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In resonant inelastic soft x-ray scattering (RIXS) from molecular and liquid systems, the interplay of ground state structural and core-excited state dynamical contributions leads to complex spectral shapes that partially allow for ambiguous interpretations. In this work, we dissect these contributions in oxygen K-edge RIXS from liquid alcohols. We use the scattering into the electronic ground state as an accurate measure of nuclear dynamics in the intermediate core-excited state of the RIXS process. We determine the characteristic time in the core-excited state until nuclear dynamics give a measurable contribution to the RIXS spectral profiles to tau(dyn) = 1.2 +/- 0.8 fs. By detuning the excitation energy below the absorption resonance we reduce the effective scattering time below sdyn, and hence suppress these dynamical contributions to a minimum. From the corresponding RIXS spectra of liquid methanol, we retrieve the "dynamic-free" density of states and find that it is described solely by the electronic states of the free methanol molecule. From this and from the comparison of normal and deuterated methanol, we conclude that the split peak structure found in the lone-pair emission region at non-resonant excitation originates from dynamics in the O-H bond in the core-excited state. We find no evidence that this split peak feature is a signature of distinct ground state structural complexes in liquid methanol. However, we demonstrate how changes in the hydrogen bond coordination within the series of linear alcohols from methanol to hexanol affect the split peak structure in the liquid alcohols. (C) 2014 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution 3.0 Unported License.
Normal diffusion in corrugated potentials with spatially uncorrelated Gaussian energy disorder famously explains the origin of non-Arrhenius exp[-sigma(2)/(k(B)T(2))] temperature dependence in disordered systems. Here we show that unbiased diffusion remains asymptotically normal also in the presence of spatial correlations decaying to zero. However, because of a temporal lack of self-averaging, transient subdiffusion emerges on the mesoscale, and it can readily reach macroscale even for moderately strong disorder fluctuations of sigma similar to 4 - 5k(B)T. Because of its nonergodic origin, such subdiffusion exhibits a large scatter in single-trajectory averages. However, at odds with intuition, it occurs essentially faster than one expects from the normal diffusion in the absence of correlations. We apply these results to diffusion of regulatory proteins on DNA molecules and predict that such diffusion should be anomalous, but much faster than earlier expected on a typical length of genes for a realistic energy disorder of several room k(B)T, or merely 0.05-0.075 eV.
The charge generation and recombination processes following photo-excitation of a low-bandgap polymer:perylene diimide photovoltaic blend are investigated by transient absorption pump-probe spectroscopy covering a dynamic range from femto-to microseconds to get insight into the efficiency-limiting photophysical processes. The several tens of picoseconds, and its efficiency is only half of that in a polymer:fullerene photoinduced electron transfer from the polymer to the perylene acceptor takes up to blend. This reduces the short-circuit current. Time-delayed collection field experiments reveal that the subsequent charge separation is strongly field-dependent, limiting the fill factor and lowering the short-circuit current in polymer:PDI devices. Upon excitation of the acceptor in the low-bandgap polymer blend, the PDI exciton undergoes charge transfer on a time scale of several tens of picoseconds. However, a significant fraction of the charges generated at the interface are quickly lost because of fast geminate recombination. This reduces the short-circuit current even further, leading to a scenario in which only around 2596 of the initial photoexcitations generate free charges that can potentially contribute to the photocurrent. In summary, the key photophysical limitations of perylene diimide as an acceptor in low-bandgap polymer blends appear at the interface between the materials, with the kinetics of both charge generation and separation inhibited as compared to that of fullerenes.
Force-free equilibria containing two vertically arranged magnetic flux ropes of like chirality and current direction are considered as a model for split filaments/prominences and filament-sigmoid systems. Such equilibria are constructed analytically through an extension of the methods developed in Titov & Demoulin and numerically through an evolutionary sequence including shear flows, flux emergence, and flux cancellation in the photospheric boundary. It is demonstrated that the analytical equilibria are stable if an external toroidal (shear) field component exceeding a threshold value is included. If this component decreases sufficiently, then both flux ropes turn unstable for conditions typical of solar active regions, with the lower rope typically becoming unstable first. Either both flux ropes erupt upward, or only the upper rope erupts while the lower rope reconnects with the ambient flux low in the corona and is destroyed. However, for shear field strengths staying somewhat above the threshold value, the configuration also admits evolutions which lead to partial eruptions with only the upper flux rope becoming unstable and the lower one remaining in place. This can be triggered by a transfer of flux and current from the lower to the upper rope, as suggested by the observations of a split filament in Paper I. It can also result from tether-cutting reconnection with the ambient flux at the X-type structure between the flux ropes, which similarly influences their stability properties in opposite ways. This is demonstrated for the numerically constructed equilibrium.
