philh ci chlorobenzene (PhCl) on a Si(111)-7 X 7 surface. We consider three different processes, namely, the electron-induced dissociation of the carbon-chlorine bond for physisorbed PhCl molecules at low temperatures and the electron- or hole-induced desorption of chemisorbed PhCl at 300 K. All processes can be induced nonlocally, i.e., up to several nanometers (nm) away from the injection site, in STM experiments. We rationalize and explain the experimental findings regarding the STM-induced dissociation using constrained DFT. The coupling of STM-induced ion resonances to nuclear degrees of freedom is simulated with AIMD using the Gadzuk averaging approach for open systems. From this data, we predict a 4 fs lifetime for the cationic resonance. For the anion model, desorption could not be observed. In addition, the same cluster models are used for transition-state theory calculations, which are compared to and validated against time-lapse STM experiments.
We present a supervised learning method to learn the propagator map of a dynamical system from partial and noisy observations. In our computationally cheap and easy-to-implement framework, a neural network consisting of random feature maps is trained sequentially by incoming observations within a data assimilation procedure. By employing Takens's embedding theorem, the network is trained on delay coordinates. We show that the combination of random feature maps and data assimilation, called RAFDA, outperforms standard random feature maps for which the dynamics is learned using batch data.
We investigate the transition from incoherence to global collective motion in a three-dimensional swarming model of agents with helical trajectories, subject to noise and global coupling. Without noise this model was recently proposed as a generalization of the Kuramoto model and it was found that alignment of the velocities occurs discontinuously for arbitrarily small attractive coupling. Adding noise to the system resolves this singular limit and leads to a continuous transition, either to a directed collective motion or to center-of-mass rotations.
The Rarita-Schwinger operator is the twisted Dirac operator restricted to 3/2-spinors. Rarita-Schwinger fields are solutions of this operator which are in addition divergence-free. This is an overdetermined problem and solutions are rare; it is even more unexpected for there to be large dimensional spaces of solutions. In this paper we prove the existence of a sequence of compact manifolds in any given dimension greater than or equal to 4 for which the dimension of the space of Rarita-Schwinger fields tends to infinity. These manifolds are either simply connected Kahler-Einstein spin with negative Einstein constant, or products of such spaces with flat tori. Moreover, we construct Calabi-Yau manifolds of even complex dimension with more linearly independent Rarita-Schwinger fields than flat tori of the same dimension.
Spherulite-related space-charge electret properties of polypropylene (PP) have been widely discussed in the past decades. In the present paper, a less-common crystalline structure in PP-transcrystalline PP-is studied regarding its electret behavior in comparison with the typical spherulitic morphology. Polarized light microscopy and differential scanning calorimetry were employed to characterize the crystallite types and crystallinities of transcrystalline and spherulitic PP. Their electret functionality is investigated by means of thermally stimulated discharge experiments, where the cross-over phenomenon is observed on transcrystalline PP films, whereas surface-potential saturation and undercharging on the surface occur on the spherulitic samples. Besides, an asymmetrical behavior of positive and negative surface-charge stabilities is found on PP with spherulites, the negatively charged spherulitic surfaces show a better charge stability. It is shown that PP electrets are very sensitive to changes in the microscopic crystalline structures and their interfaces as well as in the molecular conformations controlled through adjustments of the respective processing steps. In addition, surface and bulk nanocomposites of PP or low-density polyethylene with inorganic particles are included in the comparison. In view of recent developments in the areas of PP-based electret-fiber filters and cellular-foam ferroelectrets, the observed changes in the charge-storage properties may have particular relevance, as the required film, fiber, or foam processing might significantly modify crystalline morphologies and nano-scale interfaces in PP electrets. Limitations in the charge-storage capabilities of interface structures may also be of interest in the context of high-voltage electrical-insulation materials where reduced space-charge accumulation and slightly increased charge transport can be advantageous.
Fractional Brownian motion in superharmonic potentials and non-Boltzmann stationary distributions
(2021)
We study the stochastic motion of particles driven by long-range correlated fractional Gaussian noise (FGN) in a superharmonic external potential of the form U(x) proportional to x(2n) (n is an element of N). When the noise is considered to be external, the resulting overdamped motion is described by the non-Markovian Langevin equation for fractional Brownian motion. For this case we show the existence of long time, stationary probability density functions (PDFs) the shape of which strongly deviates from the naively expected Boltzmann PDF in the confining potential U(x). We analyse in detail the temporal approach to stationarity as well as the shape of the non-Boltzmann stationary PDF. A typical characteristic is that subdiffusive, antipersistent (with negative autocorrelation) motion tends to effect an accumulation of probability close to the origin as compared to the corresponding Boltzmann distribution while the opposite trend occurs for superdiffusive (persistent) motion. For this latter case this leads to distinct bimodal shapes of the PDF. This property is compared to a similar phenomenon observed for Markovian Levy flights in superharmonic potentials. We also demonstrate that the motion encoded in the fractional Langevin equation driven by FGN always relaxes to the Boltzmann distribution, as in this case the fluctuation-dissipation theorem is fulfilled.
The spatial magnetic properties, through-space NMR shieldings (TSNMRSs), of stable O, S and Hal analogues of N-heterocyclic carbenes (NHCs) have been calculated using the GIAO perturbation method employing the nucleus-independent chemical shift (NICS) concept and the results visualized as iso-chemical-shielding surfaces (ICSSs) of various sizes and directions. The TSNMRS values (actually the anisotropy effects measurable in H-1 NMR spectroscopy) are employed to qualify and quantify the position of the present mesomeric equilibria (carbenes <-> ylides). The results are confirmed by geometry (bond angles and bond lengths), IR spectra, UV spectra, and C-13 chemical shifts of the electron-deficient carbon centers.
