Energy Redistribution Research Articles

Potential Nonstatistical Effects on the Unimolecular Decomposition of H2O2.

An attempt is made to evaluate the nonstatistical effects in the thermal decomposition of hydrogen peroxide (H2O2). Previous experimental studies on this reaction reported an unusual pressure dependence of the rate constant indicating broader falloff behavior than expected from conventional theory. In this work, the possibility that the rate constant is affected by nonstatistical effects is investigated based on classical trajectory calculations on the global potential energy surfaces of H2O2 and H2O2 + Ar. The emphasis is on the intramolecular energy redistribution from the K-rotor, that is, the external rotor for rotation around the principal axis of least moment of inertia. The calculations for the H2O2 molecules excited above the dissociation threshold suggest that the energy redistribution from the torsion and K-rotor to vibrations can be competitive with dissociation. In particular, the slow redistribution of the energy associated with the K-rotor significantly affects the dissociation rate. The successive trajectory calculations for collisions of H2O2 with Ar show that the energy associated with the K-rotor can be collisionally transferred more efficiently than the vibrational energy. On the basis of these results and several assumptions, a simple model is proposed to account for the nonstatistical effects on the pressure-dependent thermal rate constants. The model predicts significant broadening of the falloff curve of the rate constants but still cannot fully explain the experimental data.

Research on the effectiveness of aluminum passive safety elements in cars based on computer simulation

Introduction . The research of energy-absorbing element made of aluminum alloy, which is part of the passive safety system of a racing car, is carried out in the article. Designing and testing of the energy absorbing element was performed within the framework of the technical regulations of the international student engineering competition Formula SAE. Formula SAE is an engineering competition of student teams organized by the Society of Automotive Engineers (SAE). The design and analysis of the dynamic performance of the research object were performed in the computer-aided design system (CAD) ANSYS® Workbench SpaceClaim and ANSYS Explicit Dynamics. Problem Statement . The task of this research is to analyze the effectiveness of the use of aluminum alloy as the main material for the manufacture of the energy-absorbing element of the passive safety system of the car. Theoretical Part . Eleven structures of different shapes (structures) made of aluminum alloy 6063 were developed as promising models of energy-absorbing elements. A simulation crash test (frontal impact) was carried out, as a result of which it was possible to study the flow of deformation in the structure, to find the main zones of stress and load. This study of energy-absorbing elements can be used to justify the choice of material for the manufacture of passive car safety elements by car manufacturers and machine builders. Conclusions . The result of the research is a simulated process of destruction (or deformation) of the energy-absorbing element responsible for the absorption of energy in case of a frontal impact. The dependence of the manufacturing material and the shape of the energy absorbing element on the qualitative and quantitative characteristics of the passive car safety system has been investigated. Loads and stresses appearing in the structure of energy absorbing element have been studied. The efficiency of using aluminum alloy in promising car passive safety elements has been proved. Simulations of crash-tests showed that the use of progressive materials of construction elements of passive safety of vehicles, namely, aluminum alloys in an optimized (as a result of modeling) performance allows you to achieve high levels of protection of the pilot and passengers of the vehicle. The analysis of the absorbed energy value distribution allows revealing the direction for further improvement of the car passive safety systems. The influence of energy absorbing element manufacturing material on the processes occurring during frontal impact has been established. A universal technology of crash-testing (modeling of impact processes) of an energy absorbing element with a rigid obstacle has been developed in Ansys software. The percentage ratio (redistribution) of energy absorbed by frontal elements of passive safety of the car has been investigated.

Surface waves in a linearly graded-index and an intensity-dependent index layered structure.

A new type surface wave is found that propagates in a linearly graded-index and an intensity-dependent index layered structure characterized by an abrupt change in the dielectric constant. The main surface wave characteristics are calculated analytically. The optical domain, the thickness of which increases with an increasing effective refractive index and decreases with an increasing characteristic distance, is formed. It is discovered that the characteristic distance of the graded-index medium and effective refractive index can control wave energy redistribution between the semiconductor layers.

