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We study the experimentally measured ciprofloxacin antibiotic diffusion through a gel-like artificial sputum medium (ASM) mimicking physiological conditions typical for a cystic fibrosis layer, in which regions occupied by Pseudomonas aeruginosa bacteria are present. To quantify the antibiotic diffusion dynamics we employ a phenomenological model using a subdiffusion-absorption equation with a fractional time derivative. This effective equation describes molecular diffusion in a medium structured akin Thompson’s plumpudding model; here the ‘pudding’ background represents the ASM and the ‘plums’ represent the bacterial biofilm. The pudding is a subdiffusion barrier for antibiotic molecules that can affect bacteria found in plums. For the experimental study we use an interferometric method to determine the time evolution of the amount of antibiotic that has diffused through the biofilm. The theoretical model shows that this function is qualitatively different depending on whether or not absorption of the antibiotic in the biofilm occurs. We show that the process can be divided into three successive stages: (1) only antibiotic subdiffusion with constant biofilm parameters, (2) subdiffusion and absorption of antibiotic molecules with variable biofilm transport parameters, (3) subdiffusion and absorption in the medium but the biofilm parameters are constant again. Stage 2 is interpreted as the appearance of an intensive defence build–up of bacteria against the action of the antibiotic, and in the stage 3 it is likely that the bacteria have been inactivated. Times at which stages change are determined from the experimentally obtained temporal evolution of the amount of antibiotic that has diffused through the ASM with bacteria. Our analysis shows good agreement between experimental and theoretical results and is consistent with the biologically expected biofilm response. We show that an experimental method to study the temporal evolution of the amount of a substance that has diffused through a biofilm is useful in studying the processes occurring in a biofilm. We also show that the complicated biological process of antibiotic diffusion in a biofilm can be described by a fractional subdiffusion-absorption equation with subdiffusion and absorption parameters that change over time.
Open-circuit voltages of lead-halide perovskite solar cells are improving rapidly and are approaching the thermodynamic limit. Since many different perovskite compositions with different bandgap energies are actively being investigated, it is not straightforward to compare the open-circuit voltages between these devices as long as a consistent method of referencing is missing. For the purpose of comparing open-circuit voltages and identifying outstanding values, it is imperative to use a unique, generally accepted way of calculating the thermodynamic limit, which is currently not the case. Here a meta-analysis of methods to determine the bandgap and a radiative limit for open-circuit voltage is presented. The differences between the methods are analyzed and an easily applicable approach based on the solar cell quantum efficiency as a general reference is proposed.
Recombination of free charge is a key process limiting the performance of solar cells. For low mobility materials, such as organic semiconductors, the kinetics of non-geminate recombination (NGR) is strongly linked to the motion of charges. As these materials possess significant disorder, thermalization of photogenerated carriers in the inhomogeneously broadened density of state distribution is an unavoidable process. Despite its general importance, knowledge about the kinetics of NGR in complete organic solar cells is rather limited. We employ time delayed collection field (TDCF) experiments to study the recombination of photogenerated charge in the high-performance polymer:fullerene blend PCDTBT:PCBM. NGR in the bulk of this amorphous blend is shown to be highly dispersive, with a continuous reduction of the recombination coefficient throughout the entire time scale, until all charge carriers have either been extracted or recombined. Rapid, contact-mediated recombination is identified as an additional loss channel, which, if not properly taken into account, would erroneously suggest a pronounced field dependence of charge generation. These findings are in stark contrast to the results of TDCF experiments on photovoltaic devices made from ordered blends, such as P3HT:PCBM, where non-dispersive recombination was proven to dominate the charge carrier dynamics under application relevant conditions.
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.
This work focuses on the dynamics of particles in a confined geometry with position-dependent diffusivity, where the confinement is modelled by a periodic channel consisting of unit cells connected by narrow passage ways. We consider three functional forms for the diffusivity, corresponding to the scenarios of a constant (D ₀), as well as a low (D ₘ) and a high (D d) mobility diffusion in cell centre of the longitudinally symmetric cells. Due to the interaction among the diffusivity, channel shape and external force, the system exhibits complex and interesting phenomena. By calculating the probability density function, mean velocity and mean first exit time with the Itô calculus form, we find that in the absence of external forces the diffusivity D d will redistribute particles near the channel wall, while the diffusivity D ₘ will trap them near the cell centre. The superposition of external forces will break their static distributions. Besides, our results demonstrate that for the diffusivity D d, a high dependence on the x coordinate (parallel with the central channel line) will improve the mean velocity of the particles. In contrast, for the diffusivity D ₘ, a weak dependence on the x coordinate will dramatically accelerate the moving speed. In addition, it shows that a large external force can weaken the influences of different diffusivities; inversely, for a small external force, the types of diffusivity affect significantly the particle dynamics. In practice, one can apply these results to achieve a prominent enhancement of the particle transport in two- or three-dimensional channels by modulating the local tracer diffusivity via an engineered gel of varying porosity or by adding a cold tube to cool down the diffusivity along the central line, which may be a relevant effect in engineering applications. Effects of different stochastic calculi in the evaluation of the underlying multiplicative stochastic equation for different physical scenarios are discussed.