Magnetic agnetic field generation in core-sheath jets via the kinetic Kelvin-Helmholtz instability
(2014)
We have investigated magnetic field generation in velocity shears via the kinetic Kelvin-Helmholtz instability (kKHI) using a relativistic plasma jet core and stationary plasma sheath. Our three-dimensional particle-in-cell simulations consider plasma jet cores with Lorentz factors of 1.5, 5, and 15 for both electron-proton and electron-positron plasmas. For electron-proton plasmas, we find generation of strong large-scale DC currents and magnetic fields that extend over the entire shear surface and reach thicknesses of a few tens of electron skin depths. For electron-positron plasmas, we find generation of alternating currents and magnetic fields. Jet and sheath plasmas are accelerated across the shear surface in the strong magnetic fields generated by the kKHI. The mixing of jet and sheath plasmas generates a transverse structure similar to that produced by the Weibel instability.
Based on extensive Brownian dynamics simulations we study the thermal motion of a tracer bead in a cross-linked, flexible gel in the limit when the tracer particle size is comparable to or even larger than the equilibrium mesh size of the gel. The analysis of long individual trajectories of the tracer demonstrates the existence of pronounced transient anomalous diffusion. From the time averaged mean squared displacement and the time averaged van Hove correlation functions we elucidate the many-body origin of the non-Brownian tracer bead dynamics. Our results shed new light onto the ongoing debate over the physical origin of steric tracer interactions with structured environments.
Electron-phonon scattering has been studied for silicon carbide (6H-SiC) with resonant inelastic x-ray scattering at the silicon 2p edge. The observed electron-phonon scattering yields a crystal momentum transfer rate per average phonon in 6H-SiC of 1.8 fs(-1) while it is 0.2 fs(-1) in crystalline silicon. The angular momentum transfer rate per average phonon for 6H-SiC is 0.1 fs(-1), which is much higher than 0.0035 fs(-1) obtained for crystalline silicon in a previous study. The higher electron-phonon scattering rates in 6H-SiC are a result of the larger electron localization at the silicon atoms in 6H-SiC as compared to crystalline silicon. While delocalized valence electrons can screen effectively (part of) the electron-phonon interaction, this effect is suppressed for 6H-SiC in comparison to crystalline silicon. Smaller contributions to the difference in electron-phonon scattering rates between 6H-SiC and silicon arise from the lower atomic mass of carbon versus silicon and the difference in local symmetry.
Herein we report a general liquid-mediated pathway for the growth of continuous polymeric carbon nitride (C3N4) thin films. The deposition method consists of the use of supramolecular complexes that transform to the liquid state before direct thermal condensation into C3N4 solid films. The resulting films exhibit continuous porous C3N4 networks on various substrates. Moreover, the optical absorption can be easily tuned to cover the solar spectrum by the insertion of an additional molecule into the starting complex. The strength of the deposition method is demonstrated by the use of the C3N4 layer as the electron acceptor in a polymer solar cell that exhibits a remarkable open-circuit voltage exceeding 1 V. The easy, safe, and direct synthesis of carbon nitride in a continuous layered architecture on different functional substrates opens new possibilities for the fabrication of many energy-related devices.
In this paper, we show how graphene can be utilized as a nanoscopic probe in order to characterize local opto-mechanical forces generated within photosensitive azobenzene containing polymer films. Upon irradiation with light interference patterns, photosensitive films deform according to the spatial intensity variation, leading to the formation of periodic topographies such as surface relief gratings (SRG). The mechanical driving forces inscribing a pattern into the films are supposedly fairly large, because the deformation takes place without photofluidization; the polymer is in a glassy state throughout. However, until now there has been no attempt to characterize these forces by any means. The challenge here is that the forces vary locally on a nanometer scale. Here, we propose to use Raman analysis of the stretching of the graphene layer adsorbed on top of polymer film under deformation in order to probe the strength of the material transport spatially resolved. With the well-known mechanical properties of graphene, we can obtain lower bounds on the forces acting within the film. Upon the basis of our experimental results, we can deduce that the internal pressure in the film due to grating formation can exceed 1 GPa. The graphene-based nanoscopic gauge opens new possibilities to characterize opto-mechanical forces generated within photosensitive polymer films.
Context. It is not yet clear whether magnetic fields play an essential role in shaping planetary nebulae (PNe), or whether stellar rotation alone and/or a close binary companion, stellar or substellar, can account for the variety of the observed nebular morphologies.
Aims. In a quest for empirical evidence verifying or disproving the role of magnetic fields in shaping planetary nebulae, we follow up on previous attempts to measure the magnetic field in a representative sample of PN central stars.
Methods. We obtained low-resolution polarimetric spectra with FORS2 installed on the Antu telescope of the VLT for a sample of 12 bright central stars of PNe with different morphologies, including two round nebulae, seven elliptical nebulae, and three bipolar nebulae. Two targets are Wolf-Rayet type central stars.
