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At least 793 records · Page 44

Counter-thermal flow of holes in high-mobility LaNiO 3 thin films

Measurements of electronic structure and theoretical models indicate that the Fermi surface of LaNiO 3 (LNO) is predominantly holelike, with a small electron pocket. However, measurements of the Hall and Seebeck effects yield nominally opposite signs for the dominant charge carrier type, making charge transport in LNO puzzling. Here, we combine measurements of the Hall, Seebeck, and Nernst coefficients in high-mobility epitaxial LNO thin films, and resolve this puzzle by demonstrating that the negative Seebeck coefficient is generated by the diffusion of holes from cold to hot regions of LNO. Here, we further examine this counter-thermal flow of holes by measuring the evolution of the Nernst coefficient from the diffusive to the ballistic regime, where the suppression of energy-dependent scattering leads to a reversal of the flow of holes.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

A Highly Hydroxide Conductive, Chemically Stable Anion Exchange Membrane, Poly(2,6 dimethyl 1,4 phenylene oxide)- b -Poly(vinyl benzyl trimethyl ammonium), for Electrochemical Applications

A chemically stable copolymer [poly(2,6 dimethyl 1,4 phenylene oxide)-b-poly(vinyl benzyl trimethyl ammonium)] with two ion exchange capacities, 3.2 and 2.9 meq g-1, was prepared as anion exchange membranes (AEM-3.2 and AEM-2.9). These materials showed high OH- conductivities of 138 mS.cm-1 and 106 mS.cm-1, for AEM-3.2 and AEM-2.9 respectively, at 60°C, and 95% RH. The OH- conductivity = 45 mS.cm-1 for AEM-3.2 at 60% RH and 60°C in the absence of CO2. Amongst the ions studied, only OH- is fully dissociated at high RH. The lower Ea = 10–13 kJ.mol-1 for OH- compared to F- ~ 20 kJ.mol-1 in conductivity measurements, and of H2O from self-diffusion coefficients suggests the presence of a Grotthuss hopping transport mechanism in OH- transport. PGSE-NMR of H2O and F- show that the membranes have low tortuosity, 1.8 and 1.2, and high water self-diffusion coefficients, 0.66 and 0.26 × 10-5 cm2.s-1, for AEM-3.2 and AEM-2.9 respectively. SAXS and TEM show that the membrane has several different sized water environments, ca. 62 nm, 20 nm, and 3.5 nm. The low water uptake, λ = 9–12, reduced swelling, and high OH- conductivity, with no chemical degradation over two weeks, suggests that the membrane is a strong candidate for electrochemical applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

The Cosmic Neutrino Background is within Reach of Future Neutrino Telescopes

The cosmic neutrino background (C$ν$B) can be boosted to high energies due to scatterings with energetic cosmic rays (CRs) across cosmological scales. Previous calculations focused on neutral current incoherent and coherent elastic scatterings of cosmic-ray protons off relic neutrinos. However, charged current interactions and deep inelastic scatterings are also expected to occur, which enhances the boosted relic neutrino fluxes on Earth. Here, we compute the \textit{total} diffuse boosted cosmic neutrino background (DBC$ν$B) arising from CRs at all redshifts in the Universe, accounting for neutral current and charged current elastic and deep inelastic scatterings. We find that IceCube already places an upper limit on the cosmic neutrino background overdensity in cosmological scales of ~$\mathcal{O}(100-1000)$ at $E_ν=10^{10}$ GeV, for a lightest neutrino mass of $m_ν \gtrsim 0.1$ eV. We further show that IceCube-Gen2 could test $\mathcal{O}(1-10)$ C$ν$B overdensities, and the combination of $10$ future neutrino telescopes with similar sensitivity would allow us to test the $Λ$CDM expected C$ν$B density for a lightest neutrino mass compatible with the KATRIN bound.