Gravitational-wave (GW) astrophysics is a field in full blossom. Since the landmark detection of GWs from a binary black hole on September 14th 2015, fifty-two compact-object binaries have been reported by the LIGO-Virgo collaboration. Such events carry astrophysical and cosmological information ranging from an understanding of how black holes and neutron stars are formed, what neutron stars are composed of, how the Universe expands, and allow testing general relativity in the highly-dynamical strong-field regime. It is the goal of GW astrophysics to extract such information as accurately as possible. Yet, this is only possible if the tools and technology used to detect and analyze GWs are advanced enough. A key aspect of GW searches are waveform models, which encapsulate our best predictions for the gravitational radiation under a certain set of parameters, and that need to be cross-correlated with data to extract GW signals. Waveforms must be very accurate to avoid missing important physics in the data, which might be the key to answer the fundamental questions of GW astrophysics. The continuous improvements of the current LIGO-Virgo detectors, the development of next-generation ground-based detectors such as the Einstein Telescope or the Cosmic Explorer, as well as the development of the Laser Interferometer Space Antenna (LISA), demand accurate waveform models. While available models are enough to capture the low spins, comparable-mass binaries routinely detected in LIGO-Virgo searches, those for sources from both current and next-generation ground-based and spaceborne detectors must be accurate enough to detect binaries with large spins and asymmetry in the masses. Moreover, the thousands of sources that we expect to detect with future detectors demand accurate waveforms to mitigate biases in the estimation of signals’ parameters due to the presence of a foreground of many sources that overlap in the frequency band. This is recognized as one of the biggest challenges for the analysis of future-detectors’ data, since biases might hinder the extraction of important astrophysical and cosmological information from future detectors’ data. In the first part of this thesis, we discuss how to improve waveform models for binaries with high spins and asymmetry in the masses. In the second, we present the first generic metrics that have been proposed to predict biases in the presence of a foreground of many overlapping signals in GW data.
For the first task, we will focus on several classes of analytical techniques. Current models for LIGO and Virgo studies are based on the post-Newtonian (PN, weak-field, small velocities) approximation that is most natural for the bound orbits that are routinely detected in GW searches. However, two other approximations have risen in prominence, the post-Minkowskian (PM, weak- field only) approximation natural for unbound (scattering) orbits and the small-mass-ratio (SMR) approximation typical of binaries in which the mass of one body is much bigger than the other. These are most appropriate to binaries with high asymmetry in the masses that challenge current waveform models. Moreover, they allow one to “cover” regions of the parameter space of coalescing binaries, thereby improving the interpolation (and faithfulness) of waveform models. The analytical approximations to the relativistic two-body problem can synergically be included within the effective-one-body (EOB) formalism, in which the two-body information from each approximation can be recast into an effective problem of a mass orbiting a deformed Schwarzschild (or Kerr) black hole. The hope is that the resultant models can cover both the low-spin comparable-mass binaries that are routinely detected, and the ones that challenge current models. The first part of this thesis is dedicated to a study about how to best incorporate information from the PN, PM, SMR and EOB approaches in a synergistic way. We also discuss how accurate the resulting waveforms are, as compared against numerical-relativity (NR) simulations. We begin by comparing PM models, whether alone or recast in the EOB framework, against PN models and NR simulations. We will show that PM information has the potential to improve currently-employed models for LIGO and Virgo, especially if recast within the EOB formalism. This is very important, as the PM approximation comes with a host of new computational techniques from particle physics to exploit. Then, we show how a combination of PM and SMR approximations can be employed to access previously-unknown PN orders, deriving the third subleading PN dynamics for spin-orbit and (aligned) spin1-spin2 couplings. Such new results can then be included in the EOB models currently used in GW searches and parameter estimation studies, thereby improving them when the binaries have high spins. Finally, we build an EOB model for quasi-circular nonspinning binaries based on the SMR approximation (rather than the PN one as usually done). We show how this is done in detail without incurring in the divergences that had affected previous attempts, and compare the resultant model against NR simulations. We find that the SMR approximation is an excellent approximation for all (quasi-circular nonspinning) binaries, including both the equal-mass binaries that are routinely detected in GW searches and the ones with highly asymmetric masses. In particular, the SMR-based models compare much better than the PN models, suggesting that SMR-informed EOB models might be the key to model binaries in the future. In the second task of this thesis, we work within the linear-signal ap- proximation and describe generic metrics to predict inference biases on the parameters of a GW source of interest in the presence of confusion noise from unfitted foregrounds and from residuals of other signals that have been incorrectly fitted out. We illustrate the formalism with simple (yet realistic) LISA sources, and demonstrate its validity against Monte-Carlo simulations. The metrics we describe pave the way for more realistic studies to quantify the biases with future ground-based and spaceborne detectors.
Partial synchronous states appear between full synchrony and asynchrony and exhibit many interesting properties. Most frequently, these states are studied within the framework of phase approximation. The latter is used ubiquitously to analyze coupled oscillatory systems. Typically, the phase dynamics description is obtained in the weak coupling limit, i.e., in the first-order in the coupling strength. The extension beyond the first-order represents an unsolved problem and is an active area of research. In this paper, three partially synchronous states are investigated and presented in order of increasing complexity. First, the usage of the phase response curve for the description of macroscopic oscillators is analyzed. To achieve this, the response of the mean-field oscillations in a model of all-to-all coupled limit-cycle oscillators to pulse stimulation is measured. The next part treats a two-group Kuramoto model, where the interaction of one attractive and one repulsive group results in an interesting solitary state, situated between full synchrony and self-consistent partial synchrony. In the last part, the phase dynamics of a relatively simple system of three Stuart-Landau oscillators are extended beyond the weak coupling limit. The resulting model contains triplet terms in the high-order phase approximation, though the structural connections are only pairwise. Finally, the scaling of the new terms with the coupling is analyzed.
Heat waves are increasingly common in many countries across the globe, and also in Germany, where this study is set. Heat poses severe health risks, especially for vulnerable groups such as the elderly and children. This case study explores visitors' behavior and perceptions during six weekends in the summer of 2018 at a 6-month open-air horticultural show. Data from a face-to-face survey (n = 306) and behavioral observations ( n = 2750) were examined by using correlation analyses, ANOVA, and multiple regression analyses. Differences in weather perception, risk awareness, adaptive behavior, and activity level were observed between rainy days (maximum daily temperature, 25 degrees C), warmsummer days (25 degrees-30 degrees C), and hot days (>30 degrees C). Respondents reported a high level of heat risk awareness, butmost (90%) were unaware of actual heat warnings. During hot days, more adaptive measures were reported and observed. Older respondents reported taking the highest number of adaptive measures. We observed the highest level of adaptation in children, but they also showed the highest activity level. From our results we discuss how to facilitate individual adaptation to heat stress at open-air events by taking the heterogeneity of visitors into account. To mitigate negative health outcomes for citizens in the future, we argue for tailored risk communication aimed at vulnerable groups. <br /> SIGNIFICANCE STATEMENT: People around the world are facing higher average temperatures. While higher temperatures make open-air events a popular leisure time activity in summer, heat waves are a threat to health and life. Since there is not much research on how visitors of such events perceive different weather conditions-especially hot temperatures-we explored this in our case study in southern Germany at an open-air horticultural show in the summer of 2018. We discovered deficits both in people's awareness of current heat risk and the heat adaptation they carry out themselves. Future research should further investigate risk perception and adaptation behavior of private individuals, whereas event organizers and authorities need to continually focus on risk communication and facilitate individual adaptation of their visitors.