Results. For the majority of the observed central stars, we do not find any significant evidence for the existence of surface magnetic fields. However, our measurements may indicate the presence of weak mean longitudinal magnetic fields of the order of 100 Gauss in the central star of the young elliptical planetary nebula IC 418 as well as in the Wolf-Rayet type central star of the bipolar nebula Hen 2-113 and the weak emission line central star of the elliptical nebula Hen 2-131. A clear detection of a 250 G mean longitudinal field is achieved for the A-type companion of the central star of NGC 1514. Some of the central stars show a moderate night-to-night spectrum variability, which may be the signature of a variable stellar wind and/or rotational modulation due to magnetic features.
Conclusions. Since our analysis indicates only weak fields, if any, in a few targets of our sample, we conclude that strong magnetic fields of the order of kG are not widespread among PNe central stars. Nevertheless, simple estimates based on a theoretical model of magnetized wind bubbles suggest that even weak magnetic fields below the current detection limit of the order of 100 G may well be sufficient to contribute to the shaping of the surrounding nebulae throughout their evolution. Our current sample is too small to draw conclusions about a correlation between nebular morphology and the presence of stellar magnetic fields.
A novel sample holder is introduced which allows for temperature dependent soft x-ray absorption spectroscopy of liquids in transmission mode. The setup is based on sample cells with x-ray transmissive silicon nitride windows. A cooling circuit allows for temperature regulation of the sample liquid between -10 degrees C and +50 degrees C. The setup enables to record soft x-ray absorption spectra of liquids in transmission mode with a temperature resolution of 0.5K and better. Reliability and reproducibility of the spectra are demonstrated by investigating the characteristic temperature-induced changes in the oxygen K-edge x-ray absorption spectrum of liquid water. These are compared to the corresponding changes in the oxygen K-edge spectra from x-ray Raman scattering. (C) 2014 AIP Publishing LLC.
Life and death of stationary linear response in anomalous continuous time random walk dynamics
(2014)
Linear theory of stationary response in systems at thermal equilibrium requires to find equilibrium correlation function of unperturbed responding system. Studies of the response of the systems exhibiting anomalously slow dynamics are often based on the continuous time random walk description (CTRW) with divergent mean waiting times. The bulk of the literature on anomalous response contains linear response functions like one by Cole-Cole calculated from such a CTRW theory and applied to systems at thermal equilibrium. Here we show within a fairly simple and general model that for the systems with divergent mean waiting times the stationary response at thermal equilibrium is absent, in accordance with some recent studies. The absence of such stationary response (or dying to zero non-stationary response in aging experiments) would confirm CTRW with divergent mean waiting times as underlying physical relaxation mechanism, but reject it otherwise. We show that the absence of stationary response is closely related to the breaking of ergodicity of the corresponding dynamical variable. As an important new result, we derive a generalized Cole-Cole response within ergodic CTRW dynamics with finite waiting time. Moreover, we provide a physically reasonable explanation of the origin and wide presence of 1/f noise in condensed matter for ergodic dynamics close to normal, rather than strongly deviating.
We report on oxygen K-edge soft x-ray emission spectroscopy from a liquid water jet at the Linac Coherent Light Source. We observe significant changes in the spectral content when tuning over a wide range of incident x-ray fluences. In addition the total emission yield decreases at high fluences. These modifications result from reabsorption of x-ray emission by valence-excited molecules generated by the Auger cascade. Our observations have major implications for future x-ray emission studies at intense x-ray sources. We highlight the importance of the x-ray pulse length with respect to the core-hole lifetime.
Amoebae explore their environment in a random way, unless external cues like, e. g., nutrients, bias their motion. Even in the absence of cues, however, experimental cell tracks show some degree of persistence. In this paper, we analyzed individual cell tracks in the framework of a linear mixed effects model, where each track is modeled by a fractional Brownian motion, i.e., a Gaussian process exhibiting a long-term correlation structure superposed on a linear trend. The degree of persistence was quantified by the Hurst exponent of fractional Brownian motion. Our analysis of experimental cell tracks of the amoeba Dictyostelium discoideum showed a persistent movement for the majority of tracks. Employing a sliding window approach, we estimated the variations of the Hurst exponent over time, which allowed us to identify points in time, where the correlation structure was distorted ("outliers"). Coarse graining of track data via down-sampling allowed us to identify the dependence of persistence on the spatial scale. While one would expect the (mode of the) Hurst exponent to be constant on different temporal scales due to the self-similarity property of fractional Brownian motion, we observed a trend towards stronger persistence for the down-sampled cell tracks indicating stronger persistence on larger time scales.
