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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 1,333 records · Page 74

Machine learning reveals key ion selectivity mechanisms in polymeric membranes with subnanometer pores

Designing single-species selective membranes for high-precision separations requires a fundamental understanding of the molecular interactions governing solute transport. Here, we comprehensively assess molecular-level features that influence the separation of 18 different anions by nanoporous cellulose acetate membranes. Our analysis identifies the limitations of bulk solvation characteristics to explain ion transport, highlighted by the poor correlation between hydration energy and the measured permselectivity (R 2 = 0.37). Entropy-enthalpy compensation, spanning 40 kilojoules per mole, leads to a free-energy barrier (ΔG‡) variation of only ~8 kilojoules per mole across all anions. We apply machine learning to elucidate descriptors for energetic barriers from a set of 126 collected features. Notably, electrostatic features account for 75% of the overall features used to describe ΔG‡, despite the relatively uncharged state of cellulose acetate. Our work presents an approach for studying ion transport across nanoporous membranes that could enable the design of ion-selective membranes.

36 MATERIALS SCIENCE↗

On the force exerted on a non-spherical asymmetric dust grain from homogeneous, stationary, isotropic, non-magnetized plasma

Whereas the conventional wisdom suggests that the force between non-magnetized homogeneous, stationary, isotropic plasma, and the dust grain is only possible for the case of relative plasma–grain velocity, it is shown that stationary non-spherical asymmetric dust grain immersed in stationary, non-magnetized, isotropic plasma can experience a force caused by the grain–plasma interactions. The component of the force due to scattering of plasma particles in the limit of infinite Debye length is considered analytically. Both the particle scattering and absorption force components are modeled numerically in the limits of infinite and finite Debye length using a newly developed 2D3V Aspherical Particle-in-Cell code. The code simulates interactions of dust grain of selected non-spherical asymmetric shape with plasmas using dust shape conforming coordinates. Here, the simulations confirm the existence of the force on non-spherical asymmetric grain in stationary non-magnetized plasma and show that the plasma screening effects can lead to reversal of the force direction.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Optically controllable magnetism in atomically thin semiconductors

We report evidence that ferromagnetic order in electrostatically doped, monolayer transition metal dichalcogenide (TMD) semiconductors can be stabilized and controlled at zero magnetic field by local optical pumping. We use circular dichroism (CD) in reflectivity from excitonic states as a spatially resolved probe of charge-carrier spin polarization. At electron densities $n_e$ ~ 10 12 cm -2 , a diffraction-limited, circularly polarized optical pump breaks symmetry between oppositely polarized magnetic states and stabilizes long-range magnetic order, with carrier polarization exceeding 80% over an 8 μm by 5 μm extent. In time-resolved measurements with pulsed optical excitation, we observe that magnetic interactions amplify the initial pump-induced spin polarization by more than an order of magnitude. The optical control of magnetism with local optical pumps will unlock advancements in spin and optical technologies and provides a versatile tool in the study of correlated phases in two-dimensional electron gases.

36 MATERIALS SCIENCE↗

Electronic Structure and Stability of [B 12 X 12 ] 2– (X = F–At): A Combined Photoelectron Spectroscopic and Theoretical Study

The relative stability and electron loss process of Multiply Charged Anions have been traditionally explained in terms of the classical Coulomb interaction between spatially separated charges. In this study we report the surprising properties of [B12X12]2-, X = F – At, that are counterintuitive compared to the prevailing classical description and justify their classification into a new class of MCAs. In this new class of MCAs, comprising of a “Boron core” surrounded by a “Halogen shell”, the sign of the total charge in these two regions changes along the halogen series from F to At. With the aid of photoelectron spectroscopy and electronic structure calculations we demonstrate that the behavior of these MCAs is largely determined by quantum effects rather than classical electrostatics. The second excess electron is always taken from the most positively charged region, viz. the “Boron core” for F – Br and the surrounding “Halogen shell” for I, At.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Elucidating molecular scale interactions underlying the freezing behavior of salt solutions in silica nanopores

