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At least 1,009 records · Page 56

Scanning Probe Microscopy in the Information Age

Scanning probe microscopy (SPM) has brought scientific exploration, visualization, and control to nanoscale. A plethora of measurement approaches and techniques devised around SPM enabled probing structure and functionalities crucial for virtually all areas of science. While high-resolution electron microscopy techniques preceded scanning probes, SPM effectively opened the door to probing the structure–property relationship on length scales spanning 100s of micrometers down to a single atom. As the complexity of the material systems and the scientific questions increased, so too did the SPM techniques. Substantial efforts have been dedicated toward the development of better instrumentation platforms, probes, and novel spectroscopic measurements; however, many opportunities related to data processing and acquisition in SPM are just being realized now. This chapter will describe the recent progress in data-driven SPM by giving a broad overview of the field, the foundation of the scanning tunneling microscope (STM) and the atomic force microscope (AFM), as well as a description behind the operating principles and dynamic modes. A comprehensive overview of the multi-frequency techniques, Band excitation, and general acquisition mode SPM is given, setting the context for the application of big data, machine learning, and artificial intelligence in the field of dynamic SPM.

Collins, Liam↗

One-dimensionality signature in optical conductivity of heavy-fermion CeIr 3 B 2

In low dimensions, the combined effects of interactions and quantum fluctuations can lead to dramatically new physics distinct from that existing in higher dimensions. Here, we investigate the electronic and optical properties of CeIr 3 ⁢B 2 , a quasione-dimensional (1D) Kondo lattice system, using ab initio calculations. The Ce atoms in the hexagonal crystal structure form 1D chains along the c axis, with extremely short Ce-Ce distances. The quasi-1D nature of the crystal structure is well reflected in its electronic structure. Extremely flat bands emerge within the ab plane of the Brillouin zone, yielding sharp optical transitions in the corresponding optical conductivity. Further, our calculations indicate that these prominent peaks in the optical conductivity provide a clear signature of quasi-1D heavy fermion systems.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Interplay Between Metastability and Mechanically Induced Structural Instability in CsPbBr 3 Photovoltaic Perovskite

An atomic-level understanding of the underlying structural metastability is still absent in halide perovskite photovoltaic systems. Focusing on the model material CsPbBr 3 , the impact of mechanically induced atomic structure alteration is elucidated through structural modeling and X-ray diffraction measurements. Sudden Cs–Br bond breaking drives the system metastability, where the first-order transition arises from cation-halide bond strain relief by severing the corner connectivity of the PbBr 6 units. The pressure–volume and entropy terms govern the Gibbs free-energy landscape in halide perovskites. In conclusion, metastability is revealed as a critical factor limiting the performance of lead halide perovskites under extreme but natural environments.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Permutationally Invariant Polynomial Expansions with Unrestricted Complexity

A general strategy is presented for constructing and validating permutationally invariant polynomial (PIP) expansions for chemical systems of any stoichiometry. Demonstrations are made for three categories of gas-phase dynamics and kinetics: collisional energy-transfer trajectories for predicting pressure-dependent kinetics, three-body collisions for describing transient van der Waals adducts relevant to atmospheric chemistry, and nonthermal reactivity via quasiclassical trajectories. In total, 30 systems are considered with up to 15 atoms and 39 degrees of freedom. Permutational invariance is enforced in PIP expansions with as many as 13 million terms and 13 permutationally distinct atom types by taking advantage of petascale computational resources. The quality of the PIP expansions is demonstrated through the systematic convergence of in-sample and out-of-sample errors with respect to both the number of training data and the order of the expansion, and these errors are shown to predict errors in the dynamics for both reactive and nonreactive applications. Here, the parallelized code distributed as part of this work enables the automation of PIP generation for complex systems with multiple channels and flexible user-defined symmetry constraints and for automatically removing unphysical unconnected terms from the basis set expansions, all of which are required for simulating complex reactive systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Two-dimensional quantum gas with real time control of complete Hamiltonian (Final Report)

We developed a novel quantum platform with the complete capability to control individual atoms and their mutual interactions in real time. Ultracold atoms are employed since they have the lowest temperature and decoherence. This system is the ultimate dream of quantum physicists where the Hamiltonian of every single atom, including its kinetic energy, potential energy, and interactions, can be independently programmed in real time. We also initiated a new theoretical collaboration to explore its full potential.