Herein, we report the chain-growth tin-free room temperature polymerization method to synthesize n-type perylene diimide-dithiophene-based conjugated polymers (PPDIT2s) suitable for solar cell and transistor applications. The palladium/electron-rich tri-tert-butylphosphine catalyst is effective to enable the chain-growth polymerization of anion-radical monomer Br-TPDIT-Br/Zn to PPDIT2 with a molecular weight up to Mw ≈ 50 kg mol−1 and moderate polydispersity. This is the second example of the polymerization of unusual anion-radical aromatic complexes formed in a reaction of active Zn and electron-deficient diimide-based aryl halides. As such, the discovered polymerization method is not a specific reactivity feature of the naphthalene-diimide derivatives but is rather a general polymerization tool. This is an important finding, given the significantly higher maximum external quantum efficiency that can be reached with PDI-based copolymers (32–45%) in all-polymer solar cells compared to NDI-based materials (15–30%). Our studies revealed that PPDIT2 synthesized by the new method and the previously published polymer prepared by step-growth Stille polycondensation show similar electron mobility and all-polymer solar cell performance. At the same time, the polymerization reported herein has several technological advantages as it proceeds relatively fast at room temperature and does not involve toxic tin-based compounds. Because several chain-growth polymerization reactions are well-suited for the preparation of well-defined multi-functional polymer architectures, the next target is to explore the utility of the discovered polymerization in the synthesis of end-functionalized polymers and block copolymers. Such materials would be helpful to improve the nanoscale morphology of polymer blends in all-polymer solar cells.
We demonstrate in situ recorded motion of nano-objects adsorbed on a photosensitive polymer film. The motion is induced by a mass transport of the underlying photoresponsive polymer material occurring during irradiation with interference pattern. The polymer film contains azobenzene molecules that undergo reversible photoisomerization reaction from trans- to cis-conformation. Through a multi-scale chain of physico-chemical processes, this finally results in the macro-deformations of the film due to the changing elastic properties of polymer. The topographical deformation of the polymer surface is sensitive to a local distribution of the electrical field vector that allows for the generation of dynamic changes in the surface topography during irradiation with different light interference patterns. Polymer film deformation together with the motion of the adsorbed nano-particles are recorded using a homemade set-up combining an optical part for the generation of interference patterns and an atomic force microscope for acquiring the surface deformation. The particles undergo either translational or rotational motion. The direction of particle motion is towards the topography minima and opposite to the mass transport within the polymer film. The ability to relocate particles by photo-induced dynamic topography fluctuation offers a way for a non-contact simultaneous manipulation of a large number of adsorbed particles just in air at ambient conditions.
Despite the ongoing progress in nanotechnology and its applications, the development of strategies for connecting nano-scale systems to micro- or macroscale elements is hampered by the lack of structural components that have both, nano- and macroscale dimensions. The production of nano-scale wires with macroscale length is one of the most interesting challenges here. There are a lot of strategies to fabricate long nanoscopic stripes made of metals, polymers or ceramics but none is suitable for mass production of ordered and dense arrangements of wires at large numbers. In this paper, we report on a technique for producing arrays of ordered, flexible and free-standing polymer nano-wires filled with different types of nano-particles. The process utilizes the strong response of photosensitive polymer brushes to irradiation with UV-interference patterns, resulting in a substantial mass redistribution of the polymer material along with local rupturing of polymer chains. The chains can wind up in wires of nano-scale thickness and a length of up to several centimeters. When dispersing nano-particles within the film, the final arrangement is similar to a core-shell geometry with mainly nano-particles found in the core region and the polymer forming a dielectric jacket.
We study properties of magnetohydrodynamic (MHD) eigenmodes by decomposing the data of MHD simulations into linear MHD modes-namely, the Alfven, slow magnetosonic, and fast magnetosonic modes. We drive turbulence with a mixture of solenoidal and compressive driving while varying the Alfven Mach number (M-A), plasma beta, and the sonic Mach number from subsonic to transsonic. We find that the proportion of fast and slow modes in the mode mixture increases with increasing compressive forcing. This proportion of the magnetosonic modes can also become the dominant fraction in the mode mixture. The anisotropy of the modes is analyzed by means of their structure functions. The Alfven-mode anisotropy is consistent with the Goldreich-Sridhar theory. We find a transition from weak to strong Alfvenic turbulence as we go from low to high M-A. The slow-mode properties are similar to the Alfven mode. On the other hand, the isotropic nature of fast modes is verified in the cases where the fast mode is a significant fraction of the mode mixture. The fast-mode behavior does not show any transition in going from low to high M-A. We find indications that there is some interaction between the different modes, and the properties of the dominant mode can affect the properties of the weaker modes. This work identifies the conditions under which magnetosonic modes can be a major fraction of turbulent astrophysical plasmas, including the regime of weak turbulence. Important astrophysical implications for cosmic-ray transport and magnetic reconnection are discussed.
Persistent episodes of extreme weather in the Northern Hemisphere summer have been associated with high-amplitude quasi-stationary atmospheric Rossby waves, with zonal wave numbers 6 to 8 resulting from the phenomenon of quasi-resonant amplification (QRA). A fingerprint for the occurrence of QRA can be defined in terms of the zonally averaged surface temperature field. Examining state-of-the-art [Coupled Model Intercomparison Project Phase 5 (CMIP5)] climate model projections, we find that QRA events are likely to increase by similar to 50% this century under business-as-usual carbon emissions, but there is considerable variation among climate models. Some predict a near tripling of QRA events by the end of the century, while others predict a potential decrease. Models with amplified Arctic warming yield the most pronounced increase in QRA events. The projections are strongly dependent on assumptions regarding the nature of changes in radiative forcing associated with anthropogenic aerosols over the next century. One implication of our findings is that a reduction in midlatitude aerosol loading could actually lead to Arctic de-amplification this century, ameliorating potential increases in persistent extreme weather events.
The Ornstein–Uhlenbeck process is a stationary and ergodic Gaussian process, that is fully determined by its covariance function and mean. We show here that the generic definitions of the ensemble- and time-averaged mean squared displacements fail to capture these properties consistently, leading to a spurious ergodicity breaking. We propose to remedy this failure by redefining the mean squared displacements such that they reflect unambiguously the statistical properties of any stochastic process. In particular we study the effect of the initial condition in the Ornstein–Uhlenbeck process and its fractional extension. For the fractional Ornstein–Uhlenbeck process representing typical experimental situations in crowded environments such as living biological cells, we show that the stationarity of the process delicately depends on the initial condition.