We introduce a thermofield-based formulation of the multilayer multiconfigurational time-dependent Hartree (MCTDH) method to study finite temperature effects on non-adiabatic quantum dynamics from a non-stochastic, wave function perspective. Our approach is based on the formal equivalence of bosonic many-body theory at zero temperature with a doubled number of degrees of freedom and the thermal quasi-particle representation of bosonic thermofield dynamics (TFD). This equivalence allows for a transfer of bosonic many-body MCTDH as introduced by Wang and Thoss to the finite temperature framework of thermal quasi-particle TFD. As an application, we study temperature effects on the ultrafast internal conversion dynamics in pyrazine. We show that finite temperature effects can be efficiently accounted for in the construction of multilayer expansions of thermofield states in the framework presented herein. Furthermore, we find our results to agree well with existing studies on the pyrazine model based on the pMCTDH method.
Global quantum thermometry
(2021)
A paradigm shift in quantum thermometry is proposed. To date, thermometry has relied on local estimation, which is useful to reduce statistical fluctuations once the temperature is very well known. In order to estimate temperatures in cases where few measurement data or no substantial prior knowledge are available, we build instead a method for global quantum thermometry. Based on scaling arguments, a mean logarithmic error is shown here to be the correct figure of merit for thermometry. Its full minimization provides an operational and optimal rule to postprocess measurements into a temperature reading, and it establishes a global precision limit. We apply these results to the simulated outcomes of measurements on a spin gas, finding that the local approach can lead to biased temperature estimates in cases where the global estimator converges to the true temperature. The global framework thus enables a reliable approach to data analysis in thermometry experiments.
Respect the surroundings
(2021)
Fourteen-month-olds' ability to distinguish a just learned word, /bu?k/, from its minimally different word, /du?k/, was assessed under two pre-exposure conditions: one where /b, d/-initial forms occurred in a varying vowel context and another where the vowel was fixed but the final consonant varied. Infants in the experiments benefited from the variable vowel but not from the variable final consonant context, suggesting that vowel variability but not all kinds of variability are beneficial. These results are discussed in the context of time-honored observations on the vowel-dependent nature of place of articulation cues for consonants.
In the semiclassical limit (h) over bar -> 0, we analyze a class of self-adjoint Schrodinger operators H-(h) over bar = (h) over bar L-2 + (h) over barW + V center dot id(E) acting on sections of a vector bundle E over an oriented Riemannian manifold M where L is a Laplace type operator, W is an endomorphism field and the potential energy V has non-degenerate minima at a finite number of points m(1),... m(r) is an element of M, called potential wells. Using quasimodes of WKB-type near m(j) for eigenfunctions associated with the low lying eigenvalues of H-(h) over bar, we analyze the tunneling effect, i.e. the splitting between low lying eigenvalues, which e.g. arises in certain symmetric configurations. Technically, we treat the coupling between different potential wells by an interaction matrix and we consider the case of a single minimal geodesic (with respect to the associated Agmon metric) connecting two potential wells and the case of a submanifold of minimal geodesics of dimension l + 1. This dimension l determines the polynomial prefactor for exponentially small eigenvalue splitting.
The non-equilibrium state of two oscillators with a mutual interaction and coupled to separate heat baths is discussed. Bosonic baths are considered, and an exact spectral representation for the elements of the covariance matrix is provided analytically. A wide class of spectral densities for the relevant bath modes is allowed for. The validity of the fluctuation-dissipation relation is established for global equilibrium (both baths at the same temperature) in the stationary state. Spectral measures of entanglement are suggested by comparing to the equilibrium spectrum of zero-point fluctuations. No rotating-wave approximation is applied, and anomalous heat transport from cold to hot bath, as reported in earlier work, is demonstrated not to occur.
Recent experiments and theory suggest that ground state properties and reactivity of molecules can be modified when placed inside a nanoscale cavity, giving rise to strong coupling between vibrational modes and the quantized cavity field. This is commonly thought to be caused either by a cavity-distorted Born-Oppenheimer ground state potential or by the formation of light-matter hybrid states, vibrational polaritons. Here, we systematically study the effect of a cavity on ground state properties and infrared spectra of single molecules, considering vibration-cavity coupling strengths from zero up to the vibrational ultrastrong coupling regime. Using single-mode models for Li-H and O-H stretch modes and for the NH3 inversion mode, respectively, a single cavity mode in resonance with vibrational transitions is coupled to position-dependent molecular dipole functions. We address the influence of the cavity mode on polariton ground state energies, equilibrium bond lengths, dissociation energies, activation energies for isomerization, and on vibro-polaritonic infrared spectra. In agreement with earlier work, we observe all mentioned properties being strongly affected by the cavity, but only if the dipole self-energy contribution in the interaction Hamiltonian is neglected. When this term is included, these properties do not depend significantly on the coupling anymore. Vibro-polaritonic infrared spectra, in contrast, are always affected by the cavity mode due to the formation of excited vibrational polaritons. It is argued that the quantized nature of vibrational polaritons is key to not only interpreting molecular spectra in cavities but also understanding the experimentally observed modification of molecular reactivity in cavities.
We study the probability density function (PDF) of the first-reaction times between a diffusive ligand and a membrane-bound, immobile imperfect target region in a restricted 'onion-shell' geometry bounded by two nested membranes of arbitrary shapes. For such a setting, encountered in diverse molecular signal transduction pathways or in the narrow escape problem with additional steric constraints, we derive an exact spectral form of the PDF, as well as present its approximate form calculated by help of the so-called self-consistent approximation. For a particular case when the nested domains are concentric spheres, we get a fully explicit form of the approximated PDF, assess the accuracy of this approximation, and discuss various facets of the obtained distributions. Our results can be straightforwardly applied to describe the PDF of the terminal reaction event in multi-stage signal transduction processes.
