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The valence-excited states of ferric and ferrous hexacyanide ions in aqueous solution were mapped by resonant inelastic X-ray scattering (RIXS) at the Fe L-2,L-3 and N K edges. Probing of both the central Fe and the ligand N atoms enabled identification of the metal-and ligand-centered excited states, as well as ligand-to-metal and metal-to-ligand charge-transfer excited states. Ab initio calculations utilizing the RASPT2 method were used to simulate the Fe L-2,L-3-edge RIXS spectra and enabled quantification of the covalencies of both occupied and empty orbitals of pi and sigma symmetry. We found that pi back-donation in the ferric complex is smaller than that in the ferrous complex. This is evidenced by the relative amounts of Fe 3d character in the nominally 2 pi CN- molecular orbital of 7% and 9% in ferric and ferrous hexacyanide, respectively. Utilizing the direct sensitivity of Fe L-3-edge RIXS to the Fe 3d character in the occupied molecular orbitals, we also found that the donation interactions are dominated by sigma bonding. The latter was found to be stronger in the ferric complex, with an Fe 3d contribution to the nominally 5 sigma CN- molecular orbitals of 29% compared to 20% in the ferrous complex. These results are consistent with the notion that a higher charge at the central metal atom increases donation and decreases back-donation.
Photospheric radiation can drive winds from hot, massive stars by direct momentum transfer through scattering in bound-bound transitions of atmospheric ions. The line radiation force should cause a new radiative wave mode. The dispersion relation from perturbations of the line force was analysed so far either in Sobolev approximation or for pure line absorption. The former does not include the line-driven instability, and the latter cannot account for upstream propagating, radiative waves. We consider a non-Sobolev line force that includes scattering in a simplified way, accounting however for the important line-drag effect. We derive a new dispersion relation for radiative waves, and analyse wave propagation using Fourier methods, and by numerical solution of an integro-differential equation. The existence of an upstream propagating, dispersive radiative wave mode is demonstrated.
Damage due to tropical cyclones accounts for more than 50% of all meteorologically-induced economic losses worldwide. Their nominal impact is projected to increase substantially as the exposed population grows, per capita income increases, and anthropogenic climate change manifests. So far, historical losses due to tropical cyclones have been found to increase less than linearly with a nation's affected gross domestic product (GDP). Here we show that for the United States this scaling is caused by a sub-linear increase with affected population while relative losses scale super-linearly with per capita income. The finding is robust across a multitude of empirically derived damage models that link the storm's wind speed, exposed population, and per capita GDP to reported losses. The separation of both socio-economic predictors strongly affects the projection of potential future hurricane losses. Separating the effects of growth in population and per-capita income, per hurricane losses with respect to national GDP are projected to triple by the end of the century under unmitigated climate change, while they are estimated to decrease slightly without the separation.
Ca3NbGa3Si2O14 (CNGS), a five-component crystal of lanthanum-gallium silicate group, was grown by the Czochralski method. The parameters of the elementary unit cell of the crystal were measured by powder diffraction. The independent piezoelectric strain coefficients d(11) and d(14) were determined by the triple-axis X-ray diffraction in the Bragg and Laue geometries. Excitation and propagation of surface acoustic waves (SAW) were studied by high-resolution X-ray diffraction at BESSY II synchrotron radiation source. The velocity of SAW propagation and power flow angles in the Y-, X-and yxl/+36 degrees-cuts of the CNGS crystal were determined from the analysis of the diffraction spectra. The CNGS crystal was found practically isotropic by its acoustic properties.
We study the damping processes of both incompressible and compressible magnetohydrodynamic (MHD) turbulence in a partially ionized medium. We start from the linear analysis of MHD waves, applying both single-fluid and two-fluid treatments. The damping rates derived from the linear analysis are then used in determining the damping scales of MHD turbulence. The physical connection between the damping scale of MHD turbulence and the cutoff boundary of linear MHD waves is investigated. We find two branches of slow modes propagating in ions and neutrals, respectively, below the damping scale of slow MHD turbulence, and offer a thorough discussion of their propagation and dissipation behavior. Our analytical results are shown to be applicable in a variety of partially ionized interstellar medium (ISM) phases and the solar chromosphere. The importance of neutral viscosity in damping the Alfvenic turbulence in the interstellar warm neutral medium and the solar chromosphere is demonstrated. As a significant astrophysical utility, we introduce damping effects to the propagation of cosmic rays in partially ionized ISM. The important role of turbulence damping in both transit-time damping and gyroresonance is identified.