We investigate the ergodic properties of a random walker performing (anomalous) diffusion on a random fractal geometry. Extensive Monte Carlo simulations of the motion of tracer particles on an ensemble of realisations of percolation clusters are performed for a wide range of percolation densities. Single trajectories of the tracer motion are analysed to quantify the time averaged mean squared displacement (MSD) and to compare this with the ensemble averaged MSD of the particle motion. Other complementary physical observables associated with ergodicity are studied, as well. It turns out that the time averaged MSD of individual realisations exhibits non-vanishing fluctuations even in the limit of very long observation times as the percolation density approaches the critical value. This apparent non-ergodic behaviour concurs with the ergodic behaviour on the ensemble averaged level. We demonstrate how the non-vanishing fluctuations in single particle trajectories are analytically expressed in terms of the fractal dimension and the cluster size distribution of the random geometry, thus being of purely geometrical origin. Moreover, we reveal that the convergence scaling law to ergodicity, which is known to be inversely proportional to the observation time T for ergodic diffusion processes, follows a power-law ∼T−h with h < 1 due to the fractal structure of the accessible space. These results provide useful measures for differentiating the subdiffusion on random fractals from an otherwise closely related process, namely, fractional Brownian motion. Implications of our results on the analysis of single particle tracking experiments are provided.
Pre-service physics teachers often do not recognise the relevance for their future career in their university content knowledge courses. A lower perceived relevance can, however, have a negative effect on their motivation and on their academic success. Several intervention studies have been undertaken with the goal to increase this perceived relevance. A previous study shows that conceptual physics problems used in university physics courses are perceived by pre-service physics teachers as more relevant for their future career than regular, quantitative problems. It is however not clear, what the students' meaning of the construct 'relevance' is: what makes a problem more relevant to them than another problem? To answer this question, N = 7 pre-service teachers were interviewed using the repertory grid technique, based on the personal construct theory. Nine physics problems were discussed with regards to their perceived relevance and with regards to problem properties that distinguish these problems from each other. We are able to identify six problem properties that have a positive influence on the perceived relevance. Physics problems that are based on these properties should therefore potentially have a higher perceived relevance, which can have a positive effect on the motivation of the pre-service teachers who solve these problems.
We use ultrafast x-ray diffraction to investigate the effect of expansive phononic and contractive magnetic stress driving the picosecond strain response of a metallic perovskite SrRuO3 thin film upon femtosecond laser excitation. We exemplify how the anisotropic bulk equilibrium thermal expansion can be used to predict the response of the thin film to ultrafast deposition of energy. It is key to consider that the laterally homogeneous laser excitation changes the strain response compared to the near-equilibrium thermal expansion because the balanced in-plane stresses suppress the Poisson stress on the picosecond timescale. We find a very large negative Grüneisen constant describing the large contractive stress imposed by a small amount of energy in the spin system. The temperature and fluence dependence of the strain response for a double-pulse excitation scheme demonstrates the saturation of the magnetic stress in the high-fluence regime.
Using time-resolved x-ray diffraction, we demonstrate the manipulation of the picosecond strain response of a metallic heterostructure consisting of a dysprosium (Dy) transducer and a niobium (Nb) detection layer by an external magnetic field. We utilize the first-order ferromagnetic–antiferromagnetic phase transition of the Dy layer, which provides an additional large contractive stress upon laser excitation compared to its zerofield response. This enhances the laser-induced contraction of the transducer and changes the shape of the picosecond strain pulses driven in Dy and detected within the buried Nb layer. Based on our experiment with rare-earth metals we discuss required properties for functional transducers, which may allow for novel field-control of the emitted picosecond strain pulses.
Following excited-state chemical shifts in molecular ultrafast x-ray photoelectron spectroscopy
(2022)
The conversion of photon energy into other energetic forms in molecules is accompanied by charge moving on ultrafast timescales. We directly observe the charge motion at a specific site in an electronically excited molecule using time-resolved x-ray photoelectron spectroscopy (TR-XPS). We extend the concept of static chemical shift from conventional XPS by the excited-state chemical shift (ESCS), which is connected to the charge in the framework of a potential model. This allows us to invert TR-XPS spectra to the dynamic charge at a specific atom. We demonstrate the power of TR-XPS by using sulphur 2p-core-electron-emission probing to study the UV-excited dynamics of 2-thiouracil. The method allows us to discover that a major part of the population relaxes to the molecular ground state within 220–250 fs. In addition, a 250-fs oscillation, visible in the kinetic energy of the TR-XPS, reveals a coherent exchange of population among electronic states.
Using two crystals for spontaneous parametric down-conversion in a parallel setup, we observe two-photon interference with high visibility. The high visibility is consistent with complementarity and the absence of which-path information. The observations are explained as the effects of entanglement or equivalently in terms of interfering probability amplitudes and also by the calculation of a second-order field correlation function in the Heisenberg picture. The latter approach brings out explicitly the role of the vacuum fields in the down-conversion at the crystals and in the photon coincidence counting. For comparison, we show that the Hong–Ou–Mandel dip can be explained by the same approach in which the role of the vacuum signal and idler fields, as opposed to entanglement involving vacuum states, is emphasized. We discuss the fundamental limitations of a theory in which these vacuum fields are treated as classical, stochastic fields.
Complementarity in single photon interference – the role of the mode function and vacuum fields
(2017)
Background
In earlier experiments the role of the vacuum fields could be demonstrated as the source of complementarity with respect to the temporal properties (Heuer et al., Phys. Rev. Lett. 114:053601, 2015).
Methods
Single photon first order interferences of spatially separated regions from the cone structure of spontaneous parametric down conversion allow for analyzing the role of the mode function in quantum optics regarding the complementarity principle.