74 ATOMIC AND MOLECULAR PHYSICS↗

Atomization of liquid fuels. Part I

In the present treatise we will consider chiefly the problem of solid injection in comparison with air injection. On leaving the valve or nozzle through one or more small openings, the fuel is split up into innumerable fine drops, which penetrate the combustion chamber in divergent directions in the form of a conical jet. The efficiency of this jet is judged from the following three viewpoints: 1) with respect to the fineness of atomization; 2) with respect to the direction or distribution of sprayed particles; 3) with respect to the penetration of the particles.

FUELS - TESTS↗

A physics informed model for the prediction of surface energies and the shape of metal particles

Surface energies of metal-based systems are important for determining the Wulff-constructed shapes of metal nanoparticles and understanding the stability. We have developed a physics informed method to predict the total energy of metal-based systems across a wide range of configurations. Our method has been tested against density functional theory (DFT) calculations for late transition metals. This method enables on-the-fly surface energy predictions based on the fundamental of materials property and allows for the Wulff construction of metal particles for a random number of elemental atoms and without the need for DFT calculations. By making a division between atoms in the different layers of the model system, we can improve the accuracy of the model, suggesting a dissimilarity between the electronic structure due to an alternating compression and expansion of atomic layers. We find that our model accurately and effectively provides valuable insights into the distribution and stability of nanoparticles.

Mandal, Shyama Charan (ORCID:0000000245882874)↗

A simple data-driven level finding method of many-electron atoms and heavy nuclei based on statistical outlier detection

Here, we report a simple and pure data-driven method to find new energy levels of quantum many-body systems only from observed line wavelengths. In our method, all the possible combinations are computed from known energy levels and wavelengths of unidentified lines. As each excited state exhibits many transition lines to different lower levels, the true levels should be reconstructed coincidentally from many level-line combinations, while the wrong combinations distribute randomly. Such a coincidence can be easily detected statistically. We demonstrate this statistical method by finding new levels for various atomic and nuclear systems from unidentified line lists available online.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

How the Arrangement of Platinum Atoms on Ruthenium Nanoparticles Improves Hydrogen Evolution Activity

The platinum‐ruthenium (PtRu) system is highly active for hydrogen evolution reaction (HER) in alkaline media with both Pt and Ru playing active roles in the water dissociation step that generates adsorbed hydrogen atoms. Precise control of the arrangement of Pt atoms on Ru nanoparticles can maximize the Pt‐Ru sites for water dissociation and Pt‐Pt sites for hydrogen production and can considerably improve HER catalytic performance. By directing the growth and distribution of Pt on Ru hourglass nanoparticles, the arrangement of Pt on Ru is controlled into forming Pt islands, small Pt clusters, and strings of a few Pt atoms. Calculations show that the unique atomic string arrangements of Pt on Ru is the thermodynamically favorable configuration. Additionally, these strings have a favorable combination of Pt‐Ru and Pt‐Pt sites, making the Pt‐string on Ru the most active catalyst with a more than fivefold increase in turnover frequency for alkaline HER compared to the Pt‐island on Ru catalyst. The results show how controlling the Pt atomic arrangement on Ru nanoparticle surfaces for the tuning of Pt‐Pt and Pt‐Ru neighboring sites can direct toward a more efficient HER mechanism and thereby significantly enhancing HER performance.

36 MATERIALS SCIENCE↗

Quantitative comparison between sub-millisecond time resolution single-molecule FRET measurements and 10-second molecular simulations of a biosensor protein

