Smooth Evolution Research Articles

Ultrafast Double Optical Pump Technique for Probing Charge Transfer Processes at the Electrode-Electrolyte Interface

The electrode-electrolyte interface is one of the most technologically relevant there is, as it is where charge transfer occurs in driven electrochemical reactions. The short times after heterogeneous charge transfer witness the occurrence of primordial processes, such as intramolecular rearrangement and solvation shell reorganization. Yet, probing the evolution of this interface with ultrafine time resolution (10-15—10-12 s) is highly challenging, if not impossible, with electronics-based techniques. [1] Photoinjection techniques have been used to trigger charge capture by acceptors at the electrode-electrolyte interface, which was observed with > 10-9 s time resolution from photocurrent. [2] We aim to use the aqueous electron as a test bed for probing the heterogeneous charge transfer with ultrafine time resolution. The ultrafast kinetics of this fundamental species have been studied in the bulk [3], but it was never observed at the interface. We have used ultrafast laser pulses in the ultraviolet (UV) range with the intent of triggering photoinjection from a 200 nm thick polycrystalline gold electrode to the 0.5 M Na2SO4 electrolyte. The energy of the ultraviolet photons (4.64 eV) is high enough for excited electrons to reach the LUMO of water, and exposure of the electrode to the UV laser beam indeed creates a large photovoltage. A second ultrafast pulse of lower energy (ranging from 0.31 to 1.85 eV) is used to resonantly pump the excitation after a controlled delay varying from -4 ps to 100 ps with the smaller steps being of 50 fs. This second pump pulse also causes a photovoltage change, but smaller by an order of magnitude than the photovoltage caused by the first. The photovoltage due to the second pump pulse decays at a rate that is dependent on the photon energy, which yields a resonant profile that matches the absorption profile of hot electrons in water during the solvation process. [4] For instance, the decay rate at 0.31 eV is very fast, being comparable or smaller than our 50 fs minimum step size, and is independent of pump power. At 1.85 eV, however, the photovoltage lasts for longer than 100 ps, showing that a long-lasting species endures at the gold-electrolyte interface. In between, we capture the smooth evolution of the decay kinetics. We expect this technique to enable the study of ultrafast kinetics of relevant processes directly at the electrode-electrolyte interface, giving valuable mechanistic insight on important electrochemical reactions such as the oxygen reduction reactions (ORR).

Femtosecond x-ray spectroscopy of an electrocyclic ring-opening reaction.

The ultrafast light-activated electrocyclic ring-opening reaction of 1,3-cyclohexadiene is a fundamental prototype of photochemical pericyclic reactions. Generally, these reactions are thought to proceed through an intermediate excited-state minimum (the so-called pericyclic minimum), which leads to isomerization via nonadiabatic relaxation to the ground state of the photoproduct. Here, we used femtosecond (fs) soft x-ray spectroscopy near the carbon K-edge (~284 electron volts) on a tabletop apparatus to directly reveal the valence electronic structure of this transient intermediate state. The core-to-valence spectroscopic signature of the pericyclic minimum observed in the experiment was characterized, in combination with time-dependent density functional theory calculations, to reveal overlap and mixing of the frontier valence orbital energy levels. We show that this transient valence electronic structure arises within 60 ± 20 fs after ultraviolet photoexcitation and decays with a time constant of 110 ± 60 fs.

Denoising Smooth Signals Using a Bayesian Approach: Application to Altimetry

This paper presents a novel Bayesian strategy for the estimation of smooth signals corrupted by Gaussian noise. The method assumes a smooth evolution of a succession of continuous signals that can have a numerical or an analytical expression with respect to some parameters. The proposed Bayesian model takes into account the Gaussian properties of the noise and the smooth evolution of the successive signals. In addition, a gamma Markov random field prior is assigned to the signal energies and to the noise variances to account for their known properties. The resulting posterior distribution is maximized using a fast coordinate descent algorithm whose parameters are updated by analytical expressions. The proposed algorithm is tested on satellite altimetric data demonstrating good denoising results on both synthetic and real signals. In comparison with state-of-the-art algorithms, the proposed strategy provides a good compromise between denoising quality and necessary reduced computational cost. The proposed algorithm is also shown to improve the quality of the altimetric parameters when combined with a parameter estimation or a classification strategy.