In this study, we complement the notion of equilibrium states of the radiation belts with a discussion on the dynamics and time needed to reach equilibrium. We solve for the equilibrium states obtained using 1-D radial diffusion with recently developed hiss and chorus lifetimes at constant values of Kp = 1, 3, and 6. We find that the equilibrium states at moderately low Kp, when plotted versus L shell (L) and energy (E), display the same interesting S shape for the inner edge of the outer belt as recently observed by the Van Allen Probes. The S shape is also produced as the radiation belts dynamically evolve toward the equilibrium state when initialized to simulate the buildup after a massive dropout or to simulate loss due to outward diffusion from a saturated state. Physically, this shape, intimately linked with the slot structure, is due to the dependence of electron loss rate (originating from wave-particle interactions) on both energy and L shell. Equilibrium electron flux profiles are governed by the Biot number (tau(Diffusion)/tau(loss)), with large Biot number corresponding to low fluxes and low Biot number to large fluxes. The time it takes for the flux at a specific (L, E) to reach the value associated with the equilibrium state, starting from these different initial states, is governed by the initial state of the belts, the property of the dynamics (diffusion coefficients), and the size of the domain of computation. Its structure shows a rather complex scissor form in the (L, E) plane. The equilibrium value (phase space density or flux) is practically reachable only for selected regions in (L, E) and geomagnetic activity. Convergence to equilibrium requires hundreds of days in the inner belt for E>300 keV and moderate Kp (<= 3). It takes less time to reach equilibrium during disturbed geomagnetic conditions (Kp = 3), when the system evolves faster. Restricting our interest to the slot region, below L = 4, we find that only small regions in (L, E) space can reach the equilibrium value: E similar to [200, 300] keV for L= [3.7, 4] at Kp= 1, E similar to[0.6, 1] MeV for L = [3, 4] at Kp = 3, and E similar to 300 keV for L = [3.5, 4] at Kp = 6 assuming no new incoming electrons.
We present a statistical analysis of phase space density data from the first 26 months of the Van Allen Probes mission. In particular, we investigate the relationship between the tens and hundreds of keV seed electrons and >1 MeV core radiation belt electron population. Using a cross-correlation analysis, we find that the seed and core populations are well correlated with a coefficient of approximate to 0.73 with a time lag of 10-15 h. We present evidence of a seed population threshold that is necessary for subsequent acceleration. The depth of penetration of the seed population determines the inner boundary of the acceleration process. However, we show that an enhanced seed population alone is not enough to produce acceleration in the higher energies, implying that the seed population of hundreds of keV electrons is only one of several conditions required for MeV electron radiation belt acceleration.
In this study we investigated conditions for loss of GPS signals observed by the Swarm satellites during a 2 year period, from December 2013 to November 2015. Our result shows that the Swarm satellites encountered most of the total loss of GPS signal at the ionization anomaly crests, between +/- 5 degrees and +/- 20 degrees magnetic latitude, forming two bands along the magnetic equator, and these low-latitude events mainly appear around postsunset hours from 19: 00 to 22: 00 local time. By further checking the in situ electron density measurements of Swarm, we found that practically, all the total loss of GPS signal events at low latitudes are related to equatorial plasma irregularities (EPIs) that show absolute density depletions larger than 10 x 10(11) m(-3); then, the Swarm satellites encountered for up to 95% loss of GPS signal for at least one channel and up to 45% tracked less than four GPS satellites (making precise orbit determination impossible). For those EPIs with density depletions less than 10 x 10(11) m(-3), the chance of tracked GPS signals less than four reduces to only 1.0%. Swarm also observed total loss of all GPS signal at high latitudes, mainly around local noon, and these events are related to large spatial density gradients due to polar patches or increased geomagnetic/auroral activities. We further found that the loss of GPS signals were less frequent after appropriate settings of the Swarm GPS receivers had been updated. However, the more recent period of the mission, e.g., after the GPS receiver settings have been updated, also coincides with less severe electron density depletions due to the declining solar cycle, making GPS loss events less likely. We conclude that both lower electron density gradients and appropriate GPS receiver settings reduce the probability for Swarm satellites loss of GPS signals.