Molecular Dynamics (MD) simulations seek to provide atomic-level insights into conformationally dynamic biological systems at experimentally relevant time resolutions, such as those afforded by single-molecule fluorescence measurements. However, limitations in the time scales of MD simulations and the time resolution of single-molecule measurements have challenged efforts to obtain overlapping temporal regimes required for close quantitative comparisons. Achieving such overlap has the potential to provide novel theories, hypotheses, and interpretations that can inform idealized experimental designs that maximize the detection of the desired reaction coordinate. Here, we report MD simulations at time scales overlapping with in vitro single-molecule Förster (fluorescence) resonance energy transfer (smFRET) measurements of the amino acid binding protein LIV-BP SS at sub-millisecond resolution. Computationally efficient all-atom structure-based simulations, calibrated against explicit solvent simulations, were employed for sampling multiple cycles of LIV-BP SS clamshell-like conformational changes on the time scale of seconds, examining the relationship between these events and those observed by smFRET. The MD simulations agree with the smFRET measurements and provide valuable information on local dynamics of fluorophores at their sites of attachment on LIV-BP SS and the correlations between fluorophore motions and large-scale conformational changes between LIV-BP SS domains. We further utilize the MD simulations to inform the interpretation of smFRET data, including Förster radius (R 0 ) and fluorophore orientation factor (κ 2 ) determinations. The approach we describe can be readily extended to distinct biochemical systems, allowing for the interpretation of any FRET system conjugated to protein or ribonucleoprotein complexes, including those with more conformational processes, as well as those implementing multi-color smFRET.

