Self-Assembled Bilayer Microstructure Improves Quasi-2D Perovskite Light-Emitting Diodes
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
SEARCH · Engineering Papers
Results for “self organization”
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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Supramolecular and Hybrid Bonding Polymers
Staudinger established a century ago the existence of covalent macromolecules, work that led to the development of transformative materials of great benefit to society and a “quantum leap” in our understanding of biological systems. Over the past few decades the concept of supramolecular polymers has emerged–chemical systems in which structural units bond strongly to each other non-covalently. Herein, we discuss how these dynamic systems actually exist in the natural world and can create soft materials with structures, properties, and functions beyond the ones we know in Staudinger polymers. We reflect here on the potential of novel systems in which covalent and supramolecular polymers are chemically integrated and describe them as hybrid bonding polymers. This paper describes the concept with recent examples from the Stupp laboratory, and discusses their potential functions as robotic materials that mimic living matter and structures that offer new ideas on how to recycle and reuse soft materials.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Dye Nanoaggregate Structures in MK-2, N3, and N749 Dye···TiO 2 Interfaces That Represent Dye-Sensitized Solar Cell Working Electrodes
The working electrode of a dye-sensitized solar cell (DSSC) consists of dye molecules adsorbed onto nanoparticles of a semiconductor such as TiO 2 . A reliable prediction of the DSSC photovoltaic performance of a given dye requires in-depth knowledge about the precise structure of the dye···TiO 2 interface. In this work, X-ray reflectometry (XRR) and grazing-incidence small-angle X-ray scattering (GISAXS) are employed to determine the dye···TiO 2 interfacial structure and associated dye aggregation behavior of three high-performance DSSC dyes, i.e., a metal-free organic dye, MK-2, and the two archetypal ruthenium-based organometallic dyes, N3 and N749 (Black Dye). Results show that all three dyes form nanoaggregates in dye···TiO 2 interfaces. We determine the dye nanoaggregate separations, sizes, distribution densities, and the extent of short-range order within each dye self-assembly in the longitudinal and lateral directions. Dye···TiO 2 composites fabricated using dye solutions of varying concentrations are analyzed. We find that nanoaggregates of the three dyes are separated by several hundred nanometers (158-203 nm) in dye···TiO 2 interfaces that have been fabricated using concentrated dye solutions (0.5 mM or 1.0 mM). MK-2 and N749 dyes also display smaller interparticle separations. Dye nanoparticle diameters are of the order of 156-198 nm, sizes that are comparable to the largest interparticle separations. Thus, no extraneous dye particles can be fitted into gaps between particles, so the dye self-assembly is saturated. Self-assemblies of all three dyes exhibit both lateral and longitudinal short-range order; N3 displays a particularly short coherence length along the TiO 2 surface, with extensive structured disorder along the longitudinal direction. The operation of DSSC working electrodes would therefore seem to be dependent on a dye self-assembly that may exhibit several levels of structural granularity and dye aggregation effects.
14 SOLAR ENERGY↗
Phase separation and state oscillation of active inertial particles
Active matter systems are of great interest for their novel out-of-equilibrium collective behavior. Active Brownian particles (ABPs) are known to exhibit clustering and motility-induced phase separation, and there have been many studies revealing this rich behavior in the overdamped limit of Brownian motion, where inertial effects are insignificant. In this work, we simulate an Active Inertial Particle (AIP) model where we focus on the underdamped, rather than overdamped limit, to study the interplay between particle inertia and collective behavior, such as phase separation. We show that inertia reduces particle motility due to collisions and a longer time delay for particles to regain speed, thereby suppressing phase separation relative to that observed in the overdamped limit. Additionally, we observe interesting oscillatory behavior between a phase separated steady-state and a homogeneous fluid state that results from inertia-induced collective motion within active clusters due to momentum transfer. Such oscillatory behavior has been reported for ABP systems with particle shape anisotropy, where collective motion is mediated by particle shape anisotropy. Furthermore, we confirm that there is no single characteristic frequency for the oscillatory behavior. The power spectral density is a power law in the high frequency domain, with an exponent close to -2.5.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Covalency in Fe 2 O 3 and FeO: Consequences for XPS satellite intensity
The covalent character of the interaction between the metal cation and the oxygen ligands has been examined for two Fe oxides with different nominal oxidation states, Fe(II)O, and Fe(III) 2 O 3 . The covalent character is examined for the initial, ground state configuration and for the ionic states involving the removal of a shallow core, Fe 3p, and a deep core, Fe 2p, electron. The covalency is assessed based on novel theoretical analyses of wave functions for the various cases. It is found that the covalency is considerably different for different oxidation states and for different ionized and non-ionized configurations. The changes in covalency for the ions are shown to be responsible for important changes in relaxation energies for X-Ray Photoelectron Spectroscopy (XPS) spectra and in the intensity lost from main XPS peaks to shake satellites. While these consequences are not observables themselves, they are important for the interpretation of the XPS spectra, in particular, for efforts to extract stoichiometries of these iron oxides from XPS data. This is a finding likely applicable across various 3d transition metal oxide materials.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Potential energy surfaces for high-energy N + O 2 collisions