Elucidating the influence of nanoscale confinement on the freezing behavior of salt solutions is of fundamental interest to environmental security and materials science and engineering. Specific structural information such as the coordination environment of ions in confined aqueous medium, effects on the extended hexagonal network of water molecules and their mutual non-bonding interactions in confinement are sparse in the literature along with the change in the dynamical characteristics of water in the presence of ions. To address these knowledge gaps, the current study is focused on investigating the influence of reduced dimensionality arising from nanoscale confinement on the structural evolution of salt solutions on freezing and the associated fluid–surface interactions. In this regard, operando wide-angle X-ray scattering (WAXS) measurements and classical molecular dynamics (MD) simulations are conducted with water and 0.5 M CaCl 2 , MgCl 2 and KCl solutions confined in 4 nm sized SBA-15 silica pores upon cooling from 300 K to 200 K. The freezing point of the salt solutions is depressed to 235 K which is about 10 K lower than that of confined water. The translational dynamics of confined salt solutions indicates shifts in the fragile-to-strong dynamical crossover to a lower temperature compared to pure water. The strong electrostatic attraction between the cations and the surrounding water molecules contributes to the freezing point depression in confined salt solutions. These insights unlock the molecular-scale basis and mechanisms underlying the freezing behavior of confined salt solutions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Optical Response of Periodic Arrays of Graphene Nanodisks

Doped graphene nanostructures are a promising platform for photonics due to their exceptionally strong and tunable plasmonic resonances. When placed in a periodic array configuration, the plasmons supported by the individual nanostructures interact with each other and, under the appropriate conditions, can give rise to a collective mode known as a lattice resonance. Here, for this study, we perform a comprehensive analysis of the response of periodic arrays of graphene nanodisks and identify the conditions under which the system is able to support lattice resonances. We find that the ratio between the period of the array and the wavelength of the plasmon completely determines the behavior of the system. As a consequence, strong lattice resonances are achieved for micron-size nanodisks in the terahertz regime. We develop a theoretical model valid beyond the electrostatic approximation and use it to derive closed analytical expressions for the strength, the wavelength, and the width of the optical resonance of the arrays. The theoretical framework developed in this work paves the way for facile design and discovery of emerging properties of periodic arrays of graphene nanostructures that could enable applications in photonics and plasmonics.

36 MATERIALS SCIENCE↗

Charged Particle Dynamics in the Lunar Environment

As the Artemis Program streams forward, organizations of scientists and engineers across the country have been coming together to solve the complex network of problems to once again achieve the milestone of successfully touching down on the moon. This project is no exception, and it has been an honor to work with the Electrostatics and Surface Physics Laboratory (ESPL), a lab within the Exploration Research and Technology Programs’ Spaceport Technologies Office (UB-G) located at the National Aeronautics and Space Administration at Kennedy Space Center (NASA KSC). The authors and their mentor James R. Phillips III3, in tandem with researchers from the Astrodynamics and Space Robotics Laboratory (ASRL) at the University of Central Florida (UCF), have been working on creating a state-of-the-art (SOA) granular gas dynamics model for particulate contamination prevention and mitigation purposes. In essence, the underlying objective for this project is to more accurately model the resulting electrodynamic interactions between lunar regolith grains with applications to dust mitigation and rocket engine plume surface interactions. To achieve this goal, the team has been expanding upon existing open source classical molecular dynamics code developed by Sandia National Laboratories (SNL). The following reports on the details of the problem at hand as well as the contributions that the authors have made towards resolution, including but not limited to the encoding of physical attributes and interactions for non-spherical polydisperse particle distributions within various bed geometries and preemptive data analysis implementations. Significant data analysis processes were utilized, and several original algorithms were created to perform critical evaluations, resulting in only a 0.006% error in discrepancy.

Annelisa B Esparza↗

Spacecraft Floating Potential Measurements for the Wind Spacecraft

Analysis of 8,804,545 electron velocity distribution functions, observed by the Wind spacecraft near 1 au between 2005 January 1 and 2022 January 1, was performed to determine the spacecraft floating potential, ∅ sc . Wind was designed to be electrostatically clean, which helps keep the magnitude of ∅ sc small (i.e., ∼5–9 eV for nearly all intervals) and the potential distribution more uniform. We observed spectral enhancements of ∅ sc at frequencies corresponding to the inverse synodic Carrington rotation period with at least three harmonics. The two-dimensional histogram of ∅ sc versus time also shows at least two strong peaks, with a potential third, much weaker peak. These peaks vary in time, with the intensity correlated with solar maximum. Thus, the spectral peaks and histogram peaks are likely due to macroscopic phenomena like coronal mass ejections (solar cycle dependence) and stream interaction regions (Carrington rotation dependence). The values of ∅ sc are summarized herein and the resulting data set is discussed.