Herrera, Gonzalo [MIT, MKI; Harvard U.; Virginia T↗

Resonance zones and quasi-linear diffusion coefficients for radiation belt energetic electron interaction with oblique chorus waves in the Dungey magnetosphere

The resonance regions for resonant interactions of radiation belt electrons with obliquely propagating whistler-mode chorus waves are investigated in detail in the Dungey magnetic fields that are parameterized by the intensity of uniform southward interplanetary magnetic field (IMF) Bz or, equivalently, by the values of D=(M/B{sub z,0}){sup 1/3} (where M is the magnetic moment of the dipole and B{sub z,0} is the uniform southward IMF normal to the dipole's equatorial plane). Adoption of background magnetic field model can considerably modify the determination of resonance regions. Compared to the results for the case of D = 50 (very close to the dipole field), the latitudinal coverage of resonance regions for 200 keV electrons interacting with chorus waves tends to become narrower for smaller D-values, regardless of equatorial pitch angle, resonance harmonics, and wave normal angle. In contrast, resonance regions for 1 MeV electrons tend to have very similar spatial lengths along the field line for various Dungey magnetic field models but cover different magnetic field intervals, indicative of a strong dependence on electron energy. For any given magnetic field line, the resonance regions where chorus-electron resonant interactions can take place rely closely on equatorial pitch angle, resonance harmonics, and kinetic energy. The resonance regions tend to cover broader latitudinal ranges for smaller equatorial pitch angles, higher resonance harmonics, and lower electron energies, consistent with the results in Ni and Summers [Phys. Plasmas 17, 042902, 042903 (2010)]. Calculations of quasi-linear bounce-averaged diffusion coefficients for radiation belt electrons due to nightside chorus waves indicate that the resultant scattering rates differ from using different Dungey magnetic field models, demonstrating a strong dependence of wave-induced electron scattering effect on the adoption of magnetic field model. Our results suggest that resonant wave-particle interaction processes should be implemented into a sophisticated, accurate global magnetic field model to pursue comprehensive and complete models of radiation belt electron dynamics.

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗

Defect-Driven Oxide Transformations and the Electrochemical Interphase

The redox reaction pathway is crucial to the sustainable production of the fuels and chemicals required for a carbon-neutral society. Our society is becoming increasingly dependent on devices using batteries and electrolyzers, all of which rely on a series of redox reactions. The overall properties of oxide materials make them very well suited for such electrochemical and catalytic applications due to their associated cationic redox properties and the static site-adsorbate interactions. As these technologies have matured, it has become apparent that defect-driven redox reactions, defect-coupled diffusion, and structural transformations that are both time- and rate-dependent are also critical materials processes. This change in focus, considering not only redox properties but also more complex, dynamic behaviors, represents a new research frontier in the molecular sciences as they are strongly linked to device operation and degradation and lie at the heart of various phenomena that take place at electrochemical interfaces. Fundamental studies of the structural, electronic, and chemical transformation mechanisms are key to the advancement of materials and technological innovations that could be implemented in various electrochemical systems. In this Account, we focus on recent studies and advances in characterizing and understanding the dynamic redox evolution and structural transformations that take place in model perovskites and layered oxides under reactive conditions and correlate them with degradation mechanisms and operations in electrolyzers and batteries. We show that the dynamic evolution of oxygen vacancies and cationic migration in the surface or bulk occurs at the solid-liquid interface, using a combination of different synchrotron-based Xray spectroscopies and scattering probes. Detailed redox-structure-reactivity correlation studies show how defects and diffusion processes can be tailored to drive various physical and chemical transformations in electrolyzers and batteries. We also highlight a strong correlation between oxygen redox reactivity and structural reorganization in both model thin films and particles, helping to bridge the gap between fundamental studies of the reaction mechanism and device applications. Finally, on the basis of these findings, we discuss strategies to probe and tune the redox reactivity and structural stability of the redox-active oxide interphase toward devising efficient pathways for energy and chemical harvesting.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Dynamics of CTAB in hybrid CTAB-hydroxyapatite system