Results
Here the spatial coherence properties of these vacuum fields are demonstrated as the physical reason for complementarity in these single photon quantum optical experiments. These results are directly connected to the mode picture in classical optics.
Conclusion
The properties of the involved vacuum fields selected via the measurement process are the physical background of the complementarity principle in quantum optics.
URSA-PQ
(2020)
We present a highly flexible and portable instrument to perform pump-probe spectroscopy with an optical and an X-ray pulse in the gas phase. The so-called URSA-PQ (German for ‘Ultraschnelle Röntgenspektroskopie zur Abfrage der Photoenergiekonversion an Quantensystemen’, Engl. ‘ultrafast X-ray spectroscopy for probing photoenergy conversion in quantum systems’) instrument is equipped with a magnetic bottle electron spectrometer (MBES) and tools to characterize the spatial and temporal overlap of optical and X-ray laser pulses. Its adherence to the CAMP instrument dimensions allows for a wide range of sample sources as well as other spectrometers to be included in the setup. We present the main design and technical features of the instrument. The MBES performance was evaluated using Kr M4,5NN Auger lines using backfilled Kr gas, with an energy resolution ΔE/E ≅ 1/40 in the integrating operative mode. The time resolution of the setup at FLASH 2 FL 24 has been characterized with the help of an experiment on 2-thiouracil that is inserted via the instruments’ capillary oven. We find a time resolution of 190 fs using the molecular 2p photoline shift and attribute this to different origins in the UV-pump—the X-ray probe setup.
Recent experiments show that transcription factors (TFs) indeed use the facilitated diffusion mechanism to locate their target sequences on DNA in living bacteria cells: TFs alternate between sliding motion along DNA and relocation events through the cytoplasm. From simulations and theoretical analysis we study the TF-sliding motion for a large section of the DNA-sequence of a common E. coli strain, based on the two-state TF-model with a fast-sliding search state and a recognition state enabling target detection. For the probability to detect the target before dissociating from DNA the TF-search times self-consistently depend heavily on whether or not an auxiliary operator (an accessible sequence similar to the main operator) is present in the genome section. Importantly, within our model the extent to which the interconversion rates between search and recognition states depend on the underlying nucleotide sequence is varied. A moderate dependence maximises the capability to distinguish between the main operator and similar sequences. Moreover, these auxiliary operators serve as starting points for DNA looping with the main operator, yielding a spectrum of target detection times spanning several orders of magnitude. Auxiliary operators are shown to act as funnels facilitating target detection by TFs.
We define and study in detail utraslow scaled Brownian motion (USBM) characterized by a time dependent diffusion coefficient of the form . For unconfined motion the mean squared displacement (MSD) of USBM exhibits an ultraslow, logarithmic growth as function of time, in contrast to the conventional scaled Brownian motion. In a harmonic potential the MSD of USBM does not saturate but asymptotically decays inverse-proportionally to time, reflecting the highly non-stationary character of the process. We show that the process is weakly non-ergodic in the sense that the time averaged MSD does not converge to the regular MSD even at long times, and for unconfined motion combines a linear lag time dependence with a logarithmic term. The weakly non-ergodic behaviour is quantified in terms of the ergodicity breaking parameter. The USBM process is also shown to be ageing: observables of the system depend on the time gap between initiation of the test particle and start of the measurement of its motion. Our analytical results are shown to agree excellently with extensive computer simulations.
Science education researchers have developed a refined understanding of the structure of science teachers’ pedagogical content knowledge (PCK), but how to develop applicable and situation-adequate PCK remains largely unclear. A potential problem lies in the diverse conceptualisations of the PCK used in PCK research. This study sought to systematize existing science education research on PCK through the lens of the recently proposed refined consensus model (RCM) of PCK. In this review, the studies’ approaches to investigating PCK and selected findings were characterised and synthesised as an overview comparing research before and after the publication of the RCM. We found that the studies largely employed a qualitative case-study methodology that included specific PCK models and tools. However, in recent years, the studies focused increasingly on quantitative aspects. Furthermore, results of the reviewed studies can mostly be integrated into the RCM. We argue that the RCM can function as a meaningful theoretical lens for conceptualizing links between teaching practice and PCK development by proposing pedagogical reasoning as a mechanism and/or explanation for PCK development in the context of teaching practice.
The plasmon resonance of metal nanoparticles determines their optical response in the visible spectral range. Many details such as the electronic properties of gold near the particle surface and the local environment of the particles influence the spectra. We show how the cheap but highly precise fabrication of composite nanolayers by spin-assisted layer-by-layer deposition of polyelectrolytes can be used to investigate the spectral response of gold nanospheres (GNS) and gold nanorods (GNR) in a self-consistent way, using the established Maxwell–Garnett effective medium (MGEM) theory beyond the limit of homogeneous media. We show that the dielectric function of gold nanoparticles differs from the bulk value and experimentally characterize the shape and the surrounding of the particles thoroughly by SEM, AFM and ellipsometry. Averaging the dielectric functions of the layered surrounding by an appropriate weighting with the electric field intensity yields excellent agreement for the spectra of several nanoparticles and nanorods with various cover-layer thicknesses.
In classical thermodynamic processes the unavoidable presence of irreversibility, quantified by the entropy production, carries two energetic footprints: the reduction of extractable work from the optimal, reversible case, and the generation of a surplus of heat that is irreversibly dissipated to the environment. Recently it has been shown that in the quantum regime an additional quantum irreversibility occurs that is linked to decoherence into the energy basis. Here we employ quantum trajectories to construct distributions for classical heat and quantum heat exchanges, and show that the heat footprint of quantum irreversibility differs markedly from the classical case. We also quantify how quantum irreversibility reduces the amount of work that can be extracted from a state with coherences. Our results show that decoherence leads to both entropic and energetic footprints which both play an important role in the optimization of controlled quantum operations at low temperature.