Potential energy surfaces for high-energy collisions between an oxygen molecule and a nitrogen atom are useful for modeling chemical dynamics in shock waves. In the present work, we present doublet, quartet, and sextet potential energy surfaces that are suitable for studying collisions of O 2 ( 3 Σ$^{–}_{g}$) with N( 4 S) in the electronically adiabatic approximation. Two sets of surfaces are developed, one using neural networks (NNs) with permutationally invariant polynomials (PIPs) and one with the least-squares many-body (MB) method, where a two-body part is an accurate diatomic potential and the three-body part is expressed with connected PIPs in mixed-exponential-Gaussian bond order variables (MEGs). We find, using the same dataset for both fits, that the fitting performance of the PIP-NN method is significantly better than that of the MB-PIP-MEG method, even though the MB-PIP-MEG fit uses a higher-order PIP than those used in previous MB-PIP-MEG fits of related systems (such as N 4 and N 2 O 2 ). However, the evaluation of the PIP-NN fit in trajectory calculations requires about 5 times more computer time than is required for the MB-PIP-MEG fit.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Enskog Transport Calculations with Magpie
he revised Enskog theory for mixtures has been implemented, as a library, in the LANL institutional thermochemical code Magpie. This report provides the necessary physical background and several representative examples of transport calculations with this library. The particular attention is paid to how the contributions of non-translational degrees of freedom (molecular vibrations, rotations, electronic excitations) to the energy transport can be consistently accounted for via the so called Eucken correction.
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Cloud Modeling Using Field Project Data for the Study of Precipitation Processes
The use of cloud-resolving models (CRMs) in the study of precipitation process and their relation to the large-scale environment can be generally categorized into two approaches. The first approach is so called "cloud ensemble modeling". In this approach, many clouds of different size in various stages of their lifecycles can be present at any model simulation time. Large-scale effects are derived from observations and imposed into the model as the main forcing. The advantage of this approach is that the modeled convection will be forced to have the same intensity, thermodynamic budget and organization as the obserations.This approach will also allow CRMs to perform multi-day or multi-week time integrations. The second approach usually requires initial temperature and water vapor profiles that have a medium to large CAPE, and open lateral boundary conditions are used. The modeled clouds could be termed "self-forced convection". Model improvements, such as in the microphysics, are achieved using the second approach. In cloud ensemble modeling, accurate large-scale advective tendencies for temperature and water vapor are the main forcing for the CRMs. We found that the large-scale advective terms for temperature and water vapor are not always consistent, For example, large-scale forcing could indicate strong drying which would produce cooling in the model through evaporation but not contain large-scale advective heating to compensate. This discrepancy in forcing would cause differences between the observed and modeled latent heating profiles. Good measurements of other quantities (i.e., surface fluxes and radiation) are also required to perform variational objective analysis that computes and minimizes a "cost function" that constrains the difference between the large-scale advective forcing in temperature and water vapor. With self-forced convection, accurate vertical distributions of temperature, moisture (water vapor), and horizontal winds are required. The timing of the measurements relative to cloud development is crucial (i.e., prior to cloud triggering). Microphysical measurements (i.e., the cloud number concentration and size distribution) can also be used in this second approach but are of secondary importance with cloud ensemble modeling. In this paper, data collected during TRMM field campaigns (FCs; i.e., SCSMEX, LBA and KWAJEX) which were aimed at validating TRMM products (i.e., rainfall and the vertical distribution of latent heating) will be used to examine the impact of errors in the initial conditions (e.g.., soundings an large-scale forcing) on simulated rainfall distributions and brightness. Rainfall and precipitations simulated from a CRM will also be compared with those estimated by a schocastic model.
Tao, W.-K.↗
Powering ≈50 µm Motion by a Molecular Event in DNA Crystals
A major challenge in material design is to couple nanoscale molecular and supramolecular events into desired chemical, physical, and mechanical properties at the macroscopic scale. Here, a novel self-assembled DNA crystal actuator is reported, which has reversible, directional expansion and contraction for over 50 μm in response to versatile stimuli, including temperature, ionic strength, pH, and redox potential. The macroscopic actuation is powered by cooperative dissociation or cohesion of thousands of DNA sticky ends at the designed crystal contacts. The increase in crystal porosity and cavity in the expanded state dramatically enhances the crystal capability to accommodate/encapsulate nanoparticles/proteins, while the contraction enables a “sponge squeezing” motion for releasing nanoparticles. This crystal actuator is envisioned to be useful for a wide range of applications, including powering self-propelled robotics, sensing subtle environmental changes, constructing functional hybrid materials, and working in drug controlled-release systems.