Multifunctional blazed gratings for multiband spatial filtering, retroreflection, splitting, and demultiplexing based on C2 symmetric photonic crystals

The concept of multifunctional reflection-mode gratings that are based on rod-type photonic crystals (PhCs) with C2 symmetry is introduced. The specific modal properties lead to the vanishing dependence of the first-negative-order maximum on the angle of incidence and the nearly sinusoidal redistribution of the incident-wave energy between zero order (specular reflection) and first negative diffraction order (deflection) at frequency variation. These features are key enablers of diverse functionalities and the merging of different functionalities into one structure. The elementary functionalities, of which multifunctional scenarios can be designed, include but are not restricted to multiband spatial filtering, multiband splitting, retroreflection, and demultiplexing. The proposed structures are capable of multifunctional operation in the case of a single polychromatic incident wave or multiple mono-/polychromatic waves incident at different angles. The generalized demultiplexing is possible in the case of several polychromatic waves. The aforementioned deflection properties yield merging demultiplexing with splitting in one functionality. In turn, it may contribute to more complex multifunctional scenarios. Finally, the proposed PhC gratings are studied in transmissive configuration, in which they show some unusual properties.

Damped perturbations in inviscid shear flows: van Kampen modes and Landau damping

We compare initial value and eigenvalue problems for two-dimensional perturbations of the inviscid shear flow in a channel. Singular solutions, known in plasma physics as van Kampen (vK) modes, are constructed. They form a complete set of eigenfunctions for decomposition of any initial perturbation for stable wavy perturbations. A pair of discrete modes appears to ensure completeness in the unstable case. Expansion coefficients for eigenmodes are found, and equivalence of temporal evolution obtained with the help of the evolutionary equation for vorticity and expansion over eigenmodes is presented. This alternative description of the evolution using vK modes is analogous to ones found earlier in plasma and in stellar dynamics. In particular, for stable wavy perturbations, an initial state decays first exponentially due to Landau damping, then algebraically. It has been established (numerically and analytically) that the final decay law is t−1. Also, we numerically demonstrate that Landau-damped perturbations are not true eigenmodes, but rather a superposition of vK-modes with a real frequency, which does not retain its shape over time. However, solution on contours in the complex plane may exhibit properties of a true eigenmode, that is, decay without changing its spatial form. Energy redistribution between perturbation and the flow, in stable and unstable regimes, is analyzed.

Characterization of intraseasonal fluctuations in the abyssal South China Sea: An insight into the energy pathway

Energetics of the abyssal ocean account greatly for the redistribution and dissipation of global oceanic energy. In this study, we characterize the intraseasonal fluctuations in the deep South China Sea (SCS) and evaluate the relevant energy budget using observations and numerical simulations. The results indicate substantial geographical inhomogeneity in the intraseasonal energy reservoir. The high-energy zones are located in the northwest of the Luzon Strait, northern slopes, deep western boundary current region, and southwestern cyclonic gyre region, where the intraseasonal fluctuations account for about 70% of the deep energy variability. Vorticity and divergence patterns of the intraseasonal motions are suggestive of quasigeostrophic dynamics, which are mostly attributed to the hybrid topographic–planetary Rossby waves. The flow field exhibits a weak lateral shear and appears to have symmetric instability with negative vorticity skewness, particularly over the sloping topography. Energetics analysis demonstrates that the intraseasonal fluctuations in the abyssal SCS obtain energy primarily from the upper layer through pressure work, while secondarily from advective transport and cross-scale transfer due to instability of the deep circulation. To reach equilibrium, the energy gained is mostly damped by dissipations. As another reference in the marginal sea with intensive mixing, our study highlights the potential universality in how the intraseasonal energy is fueled and dissipated in the abyss.