In classical thermodynamics irreversibility occurs whenever a non-thermal system is brought into contact with a thermal environment. Using quantum trajectories the authors here establish two energetic footprints of quantum irreversible processes, and find that while quantum irreversibility leads to the occurrence of a quantum heat and a reduction of work production, the two are not linked in the same manner as the classical laws of thermodynamics would dictate.
We study populations of globally coupled noisy rotators (oscillators with inertia) allowing a nonequilibrium transition from a desynchronized state to a synchronous one (with the nonvanishing order parameter). The newly developed analytical approaches resulted in solutions describing the synchronous state with constant order parameter for weakly inertial rotators, including the case of zero inertia, when the model is reduced to the Kuramoto model of coupled noise oscillators. These approaches provide also analytical criteria distinguishing supercritical and subcritical transitions to the desynchronized state and indicate the universality of such transitions in rotator ensembles. All the obtained analytical results are confirmed by the numerical ones, both by direct simulations of the large ensembles and by solution of the associated Fokker-Planck equation. We also propose generalizations of the developed approaches for setups where different rotators parameters (natural frequencies, masses, noise intensities, strengths and phase shifts in coupling) are dispersed.
Compared to their inorganic counterparts, organic semiconductors suffer from relatively low charge carrier mobilities. Therefore, expressions derived for inorganic solar cells to correlate characteristic performance parameters to material properties are prone to fail when applied to organic devices. This is especially true for the classical Shockley-equation commonly used to describe current-voltage (JV)-curves, as it assumes a high electrical conductivity of the charge transporting material. Here, an analytical expression for the JV-curves of organic solar cells is derived based on a previously published analytical model. This expression, bearing a similar functional dependence as the Shockley-equation, delivers a new figure of merit α to express the balance between free charge recombination and extraction in low mobility photoactive materials. This figure of merit is shown to determine critical device parameters such as the apparent series resistance and the fill factor.
Passive coherent combination of several discrete low power laser diodes is a promising way to overcome the issue of degrading beam quality when scaling single emitters to > 10W output power. Such systems would be an efficient alternative to current high power sources, yet they suffer from fatal coherence loss when operated well above threshold. We present a new way to obtain detailed coherence information for laser diode arrays using a spatial light modulator to help identify the underlying decoherence processes. Reconstruction tests of the emitted far-field distribution are conducted to evaluate the performance of our setup.
In the study of relativistic jets one of the key open questions is their interaction with the environment on the microscopic level. Here, we study the initial evolution of both electron-proton (e(-)-p(+)) and electron-positron (e(+/-)) relativistic jets containing helical magnetic fields, focusing on their interaction with an ambient plasma. We have performed simulations of "global" jets containing helical magnetic fields in order to examine how helical magnetic fields affect kinetic instabilities such as the Weibel instability, the kinetic Kelvin-Helmholtz instability (kKHI) and the Mushroom instability (MI). In our initial simulation study these kinetic instabilities are suppressed and new types of instabilities can grow. In the e(-)-p(+) jet simulation a recollimation-like instability occurs and jet electrons are strongly perturbed. In the e(+/-) jet simulation a recollimation-like instability occurs at early times followed by a kinetic instability and the general structure is similar to a simulation without helical magnetic field. Simulations using much larger systems are required in order to thoroughly follow the evolution of global jets containing helical magnetic fields.
In this paper we report an experimental and computational study of liquid acetonitrile (H3C–C[triple bond, length as m-dash]N) by resonant inelastic X-ray scattering (RIXS) at the N K-edge. The experimental spectra exhibit clear signatures of the electronic structure of the valence states at the N site and incident-beam-polarization dependence is observed as well. Moreover, we find fine structure in the quasielastic line that is assigned to finite scattering duration and nuclear relaxation. We present a simple and light-to-evaluate model for the RIXS maps and analyze the experimental data using this model combined with ab initio molecular dynamics simulations. In addition to polarization-dependence and scattering-duration effects, we pinpoint the effects of different types of chemical bonding to the RIXS spectrum and conclude that the H2C–C[double bond, length as m-dash]NH isomer, suggested in the literature, does not exist in detectable quantities. We study solution effects on the scattering spectra with simulations in liquid and in vacuum. The presented model for RIXS proved to be light enough to allow phase-space-sampling and still accurate enough for identification of transition lines in physical chemistry research by RIXS.
We study travelling chimera states in a ring of nonlocally coupled heterogeneous (with Lorentzian distribution of natural frequencies) phase oscillators. These states are coherence-incoherence patterns moving in the lateral direction because of the broken reflection symmetry of the coupling topology. To explain the results of direct numerical simulations we consider the continuum limit of the system. In this case travelling chimera states correspond to smooth travelling wave solutions of some integro-differential equation, called the Ott–Antonsen equation, which describes the long time coarse-grained dynamics of the oscillators. Using the Lyapunov–Schmidt reduction technique we suggest a numerical approach for the continuation of these travelling waves. Moreover, we perform their linear stability analysis and show that travelling chimera states can lose their stability via fold and Hopf bifurcations. Some of the Hopf bifurcations turn out to be supercritical resulting in the observation of modulated travelling chimera states.
For both Lévy flight and Lévy walk search processes we analyse the full distribution of first-passage and first-hitting (or first-arrival) times. These are, respectively, the times when the particle moves across a point at some given distance from its initial position for the first time, or when it lands at a given point for the first time. For Lévy motions with their propensity for long relocation events and thus the possibility to jump across a given point in space without actually hitting it ('leapovers'), these two definitions lead to significantly different results. We study the first-passage and first-hitting time distributions as functions of the Lévy stable index, highlighting the different behaviour for the cases when the first absolute moment of the jump length distribution is finite or infinite. In particular we examine the limits of short and long times. Our results will find their application in the mathematical modelling of random search processes as well as computer algorithms.