Robust estimation of scattering in pulsar timing analysis

We present a robust approach to incorporating models for the time-variable broadening of the pulse profile due to scattering in the ionized interstellar medium into profile-domain pulsar timing analysis. We use this approach to simultaneously estimate temporal variations in both the dispersion measure (DM) and scattering, together with a model for the pulse profile that includes smooth evolution as a function of frequency, and the pulsar's timing model. We show that fixing the scattering timescales when forming time-of-arrival estimates, as has been suggested in the context of traditional pulsar timing analysis, can significantly underestimate the uncertainties in both DM, and the arrival time of the pulse, leading to bias in the timing parameters. We apply our method using a new, publicly available, GPU accelerated code, both to simulations, and observations of the millisecond pulsar PSR J1643$-$1224. This pulsar is known to exhibit significant scattering variability compared to typical millisecond pulsars, and we find including low-frequency ($< 1$ GHz) data without a model for these scattering variations leads to significant periodic structure in the DM, and also biases the astrometric parameters at the $4\sigma$ level, for example, changing proper motion in right ascension by $0.50 \pm 0.12$. If low frequency observations are to be included when significant scattering variations are present, we conclude it is necessary to not just model those variations, but also to sample the parameters that describe the variations simultaneously with all other parameters in the model, a task for which profile domain pulsar timing is ideally suited.

Identifying the chiral d-wave superconductivity by Josephson \u03c60-states

We propose the Josephson junctions linked by a normal metal between a d + id superconductor and another d + id superconductor, a d-wave superconductor, or a s-wave superconductor for identifying the chiral d + id superconductivity. The time-reversal breaking in the chiral d-wave superconducting state is shown to result in a Josephson φ0-junction state where the current-phase relation is shifted by a phase φ0 from the sinusoidal relation, other than 0 and π. The ground-state phase difference φ0 and the critical current can be used to definitely confirm and read the information about the d + id superconductivity. A smooth evolution from conventional 0-π transitions to tunable φ0-states can be observed by changing the relative magnitude of two types of d-wave components in the d + id pairing. On the other hand, the Josephson junction involving the d + id superconductor is also the simplest model to realize a φ0- junction, which is useful in superconducting electronics and superconducting quantum computation.

A unified approach to explain contrary effects of hysteresis and smoothing in nonsmooth systems

Piecewise smooth dynamical systems make use of discontinuities to model switching between regions of smooth evolution. This introduces an ambiguity in prescribing dynamics at the discontinuity: should the dynamics be given by a limiting value on one side or other of the discontinuity, or a member of some set containing those values? One way to remove the ambiguity is to regularize the discontinuity, the most common being either to smooth it out, or to introduce a hysteresis between switching in one direction or the other across it. Here we show that the two can in general lead to qualitatively different dynamical outcomes. We then define a higher dimensional model with both smoothing and hysteresis, and study the competing limits in which hysteretic or smoothing effects dominate the behaviour, only the former of which correspond to Filippov’s standard ‘sliding modes’.

Extraction of the 3D local orientation of myocytes in human cardiac tissue using X-ray phase-contrast micro-tomography and multi-scale analysis.

This paper presents a methodology to access the 3D local myocyte arrangements in fresh human post-mortem heart samples. We investigated the cardiac micro-structure at a high and isotropic resolution of 3.5µm in three dimensions using X-ray phase micro-tomography at the European Synchrotron Radiation Facility. We then processed the reconstructed volumes to extract the 3D local orientation of the myocytes using a multi-scale approach with no segmentation. We created a simplified 3D model of tissue sample made of simulated myocytes with known size and orientations, to evaluate our orientation extraction method. Afterwards, we applied it to 2D histological cuts and to eight 3D left ventricular (LV) cardiac tissue samples. Then, the variation of the helix angles, from the endocardium to the epicardium, was computed at several spatial resolutions ranging from 3.63mm3 to 1123 µm3. We measure an increased range of 20° to 30° from the coarsest resolution level to the finest level in the experimental samples. This result is in line with the higher values measured from histology. The displayed tractography demonstrates a rather smooth evolution of the transmural helix angle in six LV samples and a sudden discontinuity of the helix angle in two septum samples. These measurements bring a new vision of the human heart architecture from macro- to micro-scale.