Enforcing detailed balance in the Borgnakke–Larsen redistribution method with temperature dependent relaxation models

For decades, it has been observed that the commonly used Borgnakke–Larsen method for energy redistribution in Direct Simulation Monte Carlo codes fails to satisfy the principle of detailed balance when coupled to a wide variety of temperature dependent relaxation models, while seemingly satisfying detailed balance when coupled to others. Many attempts have been made to remedy the issue, yet much ambiguity remains, and no consensus appears in the literature regarding the root cause of the intermittent compatibility of the Borgnakke–Larsen method with temperature dependent relaxation models. This paper alleviates that ambiguity by presenting a rigorous theoretical derivation of the Borgnakke–Larsen method's requirement for satisfying detailed balance. Specifically, it is shown that the Borgnakke–Larsen method maintains detailed balance if and only if the probability of internal-energy exchange during a collision depends only on collision invariants (e.g., total energy). The consequences of this result are explored in the context of several published definitions of relaxation temperature, including translational, total, and cell-averaged temperatures. Of particular note, it is shown that cell-averaged temperatures, which have been widely discussed in the literature as a way to ensure equilibrium is reached, also fail in a similar, although less dramatic, fashion when the aforementioned relationship is not enforced. The developed theory can be used when implementing existing or new relaxation models and will ensure that detailed balance is satisfied.

Steady State Photoisomerization Quantum Yield of Model Rhodopsin: Insights from Wavepacket Dynamics?

We simulate the nonequilibrium steady state cis-trans photoisomerization of retinal chromophore in rhodopsin on the basis of a two-state, two-mode model coupled to a thermal environment. By analyzing the systematic trends within an inhomogeneously broadened ensemble of systems, we find that the steady state reaction quantum yield (QY) correlates strongly with the excess energy above the crossing point of the system, in agreement with the prediction of the short-time dynamical wavepacket picture. However, the nontrivial dependence of the QY on the system-environment interaction indicates that a pure dynamical picture is insufficient and that environment-induced partial internal energy redistribution takes place before the reaction concludes. These results imply that a proper treatment of the photoisomerization reaction, particularly its high QY, must account for the redistribution and dissipation of energy beyond the dynamical wavepacket motion that is typically employed in the literature and that is appropriate only in the transient regime.

Secondary Currents at Very Low and High Aspect Ratios of Open Channels

The present numerical study is an attempt to better understand the effect of the aspect ratio (AR) on the velocity field characteristics of the fully-developed turbulent flow in a straight open channel by contrasting a very low and very high aspect ratio cases (AR = 1 and 12). The AR is defined as the ratio of the width of the channel in a plane normal to the flow direction, to the flow depth. The bulk velocity and water depth considered in this study are 0.75 m/s and 30 mm, respectively, which yield a Reynolds number of ReH = 22,500. The transient three-dimensional Navier-Stokes equations were numerically solved using a finite-volume approach with improved-delayed detached-eddy simulation (IDDES) turbulence model. The results revealed that the normalized components of the normal stresses by the turbulent kinetic energy k are constant over most of the velocity field, although k varies in magnitude throughout the velocity field in both AR cases. In addition, the results also revealed a strong anisotropic flow which justifies the formation of secondary currents as a means for transporting the kinetic energy. The results also reveal that both vertical and transverse components of the normal stresses are correlated to the side-recirculation zone (SRZ) and bottom-recirculation zone (BRZ), respectively, which highlights the role of the mean recirculation zones (BRZ & SRZ) in the re-distribution of the turbulent kinetic energy k in the velocity field.