Probably no other field of statistical physics at the borderline of soft matter and biological physics has caused such a flurry of papers as polymer translocation since the 1994 landmark paper by Bezrukov, Vodyanoy, and Parsegian and the study of Kasianowicz in 1996. Experiments, simulations, and theoretical approaches are still contributing novel insights to date, while no universal consensus on the statistical understanding of polymer translocation has been reached. We here collect the published results, in particular, the famous–infamous debate on the scaling exponents governing the translocation process. We put these results into perspective and discuss where the field is going. In particular, we argue that the phenomenon of polymer translocation is non-universal and highly sensitive to the exact specifications of the models and experiments used towards its analysis.
We introduce azobenzene-functionalized polyelectrolyte multilayers as efficient, inexpensive optoacoustic transducers for hyper-sound strain waves in the GHz range. By picosecond transient reflectivity measurements we study the creation of nanoscale strain waves, their reflection from interfaces, damping by scattering from nanoparticles and propagation in soft and hard adjacent materials like polymer layers, quartz and mica. The amplitude of the generated strain ε ∼ 5 × 10−4 is calibrated by ultrafast X-ray diffraction.
The power conversion efficiency (PCE) of state-of-the-art organic solar cells is still limited by significant open-circuit voltage (V-OC) losses, partly due to the excitonic nature of organic materials and partly due to ill-designed architectures. Thus, quantifying different contributions of the V-OC losses is of importance to enable further improvements in the performance of organic solar cells. Herein, the spectroscopic and semiconductor device physics approaches are combined to identify and quantify losses from surface recombination and bulk recombination. Several state-of-the-art systems that demonstrate different V-OC losses in their performance are presented. By evaluating the quasi-Fermi level splitting (QFLS) and the V-OC as a function of the excitation fluence in nonfullerene-based PM6:Y6, PM6:Y11, and fullerene-based PPDT2FBT:PCBM devices with different architectures, the voltage losses due to different recombination processes occurring in the active layers, the transport layers, and at the interfaces are assessed. It is found that surface recombination at interfaces in the studied solar cells is negligible, and thus, suppressing the non-radiative recombination in the active layers is the key factor to enhance the PCE of these devices. This study provides a universal tool to explain and further improve the performance of recently demonstrated high-open-circuit-voltage organic solar cells.
Interplay of coupling and common noise at the transition to synchrony in oscillator populations
(2016)
There are two ways to synchronize oscillators: by coupling and by common forcing, which can be pure noise. By virtue of the Ott-Antonsen ansatz for sine-coupled phase oscillators, we obtain analytically tractable equations for the case where both coupling and common noise are present. While noise always tends to synchronize the phase oscillators, the repulsive coupling can act against synchrony, and we focus on this nontrivial situation. For identical oscillators, the fully synchronous state remains stable for small repulsive coupling; moreover it is an absorbing state which always wins over the asynchronous regime. For oscillators with a distribution of natural frequencies, we report on a counter-intuitive effect of dispersion (instead of usual convergence) of the oscillators frequencies at synchrony; the latter effect disappears if noise vanishes.
The possibility to manufacture perovskite solar cells (PSCs) at low temperatures paves the way to flexible and lightweight photovoltaic (PV) devices manufactured via high-throughput roll-to-roll processes. In order to achieve higher power conversion efficiencies, it is necessary to approach the radiative limit via suppression of non-radiative recombination losses. Herein, we performed a systematic voltage loss analysis for a typical low-temperature processed, flexible PSC in n-i-p configuration using vacuum deposited C-60 as electron transport layer (ETL) and two-step hybrid vacuum-solution deposition for CH3NH3PbI3 perovskite absorber. We identified the ETL/absorber interface as a bottleneck in relation to non-radiative recombination losses, the quasi-Fermi level splitting (QFLS) decreases from similar to 1.23 eV for the bare absorber, just similar to 90 meV below the radiative limit, to similar to 1.10 eV when C-60 is used as ETL. To effectively mitigate these voltage losses, we investigated different interfacial modifications via vacuum deposited interlayers (BCP, B4PyMPM, 3TPYMB, and LiF). An improvement in QFLS of similar to 30-40 meV is observed after interlayer deposition and confirmed by comparable improvements in the open-circuit voltage after implementation of these interfacial modifications in flexible PSCs. Further investigations on absorber/hole transport layer (HTL) interface point out the detrimental role of dopants in Spiro-OMeTAD film (widely employed HTL in the community) as recombination centers upon oxidation and light exposure. [GRAPHICS] .
Ammonium salts are a reservoir of nitrogen on a cometary nucleus and possibly on some asteroids
(2020)
The measured nitrogen-to-carbon ratio in comets is lower than for the Sun, a discrepancy which could be alleviated if there is an unknown reservoir of nitrogen in comets. The nucleus of comet 67P/Churyumov-Gerasimenko exhibits an unidentified broad spectral reflectance feature around 3.2 micrometers, which is ubiquitous across its surface. On the basis of laboratory experiments, we attribute this absorption band to ammonium salts mixed with dust on the surface. The depth of the band indicates that semivolatile ammonium salts are a substantial reservoir of nitrogen in the comet, potentially dominating over refractory organic matter and more volatile species. Similar absorption features appear in the spectra of some asteroids, implying a compositional link between asteroids, comets, and the parent interstellar cloud.