Synthetic hydroxyapatite (HAp) is an important material in biomedical engineering due to its excellent biocompatibility and bioactivity. Here we report dynamics of cetyltrimethylammonium bromide (CTAB) in HAp composite, prepared by co-precipitation method, as studied by quasielastic neutron scattering (QENS) technique. It is found that the observed dynamics involved two time scales associated with fast torsional motion and segmental motion of the CTAB monomers. In addition to segmental motion of the hydrogen atoms, few undergo torsional motion as well. Torsional dynamics was described by a 2-fold jump diffusion model. The segmental dynamics of CTAB has been described assumimg the hydrogen atoms undergoing diffusion inside a sphere of confined volume. While the diffusivity is found to increase with temperature, the spherical volumes within which the hydrogen atoms are undergoing diffusion remain almost unchanged.

36 MATERIALS SCIENCE↗

Atomic dynamics in molten AlCu alloys of different compositions and at different temperatures by cold neutron scattering

The atomic motions in molten Al1-xCux (x=0.10, 0.171 and 0.25) around the eutectic composition (x=0.171) were studied by cold neutron inelastic scattering at three different temperatures (973 K, 1173 K and 1373 K). An alloy of eutectic composition containing the 63Cu isotope was also studied. Self-diffusion coefficients for the Cu ions were determined from the width of quasielastic peaks and were found to decrease slightly with increasing Cu concentration. Longitudinal current correlation functions Jl(Q,E) exhibit at all temperatures and at all compositions a shoulder at energies below 10 meV and one main maximum at higher energies. These features can be interpreted in terms of excitations of acoustic and optic nature. The shape of Jl(Q,E) is sensitive to composition, being considerably more structured for larger Cu content. This can be coupled to the existence of a prepeak in the measured zeroth moment of dynamic scattering function indicating an increased chemical ordering with increasing Cu concentration for all temperatures. Indications for an existence of a liquid–liquid phase transition are presented.

36 MATERIALS SCIENCE↗

EARLY-TIME VELOCITY AUTOCORRELATION FOR CHARGED PARTICLES DIFFUSION AND DRIFT IN STATIC MAGNETIC TURBULENCE

Using test-particle simulations, we investigate the temporal dependence of the two-point velocity correlation function for charged particles scattering in a time-independent spatially fluctuating magnetic field derived from a three-dimensional isotropic turbulence power spectrum. Such a correlation function allowed us to compute the spatial coefficients of diffusion both parallel and perpendicular to the average magnetic field. Our simulations confirm the dependence of the perpendicular diffusion coefficient on turbulence energy density and particle energy predicted previously by a model for early-time charged particle transport. Using the computed diffusion coefficients, we exploit the particle velocity autocorrelation to investigate the timescale over which the particles 'decorrelate' from the solution to the unperturbed equation of motion. Decorrelation timescales are evaluated for parallel and perpendicular motions, including the drift of the particles from the local magnetic field line. The regimes of strong and weak magnetic turbulence are compared for various values of the ratio of the particle gyroradius to the correlation length of the magnetic turbulence. Our simulation parameters can be applied to energetic particles in the interplanetary space, cosmic rays at the supernova shocks, and cosmic-rays transport in the intergalactic medium.