We study the probability density function (PDF) of the first-reaction times between a diffusive ligand and a membrane-bound, immobile imperfect target region in a restricted 'onion-shell' geometry bounded by two nested membranes of arbitrary shapes. For such a setting, encountered in diverse molecular signal transduction pathways or in the narrow escape problem with additional steric constraints, we derive an exact spectral form of the PDF, as well as present its approximate form calculated by help of the so-called self-consistent approximation. For a particular case when the nested domains are concentric spheres, we get a fully explicit form of the approximated PDF, assess the accuracy of this approximation, and discuss various facets of the obtained distributions. Our results can be straightforwardly applied to describe the PDF of the terminal reaction event in multi-stage signal transduction processes.
In the frame of a world fighting a dramatic global warming caused by human-related activities, research towards the development of renewable energies plays a crucial role. Solar energy is one of the most important clean energy sources and its role in the satisfaction of the global energy demand is set to increase. In this context, a particular class of materials captured the attention of the scientific community for its attractive properties: halide perovskites. Devices with perovskite as light-absorber saw an impressive development within the last decade, reaching nowadays efficiencies comparable to mature photovoltaic technologies like silicon solar cells. Yet, there are still several roadblocks to overcome before a wide-spread commercialization of this kind of devices is enabled. One of the critical points lies at the interfaces: perovskite solar cells (PSCs) are made of several layers with different chemical and physical features. In order for the device to function properly, these properties have to be well-matched.
This dissertation deals with some of the challenges related to interfaces in PSCs, with a focus on the interface between the perovskite material itself and the subsequent charge transport layer. In particular, molecular assemblies with specific properties are deposited on the perovskite surface to functionalize it. The functionalization results in energy level alignment adjustment, interfacial losses reduction, and stability improvement.
First, a strategy to tune the perovskite’s energy levels is introduced: self-assembled monolayers of dipolar molecules are used to functionalize the surface, obtaining simultaneously a shift in the vacuum level position and a saturation of the dangling bonds at the surface. A shift in the vacuum level corresponds to an equal change in work function, ionization energy, and electron affinity. The direction of the shift depends on the direction of the collective interfacial dipole. The magnitude of the shift can be tailored by controlling the deposition parameters, such as the concentration of the solution used for the deposition. The shift for different molecules is characterized by several non-invasive techniques, including in particular Kelvin probe. Overall, it is shown that it is possible to shift the perovskite energy levels in both directions by several hundreds of meV. Moreover, interesting insights on the molecules deposition dynamics are revealed.
Secondly, the application of this strategy in perovskite solar cells is explored. Devices with different perovskite compositions (“triple cation perovskite” and MAPbBr3) are prepared. The two resulting model systems present different energetic offsets at the perovskite/hole-transport layer interface. Upon tailored perovskite surface functionalization, the devices show a stabilized open circuit voltage (Voc) enhancement of approximately 60 meV on average for devices with MAPbBr3, while the impact is limited on triple-cation solar cells. This suggests that the proposed energy level tuning method is valid, but its effectiveness depends on factors such as the significance of the energetic offset compared to the other losses in the devices.
Finally, the above presented method is further developed by incorporating the ability to interact with the perovskite surface directly into a novel hole-transport material (HTM), named PFI. The HTM can anchor to the perovskite halide ions via halogen bonding (XB). Its behaviour is compared to that of another HTM (PF) with same chemical structure and properties, except for the ability of forming XB. The interaction of perovskite with PFI and PF is characterized through UV-Vis, atomic force microscopy and Kelvin probe measurements combined with simulations. Compared to PF, PFI exhibits enhanced resilience against solvent exposure and improved energy level alignment with the perovskite layer. As a consequence, devices comprising PFI show enhanced Voc and operational stability during maximum-power-point tracking, in addition to hysteresis reduction. XB promotes the formation of a high-quality interface by anchoring to the halide ions and forming a stable and ordered interfacial layer, showing to be a particularly interesting candidate for the development of tailored charge transport materials in PSCs.
Overall, the results exposed in this dissertation introduce and discuss a versatile tool to functionalize the perovskite surface and tune its energy levels. The application of this method in devices is explored and insights on its challenges and advantages are given. Within this frame, the results shed light on XB as ideal interaction for enhancing stability and efficiency in perovskite-based devices.
In our daily life, recurrence plays an important role on many spatial and temporal scales and in different contexts. It is the foundation of learning, be it in an evolutionary or in a neural context. It therefore seems natural that recurrence is also a fundamental concept in theoretical dynamical systems science. The way in which states of a system recur or develop in a similar way from similar initial states makes it possible to infer information about the underlying dynamics of the system. The mathematical space in which we define the state of a system (state space) is often high dimensional, especially in complex systems that can also exhibit chaotic dynamics. The recurrence plot (RP) enables us to visualize the recurrences of any high-dimensional systems in a two-dimensional, binary representation. Certain patterns in RPs can be related to physical properties of the underlying system, making the qualitative and quantitative analysis of RPs an integral part of nonlinear systems science. The presented work has a methodological focus and further develops recurrence analysis (RA) by addressing current research questions related to an increasing amount of available data and advances in machine learning techniques. By automatizing a central step in RA, namely the reconstruction of the state space from measured experimental time series, and by investigating the impact of important free parameters this thesis aims to make RA more accessible to researchers outside of physics.
The first part of this dissertation is concerned with the reconstruction of the state space from time series. To this end, a novel idea is proposed which automates the reconstruction problem in the sense that there is no need to preprocesse the data or estimate parameters a priori. The key idea is that the goodness of a reconstruction can be evaluated by a suitable objective function and that this function is minimized in the embedding process. In addition, the new method can process multivariate time series input data. This is particularly important because multi-channel sensor-based observations are ubiquitous in many research areas and continue to increase. Building on this, the described minimization problem of the objective function is then processed using a machine learning approach.
In the second part technical and methodological aspects of RA are discussed. First, we mathematically justify the idea of setting the most influential free parameter in RA, the recurrence threshold ε, in relation to the distribution of all pairwise distances in the data. This is especially important when comparing different RPs and their quantification statistics and is fundamental to any comparative study. Second, some aspects of recurrence quantification analysis (RQA) are examined. As correction schemes for biased RQA statistics, which are based on diagonal lines, we propose a simple method for dealing with border effects of an RP in RQA and a skeletonization algorithm for RPs. This results in less biased (diagonal line based) RQA statistics for flow-like data. Third, a novel type of RQA characteristic is developed, which can be viewed as a generalized non-linear powerspectrum of high dimensional systems. The spike powerspectrum transforms a spike-train like signal into its frequency domain. When transforming the diagonal line-dependent recurrence rate (τ-RR) of a RP in this way, characteristic periods, which can be seen in the state space representation of the system can be unraveled. This is not the case, when Fourier transforming τ-RR.