59 BASIC BIOLOGICAL SCIENCES↗

Large Solar-Rejection Filter

NASA utilized Image Intensified Video Cameras for ATV data acquisition from a jet flying at 12.8 km. Afterwards the video was digitized and then analyzed with a modified commercial software package, Image Systems Trackeye. Astrometric results were limited by saturation, plate scale, and imposed linear plate solution based on field reference stars. Time-dependent fragment angular trajectories, velocities, accelerations, and luminosities were derived in each video segment. It was evident that individual fragments behave differently. Photometric accuracy was insufficient to confidently assess correlations between luminosity and fragment spatial behavior (velocity, deceleration). Use of high resolution digital video cameras in future should remedy this shortcoming. A scenically accurate description of matter interpreted as a substance made up of corpuscular constituents was established during the course of the 19th century. In this description, atoms--the building blocks of the matter--form molecules. The properties of the molecules were described by chemistry or thermodynamics depending on what characteristics of the matter were investigated. In both theories, the molecules can dissociate to atoms when the kinetic energies of the atoms exceed the strength of the chemical bonds. The number of atoms is always preserved in a closed system. This is not true, however, when the matter takes up much higher energies at relativistic scales. New particles can be produced at the expense of the kinetic energy. The number of particles is no longer preserved. There are other conserved quantities, however, these quantities, the charge, baryon number, lepton number, are associated with particles that are considered elementary today. The properties and behavior of these elementary particles is the subject of Particle Physics or High Energy Physics. Practice Page: A crewmember touching a positively charged surface was thought to be galvanically isolated from the vehicle ground analogous to a bird on a high voltage power wire. Recent analysis confirms that positive floating potentials, ionospheric currents to the EVA suit, can be hazardous. The analysis is wrong in that the ionospheric plasma itself can close the circuit. Parametric analysis of very low voltage exposures (2 to 15 volts) could cause pain and/or involuntary muscle tetani or spinal cord shock. NASA worked with the Naval Health Research Center Detachment Directed Energy Bioeffects Laboratory to examine the affects electrical hazards could have on extravehicular activity using two models. The results of the two computational models were combined to predict areas of the body in which neurons of different diameters would be excited. They predicted that physiologically active current could be conducted across the crew member causing catastrophic hazards. Future work to analyze additional current paths was proposed. The FUSE spectrum of BB Dor, observed in a high state, is modeled with an accretion disk with a very low inclination (possibly lower than 10 degrees). Assuming an average WD mass of 0.8 solar mass leads to a distance of the order of approximately 650pc, consistent with the extremely low galactic reddening in its direction, and a mass accretion rate of 10 (exp -9) solar mass a year. The spectrum presents some broad and deep silicon and sulfur absorption lines, indicating that these elements are over-abundant: silicon is 3 times solar, and sulfur is 20 times solar. The FUSE spectrum of BB Dor, observed in a high state, is modeled with an accretion disk with a very low inclination (possibly lower than 10 degrees). Assuming an average WD mass of 0.8 solar mass leads to a distance of the order of approximately 650pc, consistent with the extremely low galactic reddening in its direction, and a mass accretion rate of 10 (exp -9) solar mass a year. The spectrum presents some broad and deep silicon and sulfur absorption lines, indicating that these elements are over-abundant: silicon is times solar, and sulfur is 20 times solar. From its previously observed optical emission lines, P831-57 (WD 0334 6400 or Ret 1 in A Catalog and Atlas of Cataclysmic Variables: Living Edition) has been suspected to contain an accretion disk associated with a companion star in orbit around a subdwarf star with a temperature T is greater than 21,000K. P831-57 has therefore been classified as a nova-like. However, our present observations show it to be a DA + dMe binary. The analysis of its Far Ultraviolet Spectroscopic Explorer (FUSE) spectrum (continuum and lines) reveal an average mass white dwarf (Log(g) approximately equals 7.8 plus or minus 0.1)with a temperature T approximately equals 37,000 plus or minus 500K, an extremely low projected rotational velocity, and a distance of about 115 plus or minus 5pc. The photosphere contains C, N, Si, and S (at about 1% of solar abundances). The dMe star is seen as a flux excess in near-infrared photometry and appears to show occasional flaring of about one magnitude as seen in the Harvard plates. There is no evidence of periodic variability in the spectroscopic or photometric data. We find no evidence of a an accretion disk, instead we find evidence of wind accretion as the stellar carbon abundance (N(C)/N(H) = 2.5 x 10 (exp -6) is about ten times larger than predicted by radiative levitation for such a gravity and temperature. The power needs and solutions for the space exploration and lunar mobility program are discussed. Long term missions in space and on the lunar surface require high energy batteries. Rechargeable batteries for mobility systems and portable utility pallet are needed for successful exploration missions. Nanomaterial usage increases the energy density of the cells apart from increasing the power density. The symptoms and threats from acute mountain sickness (AMS) are discussed. The underlying assumptions concerning spacecraft atmosphere mean there is a potential risk to astronauts. The baseline worst case scenario is about 25% based on direct ascent to 8.0 psia with 32% O2. The practical mitigation approach is a staged depressurization scheme. Due to the uncertainty about potential AMS risk the flight surgeon should prepare, focused research should proceed, and current analytical efforts should continue. This slide presentation reviews the threat astronauts face from acute mountain sickness (AMS). The incidence of AMS is highly variable and the risk to astronauts is unclear. However, the potential risk is higher than current EAAs suggest and precautions should be implemented. Due to the uncertain nature of the risk flight surgeons should prepare, and focused research should proceed. Quasiparticle tunneling can be understood at low temperatures using a non-equilibrium kinetic theory. Low-temperature tunneling can be suppressed using existing techniques: island-lead gap engineering, lead cooling with SIN junctions, and quasiparticle traps. The slide presentation reviews the science goals and mission planning for the proposed Jupiter System Observer (JSO). The spacecraft would accommodate 9 instruments making the instrument payload more capable than any previously flown to Jupiter. The would-be mission includes study programs for Jupiter's satellites, interior, magnetosphere and atmosphere. The power needs and solutions for the space exploration and lunar mobility program are discussed. Long term missions in space and on the lunar surface require high energy batteries. Rechargeable batteries for mobility systems and portable utility pallet are needed for successful exploration missions. Nanomaterial usage increases the energy density of the cells apart from increasing the power density. This slide presentation reviews the power requirements for the space exploration and the lunar surface mobility programs. It includes information about the specifications for high energy batteries and the power requirements for lunar rovers,

Roberts, William↗

Advanced techniques in automated high-resolution scanning transmission electron microscopy

Scanning transmission electron microscopy is a common tool used to study the atomic structure of materials. It is an inherently multimodal tool allowing for the simultaneous acquisition of multiple information channels. Despite its versatility, however, experimental workflows currently rely heavily on experienced human operators and can only acquire data from small regions of a sample at a time. Here, we demonstrate a flexible pipeline-based system for high-throughput acquisition of atomic-resolution structural data using an all-piezo sample stage applied to large-scale imaging of nanoparticles and multimodal data acquisition. As a result, the system is available as part of the user program of the Molecular Foundry at Lawrence Berkeley National Laboratory.