Many chemical reactions in biological cells occur at very low concentrations of constituent molecules. Thus, transcriptional gene-regulation is often controlled by poorly expressed transcription-factors, such as E.coli lac repressor with few tens of copies. Here we study the effects of inherent concentration fluctuations of substrate-molecules on the seminal Michaelis-Menten scheme of biochemical reactions. We present a universal correction to the Michaelis-Menten equation for the reaction-rates. The relevance and validity of this correction for enzymatic reactions and intracellular gene-regulation is demonstrated. Our analytical theory and simulation results confirm that the proposed variance-corrected Michaelis-Menten equation predicts the rate of reactions with remarkable accuracy even in the presence of large non-equilibrium concentration fluctuations. The major advantage of our approach is that it involves only the mean and variance of the substrate-molecule concentration. Our theory is therefore accessible to experiments and not specific to the exact source of the concentration fluctuations.
The existence of an intermediate transition between the glass and the Curie/melting temperatures in Poly(vinylidene fluoride) (PVDF) and some of its co- and ter-polymers has been reported by several authors. In spite (or because?) of various different explanations in the literature, the origins of the transition are still not clear. Here, we try to understand the extra transition in more detail and study it with thermal and dielectric methods on PVDF, on its co-polymers with trifluoroethylene (P(VDF-TrFE)) and tetrafluoroethylene (P(VDF-TFE)), and on its ter-polymer with trifluoroethylene and chlorofluoroethylene (P(VDF-TrFE-CFE). Based on interpretations from the literature and our experimental studies, we propose the new hypothesis that the intermediate transition should have several interrelated origins. Especially since the relevant range is not far above room temperature, better understanding and control of their properties may also have practical implications for the use of the respective polymer materials in devices.
The nucleus of Hen 2-428 is a short orbital period (4.2 h) spectroscopic binary, whose status as potential supernovae type Ia progenitor has raised some controversy in the literature. We present preliminary results of a thorough analysis of this interesting system, which combines quantitative non-local thermodynamic (non-LTE) equilibrium spectral modelling, radial velocity analysis, multi-band light curve fitting, and state-of-the art stellar evolutionary calculations. Importantly, we find that the dynamical system mass that is derived by using all available He II lines does not exceed the Chandrasekhar mass limit. Furthermore, the individual masses of the two central stars are too small to lead to an SN Ia in case of a dynamical explosion during the merger process.
This work reviews the literature on an alleged global warming 'pause' in global mean surface temperature (GMST) to determine how it has been defined, what time intervals are used to characterise it, what data are used to measure it, and what methods used to assess it. We test for 'pauses', both in the normally understood meaning of the term to mean no warming trend, as well as for a 'pause' defined as a substantially slower trend in GMST. The tests are carried out with the historical versions of GMST that existed for each pause-interval tested, and with current versions of each of the GMST datasets. The tests are conducted following the common (but questionable) practice of breaking the linear fit at the start of the trend interval ('broken' trends), and also with trends that are continuous with the data bordering the trend interval. We also compare results when appropriate allowance is made for the selection bias problem. The results show that there is little or no statistical evidence for a lack of trend or slower trend in GMST using either the historical data or the current data. The perception that there was a 'pause' in GMST was bolstered by earlier biases in the data in combination with incomplete statistical testing.
Computation of the instantaneous phase and amplitude via the Hilbert Transform is a powerful tool of data analysis. This approach finds many applications in various science and engineering branches but is not proper for causal estimation because it requires knowledge of the signal’s past and future. However, several problems require real-time estimation of phase and amplitude; an illustrative example is phase-locked or amplitude-dependent stimulation in neuroscience. In this paper, we discuss and compare three causal algorithms that do not rely on the Hilbert Transform but exploit well-known physical phenomena, the synchronization and the resonance. After testing the algorithms on a synthetic data set, we illustrate their performance computing phase and amplitude for the accelerometer tremor measurements and a Parkinsonian patient’s beta-band brain activity.
The gravitational field of a laser pulse of finite lifetime, is investigated in the framework of linearized gravity. Although the effects are very small, they may be of fundamental physical interest. It is shown that the gravitational field of a linearly polarized light pulse is modulated as the norm of the corresponding electric field strength, while no modulations arise for circular polarization. In general, the gravitational field is independent of the polarization direction. It is shown that all physical effects are confined to spherical shells expanding with the speed of light, and that these shells are imprints of the spacetime events representing emission and absorption of the pulse. Nearby test particles at rest are attracted towards the pulse trajectory by the gravitational field due to the emission of the pulse, and they are repelled from the pulse trajectory by the gravitational field due to its absorption. Examples are given for the size of the attractive effect. It is recovered that massless test particles do not experience any physical effect if they are co-propagating with the pulse, and that the acceleration of massless test particles counter-propagating with respect to the pulse is four times stronger than for massive particles at rest. The similarities between the gravitational effect of a laser pulse and Newtonian gravity in two dimensions are pointed out. The spacetime curvature close to the pulse is compared to that induced by gravitational waves from astronomical sources.
Isoflux tension propagation (IFTP) theory and Langevin dynamics (LD) simulations are employed to study the dynamics of channel-driven polymer translocation in which a polymer translocates into a narrow channel and the monomers in the channel experience a driving force fc. In the high driving force limit, regardless of the channel width, IFTP theory predicts τ ∝ f βc for the translocation time, where β = −1 is the force scaling exponent. Moreover, LD data show that for a very narrow channel fitting only a single file of monomers, the entropic force due to the subchain inside the channel does not play a significant role in the translocation dynamics and the force exponent β = −1 regardless of the force magnitude. As the channel width increases the number of possible spatial configurations of the subchain inside the channel becomes significant and the resulting entropic force causes the force exponent to drop below unity.