Finally, RA and RQA are applied to climate science in the third part and neuroscience in the fourth part. To the best of our knowledge, this is the first time RPs and RQA have been used to analyze lake sediment data in a paleoclimate context. Therefore, we first elaborate on the basic formalism and the interpretation of visually visible patterns in RPs in relation to the underlying proxy data. We show that these patterns can be used to classify certain types of variability and transitions in the Potassium record from six short (< 17m) sediment cores collected during the Chew Bahir Drilling Project. Building on this, the long core (∼ m composite) from the same site is analyzed and two types of variability and transitions are
identified and compared with ODP Site wetness index from the eastern Mediterranean. Type variability likely reflects the influence of precessional forcing in the lower latitudes at times of maximum values of the long eccentricity cycle ( kyr) of the earth’s orbit around the sun, with a tendency towards extreme events. Type variability appears to be related to the minimum values of this cycle and corresponds to fairly rapid transitions between relatively dry and relatively wet conditions.
In contrast, RQA has been applied in the neuroscientific context for almost two decades. In the final part, RQA statistics are used to quantify the complexity in a specific frequency band of multivariate EEG (electroencephalography) data. By analyzing experimental data, it can be shown that the complexity of the signal measured in this way across the sensorimotor cortex decreases as motor tasks are performed. The results are consistent with and comple- ment the well known concepts of motor-related brain processes. We assume that the thus discovered features of neuronal dynamics in the sensorimotor cortex together with the robust RQA methods for identifying and classifying these contribute to the non-invasive EEG-based development of brain-computer interfaces (BCI) for motor control and rehabilitation.
The present work is an important step towards a robust analysis of complex systems based on recurrence.
Aufgrund der Bedeutung von Experimenten im physikalischen Erkenntnisprozess, sind diese ein wesentlicher Bestandteil des Physikunterrichts. Um den Einsatz von Experimenten im Physikunterricht zu fördern, sind kompetenzorientiertes Experimentieren und die Reflexion des Einsatzes von Experimenten wichtige Ziele in Lehrkräftebildungsprogrammen. Ablaufmodelle für kompetenzorientiertes Experimentieren unterscheiden typischerweise Phasen der Fragen- und Hypothesenentwicklung, der Planung, der Erforschung und der Schlussfolgerungen. Es ist allerdings unklar, auf welche Weise angehende Physiklehrkräfte Aspekte des kompetenzorientierten Experimentierens in ihrem Unterricht in schulpraktischen Ausbildungsphasen einsetzen, auf welche Weise sie solche Unterrichtsversuche mit Experimentierbezug reflektieren und wie strukturiert (im Sinne der Ablaufmodelle) sie dabei vorgehen.
In der vorliegenden Studie wurde deshalb untersucht, auf welche Weise Praxissemesterstudierende Experimentierprozesse in ihren Unterrichtsversuchen reflektieren. Hierfür wurde betrachtet, zu welchen Anteilen die Experimentierphasen in den Reflexionen adressiert werden. Um weiterhin herauszufinden, mit welcher Qualität die Experimentplanung reflektiert wird und inwiefern sich Vorstrukturierung für die Planungsphase zeigt, wurde diese differenzierter betrachtet. Auf Basis empirischer Vorarbeiten wurde vermutet, dass Fragenentwicklung, Hypothesenbildung und Experimentplanung seltener thematisiert werden als die anderen Teilkompetenzen und dass die Planungsphase hauptsächlich stark vorstrukturierte Elemente enthält, statt den Lernenden Freiräume für selbstständige Planungen zu lassen.
Zur Untersuchung der Fragestellung wurden Kodiermanuale zur Erfassung experimentierbezogener Kompetenzen in schriftlichen Reflexionen entwickelt und validiert. Analysiert wurden 40 Reflexionstexte von 14 Studierenden des Physik-Lehramts im Praxissemester an der Universität Potsdam. Als Untersuchungsmethode wurde die qualitative Inhaltsanalyse genutzt. Die Texte wurden bezüglich der Umsetzung eines Reflexionsmodells und auf das Vorkommen der Teilkompetenzen des Experimentierzyklus untersucht.
Die Ergebnisse bestätigten das geringe Vorkommen der Fragenentwicklung und Hypothesenbildung sowie die tendenziell geschlossenen Planungsinhalte. Zudem konnte festgestellt werden, dass die Planungsphase eher oberflächlich reflektiert und vor allem Arbeitsaufträge wiedergegeben wurden. Allgemein zeigten sich hauptsächlich beschreibende Tendenzen in den Reflexionen und eher wenige Alternativen und Konsequenzen. Aus den Ergebnissen werden Implikationen für die Lehrkräftebildung im Fach Physik abgeleitet. Um die Reflexionskompetenz der angehenden Lehrkräfte zu fördern, sind Hilfestellungen während des Reflexionsprozesses und eine inhaltliche Rückmeldung notwendig. Des Weiteren sollten die angehenden Lehrkräfte für eine ausgewogenere Förderung der Teilkompetenzen in ihrem Unterricht sensibilisiert werden.
Synchronization of coupled oscillators manifests itself in many natural and man-made systems, including cyrcadian clocks, central pattern generators, laser arrays, power grids, chemical and electrochemical oscillators, only to name a few. The mathematical description of this phenomenon is often based on the paradigmatic Kuramoto model, which represents each oscillator by one scalar variable, its phase. When coupled, phase oscillators constitute a high-dimensional dynamical system, which exhibits complex behaviour, ranging from synchronized uniform oscillation to quasiperiodicity and chaos. The corresponding collective rhythms can be useful or harmful to the normal operation of various systems, therefore they have been the subject of much research.
Initially, synchronization phenomena have been studied in systems with all-to-all (global) and nearest-neighbour (local) coupling, or on random networks. However, in recent decades there has been a lot of interest in more complicated coupling structures, which take into account the spatially distributed nature of real-world oscillator systems and the distance-dependent nature of the interaction between their components. Examples of such systems are abound in biology and neuroscience. They include spatially distributed cell populations, cilia carpets and neural networks relevant to working memory. In many cases, these systems support a rich variety of patterns of synchrony and disorder with remarkable properties that have not been observed in other continuous media. Such patterns are usually referred to as the coherence-incoherence patterns, but in symmetrically coupled oscillator systems they are also known by the name chimera states.