Lynn B Wilson III↗

Biophysical studies and modelling indicate the binding preference of TAZ WW domain for LATS1 PPxY motif

Highlights: • TAZ WW domain preferentially binds to the second PPxY motif of LATS1. • Modelled structure of TAZ WW-PPxY2 is stable and adopts the typical WW fold. • Binding site residues, L143 and T150 reduce the binding affinity of TAZ WW domain. The Hippo tumor suppressor pathway is an important regulator of cell proliferation and apoptosis, and signal transduction occurs through phosphorylation of the effector protein TAZ by the serine/threonine kinase LATS1/2. Here, we report the biophysical and computational studies to characterize the interaction between TAZ and LATS1/2 through WW domain-PPxY motif binding. We show that the TAZ WW domain exhibits a binding preference for the second of the two PPxY motifs of LATS1 in vitro. We modelled the structure of the domain in complex with LATS1 PPxY2 peptide and, through molecular dynamics simulations, show that WW domain-PPxY2 complex is stable with some flexibility in the peptide region. Next, we predict and verify that L143 and T150 of the WW domain are important for TAZ binding with the PPxY2 peptide using mutational and isothermal titration calorimetric studies. Furthermore, we suggest that the electrostatic potential of charged residues within the binding pocket may influence the ligand affinity among otherwise highly similar WW domains.

60 APPLIED LIFE SCIENCES↗

Nanoparticle-Induced Disorder at Complex Liquid–Liquid Interfaces: Effects of Curvature and Compositional Synergy on Functional Surfaces

The self-assembly of surfactant monolayers at interfaces plays a sweeping role in tasks ranging from household cleaning to the regulation of the respiratory system. The synergy between different nanoscale species at an interface can yield assemblies with exceptional properties, which enhance or modulate their function. However, understanding the mechanisms underlying coassembly, as well as the effects of intermolecular interactions at an interface, remains an emerging and challenging field of study. Herein, we study the interactions of gold nanoparticles striped with hydrophobic and hydrophilic ligands with phospholipids at a liquid–liquid interface and the resulting surface-bound complexes. We show that these nanoparticles, which are themselves minimally surface active, have a direct concentration-dependent effect on the rapid reduction of tension for assembling phospholipids at the interface, implying molecular coassembly. Through the use of sum frequency generation vibrational spectroscopy, we reveal that nanoparticles impart structural disorder to the lipid molecular layers, which is related to the increased volumes that amphiphiles can sample at the curved surface of a particle. The results strongly suggest that hydrophobic and electrostatic attractions imparted by nanoparticle functionalization drive lipid–nanoparticle complex assembly at the interface, which synergistically aids lipid adsorption even when lipids and nanoparticles approach the interface from opposite phases. The use of tensiometric and spectroscopic analyses reveals a physical picture of the system at the nanoscale, allowing for a quantitative analysis of the intermolecular behavior that can be extended to other systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Results From Mars Show Electrostatic Charging of the Mars Pathfinder Sojourner Rover