The importance of plasmonic heating for the plasmondriven photodimerization of 4-nitrothiophenol
(2018)
Metal nanoparticles form potent nanoreactors, driven by the optical generation of energetic electrons and nanoscale heat. The relative influence of these two factors on nanoscale chemistry is strongly debated. This article discusses the temperature dependence of the dimerization of 4-nitrothiophenol (4-NTP) into 4,4′-dimercaptoazobenzene (DMAB) adsorbed on gold nanoflowers by Surface-Enhanced Raman Scattering (SERS). Raman thermometry shows a significant optical heating of the particles. The ratio of the Stokes and the anti-Stokes Raman signal moreover demonstrates that the molecular temperature during the reaction rises beyond the average crystal lattice temperature of the plasmonic particles. The product bands have an even higher temperature than reactant bands, which suggests that the reaction proceeds preferentially at thermal hot spots. In addition, kinetic measurements of the reaction during external heating of the reaction environment yield a considerable rise of the reaction rate with temperature. Despite this significant heating effects, a comparison of SERS spectra recorded after heating the sample by an external heater to spectra recorded after prolonged illumination shows that the reaction is strictly photo-driven. While in both cases the temperature increase is comparable, the dimerization occurs only in the presence of light. Intensity dependent measurements at fixed temperatures confirm this finding.
We present an X-ray-optical cross-correlator for the soft (> 150 eV) up to the hard X-ray regime based on a molybdenum-silicon superlattice. The cross-correlation is done by probing intensity and position changes of superlattice Bragg peaks caused by photoexcitation of coherent phonons. This approach is applicable for a wide range of X-ray photon energies as well as for a broad range of excitation wavelengths and requires no external fields or changes of temperature. Moreover, the cross-correlator can be employed on a 10 ps or 100 fs time scale featuring up to 50% total X-ray reflectivity and transient signal changes of more than 20%. (C) 2016 Author(s).
We report on light sensitive microgel particles that can change their volume reversibly in response to illumination with light of different wavelengths. To make the anionic microgels photosensitive we add surfactants with a positively charged polyamine head group and an azobenzene containing tail. Upon illumination, azobenzene undergoes a reversible photo-isomerization reaction from a trans- to a cis-state accompanied by a change in the hydrophobicity of the surfactant. Depending on the isomerization state, the surfactant molecules are either accommodated within the microgel (trans-state) resulting in its shrinkage or desorbed back into water (cis-isomer) letting the microgel swell. We have studied three surfactants differing in the number of amino groups, so that the number of charges of the surfactant head varies between 1 and 3. We have found experimentally and theoretically that the surfactant concentration needed for microgel compaction increases with decreasing number of charges of the head group. Utilization of polyamine azobenzene containing surfactants for the light triggered remote control of the microgel size opens up a possibility for applications of light responsive microgels as drug carriers in biology and medicine.
The performance of the recently commissioned spectrometer PEAXIS for resonant inelastic soft X-ray scattering (RIXS) and X-ray photoelectron spectroscopy and its hosting beamline U41-PEAXIS at the BESSY II synchrotron are characterized. The beamline provides linearly polarized light from 180 eV to 1600 eV allowing for RIXS measurements in the range 200-1200 eV. The monochromator optics can be operated in different configurations to provide either high flux with up to 10(12) photons s(-1) within the focal spot at the sample or high energy resolution with a full width at half maximum of <40 meV at an incident photon energy of similar to 400 eV. The measured total energy resolution of the RIXS spectrometer is in very good agreement with theoretically predicted values obtained by ray-tracing simulations. PEAXIS features a 5 m-long RIXS spectrometer arm that can be continuously rotated about the sample position by 106 degrees within the horizontal photon scattering plane, thus enabling the study of momentum-transfer-dependent excitations. Selected scientific examples are presented to demonstrate the instrument capabilities, including measurements of excitations in single-crystalline NiO and in liquid acetone employing a fluid cell sample manipulator. Planned upgrades of the beamline and the RIXS spectrometer to further increase the energy resolution to similar to 100 meV at 1000 eV incident photon energy are discussed.
Monolithic perovskite silicon tandem solar cells can overcome the theoretical efficiency limit of silicon solar cells. This requires an optimum bandgap, high quantum efficiency, and high stability of the perovskite. Herein, a silicon heterojunction bottom cell is combined with a perovskite top cell, with an optimum bandgap of 1.68 eV in planar p-i-n tandem configuration. A methylammonium-free FA(0.75)Cs(0.25)Pb(I0.8Br0.2)(3) perovskite with high Cs content is investigated for improved stability. A 10% molarity increase to 1.1 m of the perovskite precursor solution results in approximate to 75 nm thicker absorber layers and 0.7 mA cm(-2) higher short-circuit current density. With the optimized absorber, tandem devices reach a high fill factor of 80% and up to 25.1% certified efficiency. The unencapsulated tandem device shows an efficiency improvement of 2.3% (absolute) over 5 months, showing the robustness of the absorber against degradation. Moreover, a photoluminescence quantum yield analysis reveals that with adapted charge transport materials and surface passivation, along with improved antireflection measures, the high bandgap perovskite absorber has the potential for 30% tandem efficiency in the near future.
A synthesis route to controlled and dynamic single polymer chain folding is reported. Sequence-controlled macromolecules containing precisely located selenol moieties within a polymer chain are synthesized. Oxidation of selenol functionalities lead to diselenide bridges and induces controlled intramolecular crosslinking to generate single chain collapse. The cyclization process is successfully characterized by SEC as well as by H-1 NMR and 2D HSQC NMR spectroscopies. In order to gain insight on the molecular level to reveal the degree of structural control, the folded polymers are transformed into folded molecular brushes that are known to be visualizable as single molecule structures by AFM. The "grafting onto" approach is performed by using triazolinedione-diene reaction to graft the side chain polymers. A series of folded molecular brushes as well as the corresponding linear controls are synthesized. AFM visualization is proving the cyclization of the folded backbone by showing globular objects, where non-folded brushes show typical worm-like structures. (C) 2019 The Authors. Journal of Polymer Science published by Wiley Periodicals, Inc.