As has been shown by Watanabe and Strogatz (WS) (1993 Phys. Rev. Lett. 70 2391), a population of identical phase oscillators, sine-coupled to a common field, is a partially integrable system: for any ensemble size its dynamics reduce to equations for three collective variables. Here we develop a perturbation approach for weakly nonidentical ensembles. We calculate corrections to the WS dynamics for two types of perturbations: those due to a distribution of natural frequencies and of forcing terms, and those due to small white noise. We demonstrate that in both cases, the complex mean field for which the dynamical equations are written is close to the Kuramoto order parameter, up to the leading order in the perturbation. This supports the validity of the dynamical reduction suggested by Ott and Antonsen (2008 Chaos 18 037113) for weakly inhomogeneous populations.
Large-scale transitions in societies are associated with both individual behavioural change and restructuring of the social network. These two factors have often been considered independently, yet recent advances in social network research challenge this view. Here we show that common features of societal marginalization and clustering emerge naturally during transitions in a co-evolutionary adaptive network model. This is achieved by explicitly considering the interplay between individual interaction and a dynamic network structure in behavioural selection. We exemplify this mechanism by simulating how smoking behaviour and the network structure get reconfigured by changing social norms. Our results are consistent with empirical findings: The prevalence of smoking was reduced, remaining smokers were preferentially connected among each other and formed increasingly marginalized clusters. We propose that self-amplifying feedbacks between individual behaviour and dynamic restructuring of the network are main drivers of the transition. This generative mechanism for co-evolution of individual behaviour and social network structure may apply to a wide range of examples beyond smoking.
During the summer of 2013, a 4-month spectroscopic campaign took place to observe the variabilities in three Wolf-Rayet stars. The spectroscopic data have been analysed for WR 134 (WN6b), to better understand its behaviour and long-term periodicity, which we interpret as arising from corotating interaction regions (CIRs) in the wind. By analysing the variability of the He ii lambda 5411 emission line, the previously identified period was refined to P = 2.255 +/- 0.008 (s.d.) d. The coherency time of the variability, which we associate with the lifetime of the CIRs in the wind, was deduced to be 40 +/- 6 d, or similar to 18 cycles, by cross-correlating the variability patterns as a function of time. When comparing the phased observational grey-scale difference images with theoretical grey-scales previously calculated from models including CIRs in an optically thin stellar wind, we find that two CIRs were likely present. A separation in longitude of Delta I center dot a parts per thousand integral 90A degrees was determined between the two CIRs and we suggest that the different maximum velocities that they reach indicate that they emerge from different latitudes. We have also been able to detect observational signatures of the CIRs in other spectral lines (C iv lambda lambda 5802,5812 and He i lambda 5876). Furthermore, a DAC was found to be present simultaneously with the CIR signatures detected in the He i lambda 5876 emission line which is consistent with the proposed geometry of the large-scale structures in the wind. Small-scale structures also show a presence in the wind, simultaneously with the larger scale structures, showing that they do in fact co-exist.
Turbulence in the weakly collisional intracluster medium (ICM) of galaxies is able to generate strong thermal velocity anisotropies in the ions (with respect to the local magnetic field direction), if the magnetic moment of the particles is conserved in the absence of Coulomb collisions. In this scenario, the anisotropic pressure magnetohydrodynamic (AMHD) turbulence shows a very different statistical behaviour from the standard MHD one and is unable to amplify seed magnetic fields. This is in contrast to previous cosmological MHD simulations that are successful in explaining the observed magnetic fields in the ICM. On the other hand, temperature anisotropies can also drive plasma instabilities that can relax the anisotropy. This work aims to compare the relaxation rate with the growth rate of the anisotropies driven by the turbulence. We employ quasi-linear theory to estimate the ion scattering rate resulting from the parallel firehose, mirror and ion-cyclotron instabilities, for a set of plasma parameters resulting from AMHD simulations of the turbulent ICM. We show that the ICM turbulence can sustain only anisotropy levels very close to the instability thresholds. We argue that the AMHD model that bounds the anisotropies at the marginal stability levels can describe the Alfv,nic turbulence cascade in the ICM.