Generating Multistructured Ultrasound via Bioinspired Metaskin Patterning for Low‐Threshold and Contactless Control of Living Organisms

AbstractMetasurfaces of the subwavelength thicknesses provide a distinctive route for acoustic wave manipulation. Based on the advanced 3D printing, those judiciously designed 2D metamaterials enable intriguing effects such as abnormal reflection, transmission, and absorption. However, acoustic metasurfaces, with strong wave–structure interactions in subwavelength scales, have encountered a big challenge of being acoustically transparent due to the insufficient impedance mismatch underwater. Here, reconfigurable bioinspired metaskin patterning for generating multistructured waterborne ultrasound is proposed. The nanostructured metaskin exhibits the “lotus effect,” with the thickness of only 70 μm (≈1/20 wavelength at 1 MHz) and a tremendous impedance mismatch (≈0.0001 transmission) for ultrasound. By depositing the strippable metaskins via self‐assembly into different patterns, the focusing, the vortex, and the Talbot structured ultrasound beams are implemented, respectively. The multistructured ultrasound has the patterned intensity fields of energy redistribution, where even weak field enhancement at low frequencies can activate the living organisms directly without using microbubbles, which enables low‐threshold and contactless behavior control via the mechanical stimulus.

On the Energization of Pickup Ions Downstream of the Heliospheric Termination Shock by Comparing 0.52–55 keV Observed Energetic Neutral Atom Spectra to Ones Inferred from Proton Hybrid Simulations

We present an unprecedented comparison of ∼0.52–55 keV energetic neutral atom (ENA) heliosheath measurements, remotely sensed by the Interstellar Boundary Explorer (IBEX) mission and the Ion and Neutral Camera (INCA) on the Cassini mission, with modeled ENAs inferred from interstellar pickup protons that have been accelerated at the termination shock, using hybrid simulations, to assess the pickup ion energetics within the heliosheath. This is the first study to use hybrid simulations that are able to accurately model the acceleration of ions to tens of keV energies, which is essential in order to model ENA fluxes in the heliosheath, covering the full energy range observed by IBEX and CASSINI/INCA. The observed ENA intensities are an average value over the time period from 2009 to the end of 2012, along the Voyager 2 (V2) trajectory. The hybrid simulations upstream of the termination shock, where V2 crossed, are constrained by observations. We report an energy-dependent discrepancy between observed and simulated ENA fluxes, with the observed ENA fluxes being persistently higher than the simulated ones. Our analysis reveals that the termination shock may not accelerate pickup ions to sufficient energies to account for the observed ENA fluxes. We, thus, suggest that the further acceleration of these pickup ions is most likely occurring within the heliosheath, via additional physical processes like turbulence or magnetic reconnection. However, the redistribution of energy inside the heliosheath remains an open question.

Intramolecular vibrational energy redistribution in nucleobases: Excitation of NH stretching vibrations in adenine-uracil + H2O.

Redistribution of vibrational energy in the adenine-uracil base pair is studied when the base pair undergoes an intermolecular interaction with an overtone-bending vibration excited H2O(2νbend) molecule. Energy transfer is calculated using the structural information obtained from density functional theory in the solution of the equations of motion. Intermolecular vibrational energy transfer (VET) from H2O(2νbend) to the uracil-NH stretching mode is efficient and rapidly followed by intramolecular vibrational energy redistribution (IVR) resulting from coupling between vibrational modes. An important pathway is IVR carrying energy to the NH-stretching mode of the adenine moiety in a subpicosecond scale, the energy build-up being sigmoidal, when H2O interacts with the uracil-NH bond. The majority of intermolecular hydrogen bonds between the base pair and H2O are weakened but unbroken during the ultrafast energy redistribution period. Lifetimes of intermolecular HB are on the order of 0.5ps. The efficiency of IVR in the base pair is due to near-resonance between coupled CC and CN vibrations. The resonance also exists between the frequencies of H2O bend and NH stretch, thus facilitating VET. When H2O interacts with the NH bond at the adenine end of the base pair, energy flow in the reverse direction to the uracil-NH stretch is negligible, the unidirectionality discussed in terms of the effects of uracil CH stretches. The energy distributed in the CH bonds is found to be significant. The IVR process is found to be nearly temperature independent between 200 and 400K.

Matrix Product State Formulation of the MCTDH Theory in Local Mode Representations for Anharmonic Potentials.