79 ASTRONOMY AND ASTROPHYSICS↗

Following the Morphological Disruption by an Electrolyte of a Buried Interface

A challenge of broad interest in both materials science and biology is the study of interfaces that are buried within a structure, particularly multilayer structures. Despite the enormous costs of corrosion and many decades of corrosion research, details of the mechanisms of various sorts of corrosion are still not clear, in part due to the difficulty in interrogating the interface between the corroding metal and an organic coating, which is typically used to mitigate corrosion. Generally, the performance of such coatings is evaluated by visual inspection after exposure or by modeling impedance data, which is a process not straightforwardly connected to physical interface structures. "Rocking-curve" X-ray scattering measurements provide a means of probing such interfaces due to the ability of X-rays to penetrate materials. Here, variations in the morphology of an interface between a protective coating and a metal substrate due to exposure to an electrolyte are derived from analysis of rocking-curve data in conjunction with atomic force microscopy imaging of the outer coating surface. The interfaces of cross-linked epoxy coatings with aluminum are irreversibly changed after 12 h of contact between the electrolyte solution and the face of the coating. The character of this change varies with the molecule used to cross-link the coating. Since X-ray off-specular scattering is sensitive to changes on the nanometer scale, it is also able to register interface degradation on time scales shorter than those probed by many other techniques, potentially expediting the evaluation of coatings for protection against degradation of the interface.

36 MATERIALS SCIENCE↗

A CAREFULLY CHARACTERIZED AND TRACKED TRANS-NEPTUNIAN SURVEY: THE SIZE DISTRIBUTION OF THE PLUTINOS AND THE NUMBER OF NEPTUNIAN TROJANS

The trans-Neptunian objects (TNOs) preserve evidence of planet building processes in their orbital and size distributions. While all populations show steep size distributions for large objects, a relative deficit of Neptunian trojans and scattering objects with diameters of D < 100 km has been detected. We investigated this deficit with a 32 square degree survey, in which we detected 77 TNOs that are brighter than a limiting r-band magnitude of 24.6. Our plutino sample (18 objects in 3:2 mean-motion resonance with Neptune) shows a deficit of D < 100 km objects, rejecting a single power-law size distribution at >99% confidence. Combining our survey with the Canada–France Ecliptic Plane Survey, we perform a detailed analysis of the allowable parameters for the plutino size distribution, including knees and divots. We surmise the existence of 9000 ± 3000 plutinos with an absolute magnitude of H {sub r} ≤ 8.66 and 37000{sub −10000}{sup +12000} with H {sub r} ≤ 10.0 (95% confidence). Our survey also discovered one temporary Uranian trojan, one temporary Neptunian trojan, and one stable Neptunian trojan, for which we estimate populations of 110{sub −100}{sup +500}, 210{sub −200}{sup +900}, and 150{sub −140}{sup +600} with H {sub r} ≤ 10.0, respectively. All three populations are thus less numerous than the main belt asteroids (592 asteroids with H {sub r} ≤ 10.0). With such population sizes, the temporary Neptunian trojans cannot be previously stable trojans diffusing out of the resonance now; they must be recently captured Centaurs or scattering objects. As the bias against the detection of objects grows with larger semimajor axes, our discovery of three 3:1 resonators and one 4:1 resonator adds to the growing evidence that the high-order resonances are far more populated than is typically predicted.

79 ASTRONOMY AND ASTROPHYSICS↗

NUMERICAL INTEGRAL OF RESISTANCE COEFFICIENTS IN DIFFUSION

The resistance coefficients in the screened Coulomb potential of stellar plasma are evaluated to high accuracy. I have analyzed the possible singularities in the integral of scattering angle. There are possible singularities in the case of an attractive potential. This may result in a problem for the numerical integral. In order to avoid the problem, I have used a proper scheme, e.g., splitting into many subintervals where the width of each subinterval is determined by the variation of the integrand, to calculate the scattering angle. The collision integrals are calculated by using Romberg’s method, therefore the accuracy is high (i.e., ∼10{sup −12}). The results of collision integrals and their derivatives for −7 ≤ ψ ≤ 5 are listed. By using Hermite polynomial interpolation from those data, the collision integrals can be obtained with an accuracy of 10{sup −10}. For very weakly coupled plasma ( ψ ≥ 4.5), analytical fittings for collision integrals are available with an accuracy of 10{sup −11}. I have compared the final results of resistance coefficients with other works and found that, for a repulsive potential, the results are basically the same as others’; for an attractive potential, the results in cases of intermediate and strong coupling show significant differences. The resulting resistance coefficients are tested in the solar model. Comparing with the widely used models of Cox et al. and Thoul et al., the resistance coefficients in the screened Coulomb potential lead to a slightly weaker effect in the solar model, which is contrary to the expectation of attempts to solve the solar abundance problem.