The concept of similitude is commonly employed in the fields of fluid dynamics and engineering but rarely used in cryospheric research. Here we apply this method to the problem of ice flow to examine the dynamic similitude of isothermal ice sheets in shallow-shelf approximation against the scaling of their geometry and physical parameters. Carrying out a dimensional analysis of the stress balance we obtain dimensionless numbers that characterize the flow. Requiring that these numbers remain the same under scaling we obtain conditions that relate the geometric scaling factors, the parameters for the ice softness, surface mass balance and basal friction as well as the ice-sheet intrinsic response time to each other. We demonstrate that these scaling laws are the same for both the (two-dimensional) flow-line case and the three-dimensional case. The theoretically predicted ice-sheet scaling behavior agrees with results from numerical simulations that we conduct in flow-line and three-dimensional conceptual setups. We further investigate analytically the implications of geometric scaling of ice sheets for their response time. With this study we provide a framework which, under several assumptions, allows for a fundamental comparison of the ice-dynamic behavior across different scales. It proves to be useful in the design of conceptual numerical model setups and could also be helpful for designing laboratory glacier experiments. The concept might also be applied to real-world systems, e.g., to examine the response times of glaciers, ice streams or ice sheets to climatic perturbations.
We study the adsorption-desorption transition of polyelectrolyte chains onto planar, cylindrical and spherical surfaces with arbitrarily high surface charge densities by massive Monte Carlo computer simulations. We examine in detail how the well known scaling relations for the threshold transition demarcating the adsorbed and desorbed domains of a polyelectrolyte near weakly charged surfaces-are altered for highly charged interfaces. In virtue of high surface potentials and large surface charge densities, the Debye-Huckel approximation is often not feasible and the nonlinear Poisson-Boltzmann approach should be implemented. At low salt conditions, for instance, the electrostatic potential from the nonlinear Poisson-Boltzmann equation is smaller than the Debye-Huckel result, such that the required critical surface charge density for polyelectrolyte adsorption sigma(c) increases. The nonlinear relation between the surface charge density and electrostatic potential leads to a sharply increasing critical surface charge density with growing ionic strength, imposing an additional limit to the critical salt concentration above which no polyelectrolyte adsorption occurs at all. We contrast our simulations findings with the known scaling results for weak critical polyelectrolyte adsorption onto oppositely charged surfaces for the three standard geometries. Finally, we discuss some applications of our results for some physical-chemical and biophysical systems.
In recent decades, the Greenland Ice Sheet has been losing mass and has thereby contributed to global sea-level rise. The rate of ice loss is highly relevant for coastal protection worldwide. The ice loss is likely to increase under future warming. Beyond a critical temperature threshold, a meltdown of the Greenland Ice Sheet is induced by the self-enforcing feedback between its lowering surface elevation and its increasing surface mass loss: the more ice that is lost, the lower the ice surface and the warmer the surface air temperature, which fosters further melting and ice loss. The computation of this rate so far relies on complex numerical models which are the appropriate tools for capturing the complexity of the problem. By contrast we aim here at gaining a conceptual understanding by deriving a purposefully simple equation for the self-enforcing feedback which is then used to estimate the melt time for different levels of warming using three observable characteristics of the ice sheet itself and its surroundings. The analysis is purely conceptual in nature. It is missing important processes like ice dynamics for it to be useful for applications to sea-level rise on centennial timescales, but if the volume loss is dominated by the feedback, the resulting logarithmic equation unifies existing numerical simulations and shows that the melt time depends strongly on the level of warming with a critical slow-down near the threshold: the median time to lose 10% of the present-day ice volume varies between about 3500 years for a temperature level of 0.5 degrees C above the threshold and 500 years for 5 degrees C. Unless future observations show a significantly higher melting sensitivity than currently observed, a complete meltdown is unlikely within the next 2000 years without significant ice-dynamical contributions.