Indirect evidence (dust accumulation) has been obtained indicating that the Mars Pathfinder rover, Sojourner, experienced electrostatic charging on Mars. Lander camera images of the Sojourner rover provide distinctive evidence of dust accumulation on rover wheels during traverses, turns, and crabbing maneuvers. The sol 22 (22nd Martian "day" after Pathfinder landed) end-of-day image clearly shows fine red dust concentrated around the wheel edges with additional accumulation in the wheel hubs. A sol 41 image of the rover near the rock "Wedge" (see the next image) shows a more uniform coating of dust on the wheel drive surfaces with accumulation in the hubs similar to that in the previous image. In the sol 41 image, note particularly the loss of black-white contrast on the Wheel Abrasion Experiment strips (center wheel). This loss of contrast was also seen when dust accumulated on test wheels in the laboratory. We believe that this accumulation occurred because the Martian surface dust consists of clay-sized particles, similar to those detected by Viking, which have become electrically charged. By adhering to the wheels, the charged dust carries a net nonzero charge to the rover, raising its electrical potential relative to its surroundings. Similar charging behavior was routinely observed in an experimental facility at the NASA Lewis Research Center, where a Sojourner wheel was driven in a simulated Martian surface environment. There, as the wheel moved and accumulated dust (see the following image), electrical potentials in excess of 100 V (relative to the chamber ground) were detected by a capacitively coupled electrostatic probe located 4 mm from the wheel surface. The measured wheel capacitance was approximately 80 picofarads (pF), and the calculated charge, 8 x 10(exp -9) coulombs (C). Voltage differences of 100 V and greater are believed sufficient to produce Paschen electrical discharge in the Martian atmosphere. With an accumulated net charge of 8 x 10(exp -9) C, and average arc time of 1 msec, arcs can also occur with estimated arc currents approaching 10 milliamperes (mA). Discharges of this magnitude could interfere with the operation of sensitive electrical or electronic elements and logic circuits. Sojourner rover wheel tested in laboratory before launch to Mars. Before launch, we believed that the dust would become triboelectrically charged as it was moved about and compacted by the rover wheels. In all cases observed in the laboratory, the test wheel charged positively, and the wheel tracks charged negatively. Dust samples removed from the laboratory wheel averaged a few ones to tens of micrometers in size (clay size). Coarser grains were left behind in the wheel track. On Mars, grain size estimates of 2 to 10 mm were derived for the Martian surface materials from the Viking Gas Exchange Experiment. These size estimates approximately match the laboratory samples. Our tentative conclusion for the Sojourner observations is that fine clay-sized particles acquired an electrostatic charge during rover traverses and adhered to the rover wheels, carrying electrical charge to the rover. Since the Sojourner rover carried no instruments to measure this mission's onboard electrical charge, confirmatory measurements from future rover missions on Mars are desirable so that the physical and electrical properties of the Martian surface dust can be characterized. Sojourner was protected by discharge points, and Faraday cages were placed around sensitive electronics. But larger systems than Sojourner are being contemplated for missions to the Martian surface in the foreseeable future. The design of such systems will require a detailed knowledge of how they will interact with their environment. Validated environmental interaction models and guidelines for the Martian surface must be developed so that design engineers can test new ideas prior to cutting hardware. These models and guidelines cannot be validated without actual flighata. Electrical charging of vehicles and, one day, astronauts moving across the Martian surface may have moderate to severe consequences if large potential differences develop. The observations from Sojourner point to just such a possibility. It is desirable to quantify these results. The various lander/rover missions being planned for the upcoming decade provide the means for doing so. They should, therefore, carry instruments that will not only measure vehicle charging but characterize all the natural and induced electrical phenomena occurring in the environment and assess their impact on future missions.

Kolecki, Joseph C.↗

Electrical Manipulation of Quantum Coherence in a Two-Level Molecular System

We report the manipulation of ultrafast quantum coherence of a two-level single hydrogen molecular system by employing static electric field from the sample bias in a femtosecond terahertz scanning tunneling microscope. A H 2 molecule adsorbed on the polar Cu 2⁢ N surface develops an electric dipole and exhibits a giant Stark effect. An avoided crossing of the quantum state energy levels is derived from the resonant frequency of the single H 2 two levels in a double-well potential. The dephasing time of the initial wave packet can also be changed by applying the electric field. The electrical manipulation for different tunneling gaps in three dimensions allows quantification of the surface electrostatic fields at the atomic scale. Further, our work demonstrated the potential application of molecules as controllable two-level molecular systems.

36 MATERIALS SCIENCE↗

Large-Amplitude Electrostatic Waves Observed at a Supercritical Interplanetary Shock

We present the first observations at an interplanetary shock of large-amplitude (> 100 mV/m pk-pk) solitary waves and large-amplitude (approx.30 mV/m pk-pk) waves exhibiting characteristics consistent with electron Bernstein waves. The Bernstein-like waves show enhanced power at integer and half-integer harmonics of the cyclotron frequency with a broadened power spectrum at higher frequencies, consistent with the electron cyclotron drift instability. The Bernstein-like waves are obliquely polarized with respect to the magnetic field but parallel to the shock normal direction. Strong particle heating is observed in both the electrons and ions. The observed heating and waveforms are likely due to instabilities driven by the free energy provided by reflected ions at this supercritical interplanetary shock. These results offer new insights into collisionless shock dissipation and wave-particle interactions in the solar wind.

Wilson, L. B., III↗

Elucidating Electric Field-Induced Rate Promotion of Brønsted Acid-Catalyzed Alcohol Dehydration