79 ASTRONOMY AND ASTROPHYSICS↗

Water sub-diffusion in membranes for fuel cells

We investigate the dynamics of water confined in soft ionic nano-assemblies, an issue critical for a general understanding of the multi-scale structure-function interplay in advanced materials. We focus in particular on hydrated perfluoro-sulfonic acid compounds employed as electrolytes in fuel cells. These materials form phase-separated morphologies that show outstanding proton-conducting properties, directly related to the state and dynamics of the absorbed water. We have quantified water motion and ion transport by combining Quasi Elastic Neutron Scattering, Pulsed Field Gradient Nuclear Magnetic Resonance, and Molecular Dynamics computer simulation. Effective water and ion diffusion coefficients have been determined together with their variation upon hydration at the relevant atomic, nanoscopic and macroscopic scales, providing a complete picture of transport. We demonstrate that confinement at the nanoscale and direct interaction with the charged interfaces produce anomalous sub-diffusion, due to a heterogeneous space-dependent dynamics within the ionic nanochannels. This is irrespective of the details of the chemistry of the hydrophobic confining matrix, confirming the statistical significance of our conclusions. Our findings turn out to indicate interesting connections and possibilities of crossfertilization with other domains, including biophysics. They also establish fruitful correspondences with advanced topics in statistical mechanics, resulting in new possibilities for the analysis of Neutron scattering data.

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Study of Protein Dynamics via Neutron Spin Echo Spectroscopy

Most human body proteins' activity and functionality are related to configurational changes of entire subdomains within the protein crystal structure. The crystal structures build the basis for any calculation that describes the structure or dynamics of a protein, most of the time with strong geometrical restrictions. However, these restrictions from the crystal structure are not present in the solution. The structure of the proteins in the solution may differ from the crystal due to rearrangements of loops or subdomains on the pico to nanosecond time scale (i.e., the internal protein dynamics time regime). This study describes how slow motions on timescales of several tens of nanoseconds can be accessed using neutron scattering. In particular, the dynamical characterization of two major human proteins, an intrinsically disordered protein that lacks a well-defined secondary structure and a classical antibody protein, is addressed by neutron spin echo spectroscopy (NSE) combined with a wide range of laboratory characterization methods. Further insights into protein domain dynamics were achieved using mathematical modeling to describe the experimental neutron data and determine the crossover between combined diffusive and internal protein motions. The extraction of the internal dynamic contribution to the intermediate scattering function obtained from NSE, including the timescale of the various movements, allows further vision into the mechanical properties of single proteins and the softness of proteins in their nearly natural environment in the crowded protein solution.

59 BASIC BIOLOGICAL SCIENCES↗

Extended linear-in- T resistivity due to electron-phason scattering in moiré superlattices

Due to its incommensurate nature, moiré superlattices host not only acoustic phonons but also another type of soft collective modes called phasons. Here, we investigate the impact of electron-phason scattering on the transport properties of moiré systems. We show that the resistivity can scale linearly with temperature down to temperatures much lower than the Bloch-Grüneisen scale defined by electron kinematics on the Fermi surface. This result stems from the friction between layers, which transfers phason spectral weight to a broad diffusive low-energy peak in the mechanical response of the system. As a result, phason scattering becomes a very efficient channel for entropy production at low temperatures. We also consider the contributions of phasons to thermodynamic properties at low temperatures and find a “metallic-like” linear-in-T behavior for the specific heat, despite the fact that this behavior is due to mechanical and not electronic degrees of freedom. Finally, we discuss the implications of this finding to reports of linear-in-T resistivity in the phase diagram of twisted bilayer graphene.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Analytical model of diffuse reflectance spectrum of skin tissue