The main goal of this work is to give an overview of different types of collective behaviour in large networks of spatially distributed phase oscillators and to develop mathematical methods for their analysis. We focus on the Kuramoto models for one-, two- and three-dimensional oscillator arrays with nonlocal coupling, where the coupling extends over a range wider than nearest neighbour coupling and depends on separation. We use the fact that, for a special (but still quite general) phase interaction function, the long-term coarse-grained dynamics of the above systems can be described by a certain integro-differential equation that follows from the mathematical approach called the Ott-Antonsen theory. We show that this equation adequately represents all relevant patterns of synchrony and disorder, including stationary, periodically breathing and moving coherence-incoherence patterns. Moreover, we show that this equation can be used to completely solve the existence and stability problem for each of these patterns and to reliably predict their main properties in many application relevant situations.
Magnetic strain contributions in laser-excited metals studied by time-resolved X-ray diffraction
(2021)
In this work I explore the impact of magnetic order on the laser-induced ultrafast strain response of metals. Few experiments with femto- or picosecond time-resolution have so far investigated magnetic stresses. This is contrasted by the industrial usage of magnetic invar materials or magnetostrictive transducers for ultrasound generation, which already utilize magnetostrictive stresses in the low frequency regime.
In the reported experiments I investigate how the energy deposition by the absorption of femtosecond laser pulses in thin metal films leads to an ultrafast stress generation. I utilize that this stress drives an expansion that emits nanoscopic strain pulses, so called hypersound, into adjacent layers. Both the expansion and the strain pulses change the average inter-atomic distance in the sample, which can be tracked with sub-picosecond time resolution using an X-ray diffraction setup at a laser-driven Plasma X-ray source. Ultrafast X-ray diffraction can also be applied to buried layers within heterostructures that cannot be accessed by optical methods, which exhibit a limited penetration into metals. The reconstruction of the initial energy transfer processes from the shape of the strain pulse in buried detection layers represents a contribution of this work to the field of picosecond ultrasonics.
A central point for the analysis of the experiments is the direct link between the deposited energy density in the nano-structures and the resulting stress on the crystal lattice. The underlying thermodynamical concept of a Grüneisen parameter provides the theoretical framework for my work. I demonstrate how the Grüneisen principle can be used for the interpretation of the strain response on ultrafast timescales in various materials and that it can be extended to describe magnetic stresses. The class of heavy rare-earth elements exhibits especially large magnetostriction effects, which can even lead to an unconventional contraction of the laser-excited transducer material. Such a dominant contribution of the magnetic stress to the motion of atoms has not been demonstrated previously. The observed rise time of the magnetic stress contribution in Dysprosium is identical to the decrease in the helical spin-order, that has been found previously using time-resolved resonant X-ray diffraction. This indicates that the strength of the magnetic stress can be used as a proxy of the underlying magnetic order. Such magnetostriction measurements are applicable even in case of antiparallel or non-collinear alignment of the magnetic moments and a vanishing magnetization.
The strain response of metal films is usually determined by the pressure of electrons and lattice vibrations. I have developed a versatile two-pulse excitation routine that can be used to extract the magnetic contribution to the strain response even if systematic measurements above and below the magnetic ordering temperature are not feasible. A first laser pulse leads to a partial ultrafast demagnetization so that the amplitude and shape of the strain response triggered by the second pulse depends on the remaining magnetic order. With this method I could identify a strongly anisotropic magnetic stress contribution in the magnetic data storage material iron-platinum and identify the recovery of the magnetic order by the variation of the pulse-to-pulse delay. The stark contrast of the expansion of iron-platinum nanograins and thin films shows that the different constraints for the in-plane expansion have a strong influence on the out-of-plane expansion, due to the Poisson effect. I show how such transverse strain contributions need to be accounted for when interpreting the ultrafast out-of-plane strain response using thermal expansion coefficients obtained in near equilibrium conditions.
This work contributes an investigation of magnetostriction on ultrafast timescales to the literature of magnetic effects in materials. It develops a method to extract spatial and temporal varying stress contributions based on a model for the amplitude and shape of the emitted strain pulses. Energy transfer processes result in a change of the stress profile with respect to the initial absorption of the laser pulses. One interesting example occurs in nanoscopic gold-nickel heterostructures, where excited electrons rapidly transport energy into a distant nickel layer, that takes up much more energy and expands faster and stronger than the laser-excited gold capping layer. Magnetic excitations in rare earth materials represent a large energy reservoir that delays the energy transfer into adjacent layers. Such magneto-caloric effects are known in thermodynamics but not extensively covered on ultrafast timescales. The combination of ultrafast X-ray diffraction and time-resolved techniques with direct access to the magnetization has a large potential to uncover and quantify such energy transfer processes.
The evolution of life on Earth has been driven by disturbances of different types and magnitudes over the 4.6 million years of Earth’s history (Raup, 1994, Alroy, 2008). One example for such disturbances are mass extinctions which are characterized by an exceptional increase in the extinction rate affecting a great number of taxa in a short interval of geologic time (Sepkoski, 1986). During the 541 million years of the Phanerozoic, life on Earth suffered five exceptionally severe mass extinctions named the “Big Five Extinctions”. Many mass extinctions are linked to changes in climate
(Feulner, 2009). Hence, the study of past mass extinctions is not only intriguing, but can also provide insights into the complex nature of the Earth system. This thesis aims at deepening our understanding of the triggers of mass extinctions and how they affected life. To accomplish this, I investigate changes in climate during two of the Big Five extinctions using a coupled climate model.