Applied potentials have been demonstrated as a powerful tool to promote heterogeneous Brønsted acid catalysis by orders of magnitude, leveraging interfacial electric fields to stabilize protonated intermediates. However, the use of flat two-dimensional electrodes with inherently low active site densities limits the application of conventional thermochemical characterization techniques that can probe the nature of catalytic active sites. Here, we use kinetic analyses with an electrostatics-based model to elucidate the intricacies of potential-induced rate promotion, employing liquid-phase dehydration of 1-methylcyclopentanol catalyzed by carboxylic acid groups on carbon nanotubes as a probe system. By using a basket electrode to directly polarize catalyst powder, we demonstrate that thermocatalytic reaction rates can be promoted by 100,000-fold, exhibiting a log–linear dependence on applied potential with rate-potential scalings as high as 125 ± 4 mV per 10-fold rate increase. In agreement with model predictions, we show that lower ionic strengths attenuate potential sensitivity, resulting from a weakening of the interfacial electric field that interacts with the acidic proton. Furthermore, we experimentally confirm the model-predicted “isokinetic potential” (at ∼0.6 V vs Ag/AgCl)─the potential at which all rate scaling lines at various ionic strengths intersect, making the rate independent of ionic strength. Base titrations reveal that only ∼8% of the carboxylic acid sites are catalytically active, yet these same active sites are operational at the highest and lowest potentials. Collectively, our results provide a key methodology for modeling catalytic effects of electric fields, quantifying active sites under applied potential, and demonstrating fundamental principles of electric field-induced rate promotion.

Catalysts↗

Cyclotron side band emissions from magnetospheric electrons

Very low frequency emissions with subharmonic cyclotron frequency from magnetospheric electrons were detected by the S(3)-A satellite (Explorer 45) whose orbit is close to the magnetic equatorial plane where the wave-particle interaction is most efficient. These emissions were observed during the main phase of a geomagnetic storm in the nightside of the magnetosphere outside of the plasmasphere. During the event of these side-band emissions, the pitch angle distributions of high energy electrons (greater than 50 keV) and of energetic protons (greater than 100 keV) showed remarkable changes with time, whereas those of low energy electrons and protons remained approximately isotropic. In this type of event, emissions consist essentially of two bands, the one below the equatorial electron gyrofrequency, and the other above. The emissions below are whistler mode, and the emissions above are electrostatic mode.

Maeda, K.↗

Approximate theory of large-amplitude wave propagation

An orbit perturbation procedure is applied to the description of monochromatic, large-amplitude, electrostatic plasma wave propagation. In the lowest-order approximation, untrapped electrons are assumed to follow constant-velocity orbits and trapped electrons are assumed to execute simple harmonic motion. The deviations of these orbits from the actual orbits are regarded as perturbations. The nonlinear damping rate and frequency shift are then obtained in terms of simple functions. The results are in good agreement with previous less approximate analyses. A significant feature of the analysis is that it treats a single wave by techniques previously applied to turbulent spectra. The analysis can consequently be extended to the case of a large-amplitude wave interacting with a lower-amplitude spectrum of waves.

Kim, H.↗

Generation, saturation, and convection of electrostatic waves in Jupiter's shock foot

In this paper, a model is developed for the analysis of the electrostatic waves produced in the shock foot at Jupiter. It is shown that an ion beam instability involving the ions reflected at the shock ramp and the incoming solar-wind electrons produces waves at the observed frequencies and that saturation via orbit diffusion limits the waves to amplitudes near to what is observed. Results from a two-dimensional model of the reflected beam in the foot indicate that the waves propagate against the solar wind away from the shock ramp and are amplified up to their saturation amplitudes. The saturation results, combined with the electron temperature profile due to wave-particle interactions predicted by quasi-linear theory, reproduce a wave amplitude profile for the shock foot that is in reasonable agreement with the observations.

Moses, S. L.↗

Probing the electronic structure of graphene near and far from the Fermi level via planar tunneling spectroscopy

Scanning tunneling spectroscopy (STS) has yielded significant insight into the electronic structure of graphene and other two-dimensional (2D) materials. STS directly measures a fundamental and directly calculable quantity: single particle density of states (SPDOS). Due to experimental setup limitations, however, STS has been unable to explore 2D materials in ultrahigh magnetic fields where electron-electron interactions can drastically change the SPDOS. Recent developments in the assembly of heterostructures composed of graphene and hexagonal boron nitride have enabled a device-based alternative to potentially overcome these roadblocks. Thus far, however, these nascent efforts are incomplete in analyzing and understanding tunneling spectra and have yet to explore graphene at high magnetic fields. Here, we report an experiment at magnetic fields up to 18 T, which uses graphene tunneling field effect transistors (TFETs) to establish a clear benchmark for the measurement and analysis of graphene planar tunneling spectroscopy. We acquire gate tunable tunneling spectra of graphene and then use these data and electrostatic arguments to develop a systematic analysis scheme. This analysis reveals that TFET devices directly probe electronic structure features near and far from the Fermi level. In particular, our study yields identification of the Dirac point and numerous Landau levels as they fill and empty with charge via the application of a gate voltage. Our work demonstrates that TFET devices are a viable platform for directly probing the electronic structure of graphene and other 2D materials in high magnetic fields, where exotic electronic states emerge.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