The matrix product state formulation of the multiconfiguration time-dependent Hartree theory, MPS-MCTDH, reported previously [Kurashige, J. Chem. Phys. 2018, 19, 194114] is extended to realistic anharmonic potentials with n-mode representations beyond the linear vibronic coupling model. For realistic vibrational potentials, the local mode representation should give a more compact representation of the potentials, i.e., lowering the dimensionality of the entanglements, than the normal coordinates, and the MPS-MCTDH formulation should work more efficiently and maintain the accuracy with a small bond dimension of the MPS ansatz. In fact, it was confirmed that the use of the local coordinates made the interaction matrices diagonal dominant and the number of terms in the n-body expansion of the potentials was significantly reduced. The method was applied to the IR spectrum of the CH2O molecule, the zero-point energies, and the vibrational energy redistribution dynamics of polyenes C2nH2n+2. The results showed that the efficiency of the MPS-MCTDH method is significantly accelerated by the use of local coordinates even if the long-range interactions are included in the potential.

Suppression and Enhancement of Thermal Chemical Rates in a Cavity

The observed modification of thermal chemical rates in Fabry-Perot cavities remains a poorly understood effect theoretically. Recent breakthroughs explain some of the observations through the Grote-Hynes theory, where the cavity introduces friction with the reaction coordinate, thus reducing the transmission coefficient and the rate. The regime of rate enhancement, the observed sharp resonances at varying cavity frequencies, and the survival of these effects in the collective regime remain mostly unexplained. In this Letter, we consider the cis-trans isomerization of HONO atomistically using an ab initio potential energy surface. We evaluate the transmission coefficient using the reactive flux method and identify the conditions for rate acceleration. In the underdamped, low-friction regime of the reaction coordinate, the cavity coupling enhances the rate with increasing coupling strength until reaching the Kramers turnover point. Sharp resonances in this regime are related to cavity-enabled energy redistribution channels.

Can the abyss swallow gravitational waves or why do we not observe echoes?

Here we propose a simple explanation why echoes from wormholes mimicking black holes may be so small that they cannot be observed. The essence of the effect is in the redistribution of the initial energy of gravitational wave among multiple universes, connected by a wormhole.

Solar Flare Heating with Turbulent Suppression of Thermal Conduction

During solar flares, plasma is typically heated to very high temperatures, and the resulting redistribution of energy via thermal conduction is a primary mechanism transporting energy throughout the flaring solar atmosphere. The thermal flux is usually modeled using Spitzer’s theory, which is based on local Coulomb collisions between the electrons carrying the thermal flux and those in the background. However, often during flares, temperature gradients become sufficiently steep that the collisional mean free path exceeds the temperature-gradient scale size, so that thermal conduction becomes inherently nonlocal. Further, turbulent angular scattering, which is detectable in nonthermal widths of atomic emission lines, can also act to increase the collision frequency and thus suppress the heat flux. Recent work by Emslie & Bian extended Spitzer’s theory of thermal conduction to account for both nonlocality and turbulent suppression. We have implemented their theoretical expression for the heat flux (which is a convolution of the Spitzer flux with a kernel function) into the RADYN flare-modeling code and performed a parameter study to understand how the resulting changes in thermal conduction affect the flare dynamics and hence the radiation produced. We find that models with reduced heat fluxes predict slower bulk flows, less intense line emission, and longer cooling times. By comparing the features of atomic emission lines predicted by the models with Doppler velocities and nonthermal line widths deduced from a particular flare observation, we find that models with suppression factors between 0.3 and 0.5 relative to the Spitzer value best reproduce the observed Doppler velocities across emission lines forming over a wide range of temperatures. Interestingly, the model that best matches the observed nonthermal line widths has a kappa-type velocity distribution function.