During the Devonian (419.2–358.9 million years ago) the first vascular plants and vertebrates evolved on land while extinction events occurred in the ocean (Algeo et al., 1995). The causes of these formative changes, their interactions and their links to changes in climate are still poorly understood. Therefore, we explore the sensitivity of the Devonian climate to various boundary conditions using an intermediate-complexity climate model (Brugger et al., 2019). In contrast to Le Hir et al. (2011), we find only a minor biogeophysical effect of changes in vegetation cover due to unrealistically high soil albedo values used in the earlier study. In addition, our results cannot support the strong influence of orbital parameters on the Devonian climate, as simulated with a climate model with a strongly simplified ocean model (De Vleeschouwer et al., 2013, 2014, 2017). We can only reproduce the changes in Devonian climate suggested by proxy data by decreasing atmospheric CO2. Still, finding agreement between the evolution of sea surface temperatures reconstructed from proxy data (Joachimski et al., 2009) and our simulations remains challenging and suggests a lower δ18O ratio of Devonian seawater. Furthermore, our study of the sensitivity of the Devonian climate reveals a prevailing mode of climate variability on a timescale of decades to centuries. The quasi-periodic ocean temperature fluctuations are linked to a physical mechanism of changing sea-ice cover, ocean convection and overturning in high northern latitudes.
In the second study of this thesis (Dahl et al., under review) a new reconstruction of atmospheric CO2 for the Devonian, which is based on CO2-sensitive carbon isotope fractionation in the earliest vascular plant fossils, suggests a much earlier drop of atmo- spheric CO2 concentration than previously reconstructed, followed by nearly constant CO2 concentrations during the Middle and Late Devonian. Our simulations for the Early Devonian with identical boundary conditions as in our Devonian sensitivity study (Brugger et al., 2019), but with a low atmospheric CO2 concentration of 500 ppm, show no direct conflict with available proxy and paleobotanical data and confirm that under the simulated climatic conditions carbon isotope fractionation represents a robust proxy for atmospheric CO2. To explain the earlier CO2 drop we suggest that early forms of vascular land plants have already strongly influenced weathering. This new perspective on the Devonian questions previous ideas about the climatic conditions and earlier explanations for the Devonian mass extinctions.
The second mass extinction investigated in this thesis is the end-Cretaceous mass extinction (66 million years ago) which differs from the Devonian mass extinctions in terms of the processes involved and the timescale on which the extinctions occurred. In the two studies presented here (Brugger et al., 2017, 2021), we model the climatic effects of the Chicxulub impact, one of the proposed causes of the end-Cretaceous extinction, for the first millennium after the impact. The light-dimming effect of stratospheric sulfate aerosols causes severe cooling, with a decrease of global annual mean surface air temperature of at least 26◦C and a recovery to pre-impact temperatures after more than 30 years. The sudden surface cooling of the ocean induces deep convection which brings nutrients from the deep ocean via upwelling to the surface ocean. Using an ocean biogeochemistry model we explore the combined effect of ocean mixing and iron-rich dust originating from the impactor on the marine biosphere. As soon as light levels have recovered, we find a short, but prominent peak in marine net primary productivity. This newly discovered mechanism could result in toxic effects for marine near-surface ecosystems. Comparison of our model results to proxy data (Vellekoop et al., 2014, 2016, Hull et al., 2020) suggests that carbon release from the terrestrial biosphere is required in addition to the carbon dioxide which can be attributed to the target material. Surface ocean acidification caused by the addition of carbon dioxide and sulfur is only moderate. Taken together, the results indicate a significant contribution of the Chicxulub impact to the end-Cretaceous mass extinction by triggering multiple stressors for the Earth system.
Although the sixth extinction we face today is characterized by human intervention in nature, this thesis shows that we can gain many insights into future extinctions from studying past mass extinctions, such as the importance of the rate of change (Rothman, 2017), the interplay of multiple stressors (Gunderson et al., 2016), and changes in the carbon cycle (Rothman, 2017, Tierney et al., 2020).
Any physical system can be described on the level of interacting particles, thus it is of fundamental importance to improve the scientific understanding of interacting many-body systems. This thesis experimentally addresses specific quasi-particle interactions, namely interactions be- tween electrons and between electrons and phonons. It describes the consequential effects of those processes on the electronic structure and the core-hole relaxation pathways in 3d metals. Despite the great amount of experimental and theoretical studies of these interactions and their impact on the behavior of solid-state matter, there are still open questions concerning the cor- responding physical, chemical and mechanical properties of solid-state matter. Especially, the study of 3d metals and their compounds is a great experimental challenge, since those exhibit a variety of spectral features originating from many-body effects such as multiplet splitting, shake up/off satellites, vibrationally excited states or more complex effects like superconductivity and ultrafast demagnetization. In X-ray spectroscopy, these effects often produce overlapping fea- tures, complicating the analysis and limiting the understanding. In this thesis, to overcome the limitations set by conventional X-ray spectroscopy, two different experimental approaches were successfully refined, namely Auger electron photoelectron coincidence spectroscopy (APECS) and temperature-dependent X-ray emission spectroscopy (tXES), which enabled the separation of different core-hole relaxation pathways and the isolation of the impact of specific many-body interactions in the experimental spectra. APECS was utilized at the new Coincidence electron spectroscopy for chemical analysis (Co- ESCA) station at BESSY II to study the core-hole decay and electron-correlation effects in single- crystal Ni, Cu and Co. The observation of photoelectrons in coincidence with Auger electrons allows for the separation of the initial and final state effects in the Auger electron spectra. The results show that a Cu LV V Auger spectrum can be represented by broadened atomic multiplets confirming the localized nature of the intermediate core-hole states. In contrast, the Co LV V Auger spectrum is band-like and can be represented by the self-convolution of the valence band. Ni behaves mixed, localized and itinerant. Thus, the Ni Auger spectrum can only be represented by a mixture of atomic multiplet peaks and the self-convoluted valence band. In the case of Ni, the LV V Auger electrons in coincidence with the 6 eV satellite photoelectrons were also stud- ied. Utilizing the core-hole clock method, the lifetime of the localized double-hole intermediate 2 p53d9 states of 1.8 fs could be determined. However, a fraction of these states delocalizes before the Auger decay contributing to the main peak. A similar delocalization was observed for the double-hole states produced by the L2L3M4,5 Coster-Kronig process. Additionally, the influence of surface oxidation on the Ni(111) 3p levels was studied with APECS. The Ni 3p PES spectrum is broad and featureless, due to overlapping many-body effects and gives little chance for exact analysis using conventional photoelectron spectroscopy. Utilizing APECS or precisely the final state selectivity of the method, the spectral width of the 3p levels could be narrowed and their positions and the spin-orbit splitting were determined. Moreover, due to the surface sensitivity of the method, the chemically shifted 3p photoelectron peaks originating from the oxidized surface and the bulk Ni were disentangled. For the study of the atomic electron-phonon spin-flip scattering in 3d metals as a spin-relaxation channel, the tXES method at the SolidFlexRIXS station was developed. The atomic spin-flip scat- tering was studied in single-crystal Ni, Cu, Co and in FeNi alloys, which show considerable dif- ferences in their behavior. The scattering rate in Ni increases with temperature, whereas the rate in Cu and Co remains constant within the measured temperature range up to 1000 K. In FeNi alloys, our results reveal that the spin-flip scattering is restricted by sublattice exchange energies J. The electron-phonon scattering driven spin-flips only appear in the case where the thermal energy ex- ceeds the exchange energy kT > J. This thresholding is an important microscopic process for the description of the sublattice dynamics in alloys, but as shown also relevant for elemental magnetic systems. Overall, the results strongly indicate that the spin-flip probability is correlated with the exchange energy, which might become an important parameter in the ultrafast demagnetization debate. Taken together, the applied experimental approaches allowed to study complex many-body effects in 3d metals. The results show that utilizing APECS enabled the distinction and clear assignment of otherwise overlapping features in AES or PES spectra of Ni, Cu, Co and NiO. This is of fundamental importance for the basic understanding of photoionization and core-hole decay processes but also for the chemical analysis in applied science. The measurement of the atomic electron-phonon spin-flip scattering rate utilizing tXES shows that the electron-phonon spin-flip scattering is a relevant atomic process for the macroscopic demagnetization process. Additionally, a temperature-dependent thresholding mechanism was discovered, which introduces an important dynamic factor into the electron-phonon spin-flip model.