Mean curvature flow of Reifenberg sets

In this paper, we prove short time existence and uniqueness of smooth evolution by mean curvature in $\mathbb{R}^{n+1}$ starting from any $n$-dimensional $(\varepsilon,R)$-Reifenberg flat set with $\varepsilon$ sufficiently small. More precisely, we show that the level set flow in such a situation is non-fattening and smooth. These sets have a weak metric notion of tangent planes at every small scale, but the tangents are allowed to tilt as the scales vary. As this class is wide enough to include some fractal sets, this provides the first example (when $n>1$) of unique smoothing by mean curvature flow of sets with Hausdorff dimension $> n$.

Identified Two-particle Correlations and Quantum Number Conservations in p-p and Pb-Pb Collisions at LHC Energies

In this paper we continue the investigation of the effect of quantum number conservations of pions, kaons, and protons, with very high transverse momenta (up to 25 GeV/c), during parton fragmentation and hadronization in p-p and Pb-Pb collisions at LHC energies [1, 2]. The strength of the conservation effects are studied by identified two-particle correlations in Monte Carlo generated events in the mid-rapidity region (|η| < 1). The simulated p-p events were generated with PYTHIA 8 [5], using its main default settings, at , , , and . In parallel to this, HIJING 1.36 [6] was used to generate Pb-Pb events at with centralities 0 – 10%, 30 – 40% and 80 – 90%. The extracted identified associated hadron spectra for charged pion, kaon, and proton show identified trigger-hadron dependent splitting between oppositely charged associated particle species in any nucleus-nucleus collisions. The Pb-Pb data exhibits a peculiar splitting pattern as a function of the transverse momentum of the associated particle pT,assoc both on the near and away side that is different from the patterns observed in p-p collisions. The splitting shows smooth evolution with collision energy and event multiplicity in p-p collisions while in Pb-Pb collisions different trend were observed for kaons and protons.

Bifurcation induced by the aspect ratio in a turbulent von Kármán swirling flow.

We evaluate the effect of the aspect ratio, i.e., the distance between the propellers H divided by the diameter D, on the slow dynamics of a von Kármán swirling flow driven by two propellers in a closed cylinder. We use a cell with a fixed diameter D but where the distance between the propellers can be turned continuously and where the inertia from the propellers can also be changed using different gears. No change on the dynamics is observed when the momentum of inertia is modified. Some dramatic changes of the shear layer position are observed modifying the aspect ratio Γ=H/D. A bifurcation of the shear layer position appears. Whereas for low Γ the shear layer position has a smooth evolution when turning the asymmetry between the rotation frequency of the propellers, for high Γ the transition becomes abrupt and a symmetry breaking appears. Secondly we observe that the spontaneous reversals with large residence times already observed in this experiment for Γ=1 [de la Torre and Burguete, Phys. Rev. Lett. 99, 054101 (2007)PRLTAO0031-900710.1103/PhysRevLett.99.054101] exist only in a narrow window of aspect ratio. We show using an experimental study of the mean flow structure and a numerical approach based on a Langevin equation with colored noise that the shear layer position seems to be decided by the mean flow structure, whereas the reversals are linked to the spatial distribution of the turbulent fluctuations in the cell.

Gradual refinement types

Refinement types are an effective language-based verification technique. However, as any expressive typing discipline, its strength is its weakness, imposing sometimes undesired rigidity. Guided by abstract interpretation, we extend the gradual typing agenda and develop the notion of gradual refinement types, allowing smooth evolution and interoperability between simple types and logically-refined types. In doing so, we address two challenges unexplored in the gradual typing literature: dealing with imprecise logical information, and with dependent function types. The first challenge leads to a crucial notion of locality for refinement formulas, and the second yields novel operators related to type- and term-level substitution, identifying new opportunity for runtime errors in gradual dependently-typed languages. The gradual language we present is type safe, type sound, and satisfies the refined criteria for gradually-typed languages of Siek et al. We also explain how to extend our approach to richer refinement logics, anticipating key challenges to consider.

Incorporation of Soft Particles into Lipid Vesicles: Effects of Particle Size and Elasticity.