Effect of the Heterovalent Doping of TiO2 with Sc3+ and Nb5+ on the Defect Distribution and Photocatalytic Activity

Two series of Sc3+- and Nb5+-doped TiO2 (rutile) samples were synthesized and characterized by SEM, ICPE spectroscopy, XPS, and BET methods. Photocatalytic activity of the doped TiO2 samples was tested in photocatalytic degradation of phenol. Dependences of the photocatalytic activities of the doped TiO2 samples demonstrate a volcano-like behavior, indicating the existence of the optimal dopant concentrations to achieve the highest activity of photocatalysts. Remarkably, the optimal dopant concentrations correspond to the extrema observed in work function dependences on the dopant concentrations, that indicates a significant energy redistribution of the defect states within the bandgap of TiO2. Such a redistribution of the defect states is also proven by the alterations of the optical and EPR spectra of the intrinsic Ti3+ defect states in TiO2. Based on the analysis of the experimental results, we conclude that both Sc3+ and Nb5+ doping of TiO2 results in redistribution of the defect states and the optimal dopant concentrations correspond to the defect structures, which are ineffective in charge carrier recombination, that ultimately leads to the higher photocatalytic activity of doped TiO2.

Enhancing laser-nanoparticle interactions by diffused laser beams: efficient size-reduction of nanoparticles

Generally speaking, a laser beam with a good spatial profile such as flat-top or Gaussian (TEM00 mode) shape is considered to be a prerequisite to maximize laser-matter interactions. On the contrary, we show that if the process of interest has a threshold in terms of laser fluence or intensity, a diffused laser beam can do a good job of inducing the process. As an example, we demonstrate the efficient size-reduction of colloidal nanoparticles by a diffused laser beam and identify that the physical origin of this counterintuitive results is a redistribution of laser energy, i.e. formation of speckles through a diffuser where the local laser fluence exceeds the size-reduction threshold. We report the systematic results for silver and gold nanoparticles.

Constraints onTESSalbedos for five hot Jupiters

ABSTRACTPhotometric observations of occultations of transiting exoplanets can place important constraints on the thermal emission and albedos of their atmospheres. We analyse photometric measurements and derive geometric albedo (Ag) constraints for five hot Jupiters observed with TESS in the optical: WASP-18 b, WASP-36 b, WASP-43 b, WASP-50 b, and WASP-51 b. For WASP-43 b, our results are complemented by a VLT/HAWK-I observation in the near-infrared at $2.09\, \mu$m. We derive the first geometric albedo constraints for WASP-50 b and WASP-51 b: Ag < 0.445 and Ag < 0.368, respectively. We find that WASP-43 b and WASP-18 b are both consistent with low geometric albedos (Ag < 0.16) even though they lie at opposite ends of the hot Jupiter temperature range with equilibrium temperatures of ∼1400 K and ∼2500 K, respectively. We report self-consistent atmospheric models that explain broad-band observations for both planets from TESS, HST, Spitzer, and VLT/HAWK-I. We find that the data of both hot Jupiters can be explained by thermal emission alone and inefficient day–night energy redistribution. The data do not require optical scattering from clouds/hazes, consistent with the low geometric albedos observed.

Cavity-Modified Unimolecular Dissociation Reactions via Intramolecular Vibrational Energy Redistribution.

While the emerging field of vibrational polariton chemistry has the potential to overcome traditional limitations of synthetic chemistry, the underlying mechanism is not yet well understood. Here, we explore how the dynamics of unimolecular dissociation reactions that are rate-limited by intramolecular vibrational energy redistribution (IVR) can be modified inside an infrared optical cavity. We study a classical model of a bent triatomic molecule, where the two outer atoms are bound by anharmonic Morse potentials to the center atom coupled to a harmonic bending mode. We show that an optical cavity resonantly coupled to particular anharmonic vibrational modes can interfere with IVR and alter unimolecular dissociation reaction rates when the cavity mode acts as a reservoir for vibrational energy. These results lay the foundation for further theoretical work toward understanding the intriguing experimental results of vibrational polaritonic chemistry within the context of IVR.