In this paper, we report X-ray absorption and core-level electron spectra of the nucleobase derivative 2-thiouracil at the sulfur L1- and L2,3-edges. We used soft X-rays from the free-electron laser FLASH2 for the excitation of isolated molecules and dispersed the outgoing electrons with a magnetic bottle spectrometer. We identified photoelectrons from the 2p core orbital, accompanied by an electron correlation satellite, as well as resonant and non-resonant Coster–Kronig and Auger–Meitner emission at the L1- and L2,3-edges, respectively. We used the electron yield to construct X-ray absorption spectra at the two edges. The experimental data obtained are put in the context of the literature currently available on sulfur core-level and 2-thiouracil spectroscopy.
In this paper, we report X-ray absorption and core-level electron spectra of the nucleobase derivative 2-thiouracil at the sulfur L1- and L2,3-edges. We used soft X-rays from the free-electron laser FLASH2 for the excitation of isolated molecules and dispersed the outgoing electrons with a magnetic bottle spectrometer. We identified photoelectrons from the 2p core orbital, accompanied by an electron correlation satellite, as well as resonant and non-resonant Coster–Kronig and Auger–Meitner emission at the L1- and L2,3-edges, respectively. We used the electron yield to construct X-ray absorption spectra at the two edges. The experimental data obtained are put in the context of the literature currently available on sulfur core-level and 2-thiouracil spectroscopy.
We consider a sequential cascade of molecular first-reaction events towards a terminal reaction centre in which each reaction step is controlled by diffusive motion of the particles. The model studied here represents a typical reaction setting encountered in diverse molecular biology systems, in which, e.g. a signal transduction proceeds via a series of consecutive 'messengers': the first messenger has to find its respective immobile target site triggering a launch of the second messenger, the second messenger seeks its own target site and provokes a launch of the third messenger and so on, resembling a relay race in human competitions. For such a molecular relay race taking place in infinite one-, two- and three-dimensional systems, we find exact expressions for the probability density function of the time instant of the terminal reaction event, conditioned on preceding successful reaction events on an ordered array of target sites. The obtained expressions pertain to the most general conditions: number of intermediate stages and the corresponding diffusion coefficients, the sizes of the target sites, the distances between them, as well as their reactivities are arbitrary.
We consider a sequential cascade of molecular first-reaction events towards a terminal reaction centre in which each reaction step is controlled by diffusive motion of the particles. The model studied here represents a typical reaction setting encountered in diverse molecular biology systems, in which, e.g. a signal transduction proceeds via a series of consecutive 'messengers': the first messenger has to find its respective immobile target site triggering a launch of the second messenger, the second messenger seeks its own target site and provokes a launch of the third messenger and so on, resembling a relay race in human competitions. For such a molecular relay race taking place in infinite one-, two- and three-dimensional systems, we find exact expressions for the probability density function of the time instant of the terminal reaction event, conditioned on preceding successful reaction events on an ordered array of target sites. The obtained expressions pertain to the most general conditions: number of intermediate stages and the corresponding diffusion coefficients, the sizes of the target sites, the distances between them, as well as their reactivities are arbitrary.
In this work, we investigate the potassium excess absorption around 7699 Å of the exoplanets HD189733b and HD209458b. For this purpose, we used high-spectral resolution transit observations acquired with the 2 × 8.4 m Large Binocular Telescope (LBT) and the Potsdam Echelle Polarimetric and Spectroscopic Instrument (PEPSI). For a bandwidth of 0.8 Å, we present a detection >7σ with an absorption level of 0.18 per cent for HD189733b. Applying the same analysis to HD209458b, we can set 3σ upper limit of 0.09 per cent, even though we do not detect a K-excess absorption. The investigation suggests that the K feature is less present in the atmosphere of HD209458b than in the one of HD189733b. This comparison confirms previous claims that the atmospheres of these two planets must have fundamentally different properties.
The study of exoplanet atmospheres showed large diversity compared to the planets in our Solar system. Especially Jupiter-type exoplanets orbiting their host star in close orbits, the so-called hot and ultra-hot Jupiters, have been studied in detail due to their enhanced atmospheric signature. Due to their tidally locked status, the temperature difference between the day- and nightside triggers atmospheric winds that can lead to various fingerprints in the observations. Spatially resolved absorption lines during transit such as sodium (Na) could be a good tracer for such winds. Different works resolved the Na absorption lines on different exoplanets which show different line widths. Assuming that this could be attributed to such zonal jet streams, this work models the effect of such winds on synthetic absorption lines. For this, transiting Jupiter-type planets with rotational velocities similar to hot and ultra-hot Jupiter are considered. The investigation shows that high wind velocities could reproduce the broadening of Na-line profiles inferred in different high-resolution transit observations. There is a tendency that the broadening values decrease for planets with lower equilibrium temperature. This could be explained by atmospheric drag induced by the ionization of alkali lines that slow down the zonal jet streams, favouring their existence on hot Jupiter rather than ultra-hot Jupiter.