The interaction between particles and lipid biomembranes plays an essential role in many fields such as endocytosis, drug delivery, and intracellular traffic. Here we conduct a theoretical study on the incorporation of elastic particles of different sizes and rigidities into a lipid vesicle through adhesive wrapping. It is shown that while the incorporation of relatively small particles involves smooth shape evolution, the vesicle wrapping of large particles exhibits a discontinuous shape transition, followed by a protrusion of the vesicle membrane at infinitesimal cost of elastic deformation energy. Moreover, softer particles require stronger adhesion energy to achieve successful internalization and delay the onset of discontinuous shape transition to a higher wrapping degree. Depending on the adhesion energy, particle-vesicle size, and rigidity ratios, and the spontaneous curvature of the vesicle, a rich variety of wrapping phase diagrams consisting of stable and metastable states of no-wrapping, partial-wrapping, and full-wrapping are established. The underlying mechanism of the discontinuous shape transformation of the vesicle and the relation between the uptake proneness and uptake efficiency are discussed. These results shed further light on the elasticity effects in cellular uptake of elastic particles and may provide rational design guidelines for controlled endocytosis and diagnostics delivery.

Low Bit-Rate Speech Codec Based on a Long-Term Harmonic Plus Noise Model

The long-term harmonic plus noise model (LT-HNM) for speech shows an interesting data compression, since it exploits the smooth evolution of the time trajectories of the short-term harmonic plus noise model parameters, by applying a discrete cosine model (DCM). In this paper, we extend the LT-HNM to a complete low bit-rate speech coder. A Normalized Split Vector Quantization (NSVQ) is proposed to quantize the variable dimension LT-DCM vectors. The NSVQ is designed according to the properties of the DCM vectors obtained from a standard speech database. The obtained LT-HNM coder reaches an average bit-rate of 2.7kbps for wideband speech. The proposed coder is evaluated in terms of modeling and coding errors, bit-rate, listening quality and intelligibility. Index Terms Low bit-rate, speech coding, long term modeling, harmonic plus noise model, variable dimension vector quantization.

Dependence of Energy of Two-Phase Elastic Medium on Phase Interface

For smooth evolution of an arbitrary phase location in a composite medium we prove that the equilibrium energy of this medium is continuously time-differentiable and compute the derivative.

Slow Preconditioning for the Abrupt Convective Jump over the Northwest Pacific during Summer

Abstract The rapid intensification of convective activity in mid-July over the northwest Pacific marks the final stage of the Asian summer monsoon, accompanied by major shifts in regional rainfall and circulation patterns. An entraining plume model is used to investigate the physical processes underlying the abrupt convective jump. Despite little change in sea surface temperature (SST), gradual lower-troposphere mixing leads to a threshold transition in the model as follows. Before mid-July, although SST is already high (29°C), the convective plume is inhibited by the capping inversion above the trade cumulus boundary layer. As the lower troposphere is gradually mixed, the boundary layer top rises with reduced atmospheric stability and increased humidity in the lower troposphere. These factors weaken the inhibition effect of the inversion on the entraining plume. As soon as the plume is able to overcome the inversion barrier, it can rise all the way to the upper troposphere. This marks an abrupt threshold transition to a deep convection regime with heavy rainfall. The convective available potential energy (CAPE) of the entraining plume is found to be a better indicator of the rainfall intensity compared to the conventional undiluted CAPE. The latter fails to capture the onset by neglecting interactions between convective clouds and the environment. Current general circulation models (GCMs) fail to capture the abrupt convective jump and instead simulate a rather smooth seasonal evolution of rainfall. Compared to observations, GCMs simulate a higher trade cumulus top with excessive mixing in the lower troposphere. Convection is no longer inhibited by the inversion barrier, and rainfall simply follows the smooth variation of SST.

Variational integration in endochronic theory for small strain elastoplastodynamics

AbstractThis paper presents a basic endochronic plasticity model with isotropic hardening for small strain theory according to Valanis. The key point of this model is a convolution integral over an intrinsic time scale involving past values of the strain measure and a so‐called memory kernel which leads to a smooth evolution equation for the internal variable. For the temporal discretization of the underlying constitutive equations and the resulting evolution equation we use higher order accurate variational integrators (VI). The remarkable feature is the fact that we approximate the position vector in terms of velocities according to partitioned Runge‐Kutta methods (pRK). As a representative model problem serves a quasistatic, uniaxial tensile testing as well as a dynamic, elastoplastic cantilever beam with a smooth plasticity model according to the Valanis framework. (© 2016 Wiley‐VCH Verlag GmbH &amp; Co. KGaA, Weinheim)