4D-STEM↗

Visualizing the Three-Dimensional Arrangement of Hydrogen Atoms in Organic Molecules by Coulomb Explosion Imaging

Structure-sensitive methods based on femtosecond light or electron pulses are now making it possible to measure how molecular structures change during light-induced processes. Despite significant progress, high-fidelity imaging of nuclear positions remains a challenge even for relatively small molecular systems and, notably, regarding the positions of hydrogen atoms. As demonstrated in recent work, X-ray-induced Coulomb explosion imaging (CEI) may overcome this obstacle, as its sensitivity does not depend on the mass of the imaged atoms. The photoinduced ring opening of the heterocyclic molecule 2(5 H )-thiophenone has attracted recent interest. Here, in this work, we show that CEI offers a powerful route to imaging the peripheral H atoms in this molecule and thus, more generally, to tracking detailed nuclear motions (e.g., isomerizations) in organic molecules on ultrafast time scales. Specifically, we record momentum-space Coulomb explosion images that report on the three-dimensional positioning of all nuclei within the molecule, for instance, distinguishing H atoms in C–H bonds that lie within or are directed out of the plane defined by the heavy atoms. The prospect of imaging peripheral H atoms to probe photochemical dynamics is explored by coupling ab initio molecular dynamics with classical Coulomb explosion simulations, thereby differentiating potential photoproduct isomers, including those whose structures primarily differ in the position of the hydrogens.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Bridging Atomic Solvation Environment with Electrochemical Properties for the Bis(trifluoromethylsulfonyl)imide-Based Divalent Cation Electrolytes for the Next-Generation Energy Storage Systems

A deep molecular-level understanding of the multivalent electrolyte and its correlation with the electrochemical properties is crucial for designing optimized electrolytes for next-generation rechargeable batteries. Comprehensive knowledge of the atomic level of the solvation structure and its connection with electrochemical stability and ion transport properties is especially critical. However, the interaction of these three components coupled with clear atomistic insights is lacking in the literature. Here, our current contribution evaluates representative electrolytes with the bis(trifluoromethanesulfonyl)imide (TFSI) anions for multivalent cations of Mg, Ca, and Zn, at different ionic conditions with and without a cosolvated environment in ether-based solvent. Two critical problems are investigated: first, resolving the solvation structures in the electrolyte solutions as a function of concentrations through pair distribution function analysis and the corresponding electrochemical transport properties; second, unmasking the quantitative correlation of the atomistic environment with both electrochemical kinetics and cation dependence. We discovered that the magnesium- and calcium-based electrolytes display versatile coordination lengths but poor average anodic stability due to ion pairing with TFSI - . On the contrary, the zinc-based electrolytes show the shortest solvent coordination lengths, shielding the Zn cation from rigid solvent interactions and resulting in the highest anodic stabilities. Calcium-based electrolytes exhibit the longest and most concentration-independent coordination lengths. This work provides valuable insights into the molecular structural and electrochemical features of diverse multivalent electrolyte systems with cations in various solvation environments, emphasizing the importance of the solvation structure and construction in designing high-performance electrolytes.

cation coordination↗

Differences in water and vapor transport through angstrom-scale pores in atomically thin membranes

Abstract The transport of water through nanoscale capillaries/pores plays a prominent role in biology, ionic/molecular separations, water treatment and protective applications. However, the mechanisms of water and vapor transport through nanoscale confinements remain to be fully understood. Angstrom-scale pores (~2.8–6.6 Å) introduced into the atomically thin graphene lattice represent ideal model systems to probe water transport at the molecular-length scale with short pores (aspect ratio ~1–1.9) i.e., pore diameters approach the pore length (~3.4 Å) at the theoretical limit of material thickness. Here, we report on orders of magnitude differences (~80×) between transport of water vapor (~44.2–52.4 g m −2 day −1 Pa −1 ) and liquid water (0.6–2 g m −2 day −1 Pa −1 ) through nanopores (~2.8–6.6 Å in diameter) in monolayer graphene and rationalize this difference via a flow resistance model in which liquid water permeation occurs near the continuum regime whereas water vapor transport occurs in the free molecular flow regime. We demonstrate centimeter-scale atomically thin graphene membranes with up to an order of magnitude higher water vapor transport rate (~5.4–6.1 × 10 4 g m −2 day −1 ) than most commercially available ultra-breathable protective materials while effectively blocking even sub-nanometer (>0.66 nm) model ions/molecules.

36 MATERIALS SCIENCE↗