Fabrication of Au@Pt multibranched nanoparticles and their application to in situ SERS monitoring
(2014)
Here, we present an Au@Pt core-shell multibranched nanoparticle as a new substrate capable of in situ surface-enhanced Raman scattering (SERS), thereby enabling monitoring of the catalytic reaction on the active surface. By careful control of the amount of Pt deposited bimetallic Au@Pt, nanoparticles with moderate performance both for SERS and catalytic activity were obtained. The Pt-catalyzed reduction of 4-nitrothiophenol by borohydride was chosen as the model reaction. The intermediate during the reaction was captured and clearly identified via SERS spectroscopy. We established in situ SERS spectroscopy as a promising and powerful technique to investigate in situ reactions taking place in heterogeneous catalysis.
Herein, we report the use of upconversion agents to modify graphite carbon nitride (g-C3N4) by direct thermal condensation of a mixture of ErCl3 center dot 6H(2)O and the supramolecular precursor cyanuric acid-melamine. We show the enhancement of g-C3N4 photoactivity after Er3+ doping by monitoring the photodegradation of Rhodamine B dye under visible light. The contribution of the upconversion agent is demonstrated by measurements using only a red laser. The Er3+ doping alters both the electronic and the chemical properties of g-C3N4. The Er3+ doping reduces emission intensity and lifetime, indicating the formation of new, nonradiative deactivation pathways, probably involving charge-transfer processes.
This Letter reports the discovery of a remarkably hard spectrum source, HESS J1641-463, by the High Energy Stereoscopic System (H.E.S.S.) in the very high energy (VHE) domain. HESS J1641-463 remained unnoticed by the usual analysis techniques due to confusion with the bright nearby source HESS J1640-465. It emerged at a significance level of 8.5 standard deviations after restricting the analysis to events with energies above 4 TeV. It shows a moderate flux level of phi(E > 1TeV) = (3.64 +/- 0.44(stat)+/- 0.73(sys)) x 10(-13) cm(-2) s(-1), corresponding to 1.8% of the Crab Nebula flux above the same energy, and a hard spectrum with a photon index of Gamma = 2.07 +/- 0.11(stat)+/- 0.20(sys). It is a point-like source, although an extension up to a Gaussian width of sigma = 3 arcmin cannot be discounted due to uncertainties in the H.E.S.S. point-spread function. The VHE gamma-ray flux of HESS J1641-463 is found to be constant over the observed period when checking time binnings from the year-by-year to the 28 minute exposure timescales. HESS J1641-463 is positionally coincident with the radio supernova remnant SNR G338.5+0.1. No X-ray candidate stands out as a clear association; however, Chandra and XMM-Newton data reveal some potential weak counterparts. Various VHE gamma-ray production scenarios are discussed. If the emission from HESS J1641-463 is produced by cosmic ray protons colliding with the ambient gas, then their spectrum must extend close to 1 PeV. This object may represent a source population contributing significantly to the galactic cosmic ray flux around the knee.
Herein, we report the facile synthesis of an efficient roll-like carbon nitride (C3N4) photocatalyst for hydrogen production using a supramolecular complex composed of cyanuric acid, melamine, and barbituric acid as the starting monomers. Optical and photocatalytic investigations show, along with the known red shift of absorption into the visible region, that the insertion of barbituric acid results in the in situ formation of in-plane heterojuctions, which enhance the charge separation process under illumination. Moreover, platinum as the standard cocatalyst in photocatalysis could be successfully replaced with first row transition metal salts and complexes under retention of 50% of the catalytic activity. Their mode of deposition and interaction with the semiconductor was studied in detail. Utilization of the supramolecular approach opens new opportunities to manipulate the charge transfer process within carbon nitride with respect to the design of a more efficient carbon nitride photocatalyst with controlled morphology and optical properties.
The membrane and actin cortex of a motile cell can autonomously differentiate into two states, one typical of the front, the other of the tail. On the substrate-attached surface of Dictyostelium discoideum cells, dynamic patterns of front-like and tail-like states are generated that are well suited to monitor transitions between these states. To image large-scale pattern dynamics independently of boundary effects, we produced giant cells by electric-pulse-induced cell fusion. In these cells, actin waves are coupled to the front and back of phosphatidylinositol (3,4,5)-trisphosphate (PIP3)-rich bands that have a finite width. These composite waves propagate across the plasma membrane of the giant cells with undiminished velocity. After any disturbance, the bands of PIP3 return to their intrinsic width. Upon collision, the waves locally annihilate each other and change direction; at the cell border they are either extinguished or reflected. Accordingly, expanding areas of progressing PIP3 synthesis become unstable beyond a critical radius, their center switching from a front-like to a tail-like state. Our data suggest that PIP3 patterns in normal-sized cells are segments of the self-organizing patterns that evolve in giant cells.