High-precision abundances of Sc, Mn, Cu, and Ba in solar twins

A previous study of correlations between element abundance ratios, [X/Fe], and ages of solar twin stars is extended to include Sc, Mn, Cu, and Ba. HARPS spectra with S/N > 600 are used to derive very precise (+/- 0.01 dex) differential abundances, and stellar ages with internal errors less than 1 Gyr are obtained by interpolation in the logg - Teff diagram between isochrones calculated with the Aarhus Stellar Evolution Code. For stars younger than 6 Gyr, [X/Fe] is tightly correlated with stellar age for all elements. For ages between 6 and 9 Gyr, the [X/Fe] - age correlations break down and the stars split up into two groups having respectively high and low [X/Fe] for the odd-Z elements. It is concluded that while stars in the solar neighborhood younger than about 6 Gyr were formed from interstellar gas with a smooth chemical evolution, older stars have originated from regions enriched by supernovae with different neutron excesses. Furthermore, the correlations between abundance ratios and stellar age suggest that: i) Sc is made in Type II supernovae along with the alpha-capture elements, ii) the Type II to Ia SNe yield ratio is about the same for Mn and Fe, iii) Cu is mainly made by the weak s-process in massive stars, iv) the Ba/Y yield ratio for AGB stars increases with decreasing stellar mass, v) [Y/Mg] and [Y/Al] can be used as "chemical clocks" when determining ages of solar metallicity stars.

Morphology and kinematics of the gas envelope of the variable AGB star π1 Gruis**This paper makes use of the following ALMA data: ADS/JAO.ALMA# . ALMA is a partnership of ESO (representing its member states), NSF (USA) and NINS (Japan), together with NRC (Canada) and NSC and ASIAA (Taiwan), and KASI (Republic of Korea) in cooperation with the Republic of Chile.

Observations of the 12CO(3–2) emission from the circumstellar envelope (CSE) of the variable star π1 Gru using the compact array of the ALMA observatory have been recently made accessible to the public. An analysis of the morphology and kinematics of the CSE is presented with a result very similar to that obtained earlier for 12CO(2–1) emission using the Submillimeter Array. A quantitative comparison is made using their flared disk model. A new model is presented that provides a significantly better description of the data, using radial winds and smooth evolutions of the radio emission and wind velocity from the stellar equator to the poles.

Aspects of the momentum dependence of the equation of state and of the residualNNcross section, and their effects on nuclear stopping

With the semiclassical Landau-Vlasov transport model we studied the stopping observable $R_E$, the energy-based isotropy ratio, for the $^{129}$Xe\,+\,$^{120}$Sn reaction at beam energies spanning 12$A$ to 100$A$ MeV. We investigated the impacts of the nonlocality of the nuclear mean field, of the in-medium modified nucleon-nucleon ($NN$) cross section and of the reaction centrality. A fixed set of model parameters yields $R_E$ values that favorably compare with the experimental ones, but only for energies below the Fermi energy $E_F$. Above $E_F$ agreement is readily possible, but by a smooth evolution with energy of the parameter that controls the in-medium modification of $NN$ cross section. By comparing the simulation correction factor ${\cal F}$ applied to the free $NN$ cross section with the one deduced from experimental data [Phys.\ Rev.\ C\,{\bf 90}, 064602 (2014)], we infer that the zero-range mean field almost entirely reproduces it. Also, in accordance with what has been deduced from experimental data, around $E_F$ a strong reduction of the free $NN$ cross section is found. In order to test the impact of sampling central collisions by multiplicity an event generator (HIPSE) was used. We obtain that high multiplicity events are spread over a broad impact parameter range, but it turns out that this has a small effect on the observable $R_E$ and, thus, on ${\cal F}$ as well.

Development and application of an accelerated biofouling test in flat cell

This paper discusses the steps followed to establish an accelerated reverse osmosis membrane biofouling test protocol. Easily bioassimilable nutrients were dosed into water from the Ebro River which was fed into a membrane flat cell pilot plant. The membrane biofouling results were determined by measuring adenosine triphosphate and total organic carbon extracted from the exposed membrane and feed spacer. This strategy was chosen because the equipment does not have pressure drop measurement capability and the observed change in flux or salt rejection was not significant under the testing conditions. The duration of the experiment was set to 3 d to enable rapid screening of different membrane types, yet enable a smooth evolution of biofilm. This study determined that achieving a similar amount of biofouling in each of the three cells was very sensitive to the level of bioassimilable nutrients were dosed to the water. For the Ebro River water, 0.2 mg/L of carbon, 0.04 mg/L of nitrogen, and 0.02 mg/L of phosphorous was determined to provide the best result.