We have derived simple analytical expressions that enable highly accurate calculation of diffusely reflected light signals of skin in the spectral range from 450 to 800 nm at a distance from the region of delivery of exciting radiation. The expressions, taking into account the dependence of the detected signals on the refractive index, transport scattering coefficient, absorption coefficient and anisotropy factor of the medium, have been obtained in the approximation of a two-layer medium model (epidermis and dermis) for the same parameters of light scattering but different absorption coefficients of layers. Numerical experiments on the retrieval of the skin biophysical parameters from the diffuse reflectance spectra simulated by the Monte Carlo method show that commercially available fibre-optic spectrophotometers with a fixed distance between the radiation source and detector can reliably determine the concentration of bilirubin, oxy- and deoxyhaemoglobin in the dermis tissues and the tissue structure parameter characterising the size of its effective scatterers. We present the examples of quantitative analysis of the experimental data, confirming the correctness of estimates of biophysical parameters of skin using the obtained analytical expressions. (biophotonics)

72 PHYSICS OF ELEMENTARY PARTICLES AND FIELDS↗

Anion exchange membranes composed of a poly(2,6-dimethyl-1,4-phenylene oxide) random copolymer functionalized with a bulky phosphonium cation

A random copolymer, tris(2,4,6-trimethoxyphenyl) phosphonium functionalized poly(2,6-dimethyl-1,4-phenylene oxide) (PPO-TPQP) was cast from three different solvents: dimethyl sulfoxide (DMSO), ethyl lactate, or a 41:59 vol% mixture of DMSO and ethyl lactate. Solvents were selected via analysis of the Hansen solubility parameters to vary the phase separation of the polymer in the films. An optimized mixture of DMSO and ethyl lactate chosen for film fabrication and this film was contrasted with films cast from the neat constituent solvents. Atomic force microscopy identified domains from nanometer to tens of nanometer sizes, while the light microscopy showed features on the order of micron. SAXS revealed a cation scattering peak with a d-spacing from 7 to 15 A. Trends in conductivity and water diffusion for the membranes vary depending on the solvent from which they are cast. The mixed solvent cast membrane shows a linear Arrhenius behavior indicating fully dissociated cationic/anionic groups, and has the highest bromide conductivity of 3 mS/cm at 95% RH, 90 degrees C. The ethyl lactate cast membrane shows a linear Arrhenius relation in conductivity, but a Vogel-Tamman-Fulcher behavior in its water self-diffusion. While water increases bromide dissociation, water and bromide transport in these films seems to be decoupled. This is particularly true for the film cast from ethyl lactate.

Liu, Ye↗

Relativistic electron precipitation events driven by electromagnetic ion-cyclotron waves

We adopt a canonical approach to describe the stochastic motion of relativistic belt electrons and their scattering into the loss cone by nonlinear EMIC waves. The estimated rate of scattering is sufficient to account for the rate and intensity of bursty electron precipitation. This interaction is shown to result in particle scattering into the loss cone, forming ∼10 s microbursts of precipitating electrons. These dynamics can account for the statistical correlations between processes of energization, pitch angle scattering, and relativistic electron precipitation events, that are manifested on large temporal scales of the order of the diffusion time ∼tens of minutes.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Elastic scattering by hot electrons and apparent lifetime of longitudinal optical phonons in gallium nitride

Longitudinal optical (LO) phonons in GaN generated in the channel of high electron mobility transistors (HEMT) are shown to undergo nearly elastic scattering via collisions with hot electrons. The net result of these collisions is the diffusion of LO phonons in the Brillouin zone causing reduction of phonon and electron temperatures. This previously unexplored diffusion mechanism explicates how an increase in electron density causes reduction of the apparent lifetime of LO phonons, obtained from the time resolved Raman studies and microwave noise measurements, while the actual decay rate of the LO phonons remains unaffected by the carrier density. Therefore, the saturation velocity in GaN HEMT steadily declines with increased carrier density, in a qualitative agreement with experimental results.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