This paper describes a strategy for preparing photosensitive polymeric grafts on flat solid surfaces by loading diblock-copolymer or homopolymer brushes with cationic azobenzene-containing surfactants. In contrast to previous work, we utilize photosensitive surfactants that bear positively-charged polyamine head groups whose charge varies between 1(+) and 3(+). Poly(methylmethacrylate-b-methacrylic acid) (PMMA-b-PMAA) brushes were prepared by employing atom transfer radical polymerization, where the bottom poly(methyl methacrylate) block was grown first followed by the synthesis of t-butyl methacrylate block that after de-protection yielded poly(methacrylic acid). We used PMMA-b-PMAA brushes with constant grafting density and length of the PMMA block, and three different lengths of the PMAA block. The azobenzene-based surfactants attached only to the PMAA block. The degree of binding (i.e., the number of surfactant molecules per binding site on the brush backbone) of the surfactants to the brush depends strongly on the valence of the surfactant head-group; within the brushes the concentration of the surfactant carrying unit charge is larger than that of multivalent surfactants. We detect pronounced response of the brush topography on irradiation with UV interference pattern even at very low degree of binding (as small as 0.08) of multi-valence surfactant. Areas on the sample that receive the highest UV dose exhibit chain scission. By removing the ruptured chains from the substrate via good solvent, one uncovers a surface topographical relief grating, whose spatial arrangement follows the intensity distribution of the UV light on the sample during irradiation. Due to strong coupling of the multi-valence surfactants to the polymer brush, it was possible in some cases to completely remove the polyelectrolyte block from the PMMA layer. The application of multi-valence azobenzene surfactants for triggering brush photosensitive has important advantage over usage of surfactant with unit charge because relative to single-valence surfactants much lower concentrations of the multivalent surfactant are needed to achieve comparable response upon UV irradiation. (C) 2016 Elsevier Ltd. All rights reserved.
Nearly all types of massive stars with radiatively driven stellar winds are X-ray sources that can be observed by the presently operating powerful X-ray telescopes. In this review I briefly address recent advances in our understanding of stellar winds obtained from X-ray observations. X-rays may strongly influence the dynamics of weak winds of main sequence B-type stars. X-ray pulsations were detected in a beta Cep type variable giving evidence of tight photosphere-wind connections. The winds of OB dwarfs with subtypes later than O9V may be predominantly in a hot phase, and X-ray observations offer the best window for their studies. The X-ray properties of OB super giants are largely determined by the effects of radiative transfer in their clumped stellar winds. The recently suggested method to directly measure mass-loss rates of O stars by fitting the shapes of X-ray emission lines is considered but its validity cannot be confirmed. To obtain robust quantitative information on stellar wind parameters from X-ray spectroscopy, a multiwavelength analysis by means of stellar atmosphere models is required. Independent groups are now performing such analyses with encouraging results. Joint analyses of optical, UV, and X-ray spectra of OB supergiants yield consistent mass-loss rates. Depending on the adopted clumping parameters, the empirically derived mass-loss rates are a factor of a few smaller or comparable to those predicted by standard recipes (Vink et al., 2001). All sufficiently studied O stars display variable X-ray emission that might be related to corotating interaction regions in their winds. In the latest stages of stellar evolution, single red supergiants (RSG) and luminous blue variable (LBV) stars do not emit observable amounts of X-rays. On the other hand, nearly all types of Wolf-Rayet (WR) stars are X-ray sources. X-ray spectroscopy allows a sensitive probe of WR wind abundances and opacities. (C) 2016 COSPAR. Published by Elsevier Ltd. All rights reserved.
We present an optically induced remanent photostriction in BiFeO3, resulting from the photovoltaic effect, which is used to modify the ferromagnetism of Ni film in a hybrid BiFeO3/Ni structure. The 75% change in coercivity in the Ni film is achieved via optical and nonvolatile control. This photoferromagnetic effect can be reversed by static or ac electric depolarization of BiFeO3. Hence, the strain dependent changes in magnetic properties are written optically, and erased electrically. Light-mediated straintronics is therefore a possible approach for low-power multistate control of magnetic elements relevant for memory and spintronic applications.