36 MATERIALS SCIENCE↗
PySpawn: Software for Nonadiabatic Quantum Molecular Dynamics
The ab initio multiple spawning (AIMS) method enables nonadiabatic quantum molecular dynamics simulations in an arbitrary number of dimensions, with potential energy surfaces provided by electronic structure calculations performed on-the-fly. However, the intricacy of the AIMS algorithm complicates software development, deployment on modern shared computer resources, and post-simulation data analysis. PySpawn is a nonadiabatic molecular dynamics software package that addresses these issues. Here, the program is designed to be easily interfaced with electronic structure software, and an interface to the TeraChem software package is described here. PySpawn introduces a task-based reorganization of the AIMS algorithm, allowing fine-grained restart capability and setting the stage for efficient parallelization in a future release. PySpawn includes a user-friendly and interactive Python analysis module that will enable novice users to painlessly adopt AIMS. As a demonstration of PySpawn’s simulation capability and analysis module, we report complete active space self-consistent field–based AIMS simulations of the 1,2- dithienyl-1,2-dicyanoethene molecule, a promising molecular photoswitch.
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Design and Preparation of Nematic Colloidal Particles
Colloidal systems are abundant in technology, in biomedical settings, and in our daily life. The so-called “colloidal atoms” paradigm exploits interparticle interactions to self-assemble colloidal analogs of atomic and molecular crystals, liquid crystal glasses, and other types of condensed matter from nanometer- or micrometer-sized colloidal building blocks. Nematic colloids, which comprise colloidal particles dispersed within an anisotropic nematic fluid host medium, provide a particularly rich variety of physical behaviors at the mesoscale, not only matching but even exceeding the diversity of structural and phase behavior in conventional atomic and molecular systems. This feature article, using primarily examples of works from our own group, highlights recent developments in the design, fabrication, and self-assembly of nematic colloidal particles, including the capabilities of preprogramming their behavior by controlling the particle’s surface boundary conditions for liquid crystal molecules at the colloidal surfaces as well as by defining the shape and topology of the colloidal particles. Here recent progress in defining particle-induced defects, elastic multipoles, self-assembly, and dynamics is discussed along with open issues and challenges within this research field.
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Operation of a Modular 3D-Pixelated Liquid Argon Time-Projection Chamber in a Neutrino Beam
The 2x2 Demonstrator, a prototype for the Deep Underground Neutrino Experiment (DUNE) liquid argon (LAr) Near Detector, was exposed to the Neutrinos from the Main Injector (NuMI) neutrino beam at Fermi National Accelerator Laboratory (Fermilab). This detector is a prototype of a new modular design for a liquid argon time-projection chamber (LArTPC), comprising a two-by-two array of four modules, each further segmented into two optically isolated LArTPCs. The 2x2 Demonstrator features a number of pioneering technologies, including a low-profile resistive field shell to establish drift fields, native 3D ionization pixelated imaging, and a high-coverage dielectric light readout system. The 2.4-tonne active mass detector is flanked upstream and downstream by supplemental solid-scintillator tracking planes, repurposed from the MINERvA experiment, which track ionizing particles exiting the argon volume. The antineutrino beam data collected by the detector over a 4.5 day period in 2024 include over 30,000 neutrino interactions in the LAr active volume—the first neutrino interactions reported by a DUNE detector prototype. During its physics-quality run, the 2x2 Demonstrator operated at a nominal drift field of 500 V/cm and maintained good LAr purity, with a stable electron lifetime of approximately 1.25 ms. This paper describes the detector and supporting systems, summarizes the installation and commissioning, and presents the initial validation of collected NuMI beam and off-beam self-triggers. In addition, it highlights observed interactions in the detector volume, including candidate muon antineutrino events.
47 OTHER INSTRUMENTATION↗
Free shear flows - Organized structures and effects of excitation
Recent studies of free shear flows are reviewed. Included are experimental studies of: excited and unexcited circular and elliptic jets, plane wake and mixing layers, and effects of excitation on augmentation and reduction of jet turbulence and jet noise. It is shown that proper excitation can produce both large increases and large decreases in turbulence and Reynolds stress level, mixing and noise generation, suggesting promising technological applications of self-excited jets such as whistler jets. It is also argued that 'ribs' or longitudinal vortices play an important role in production and mixing in free, and perhaps all, turbulent shear flows. The 'cut-and-connect' interaction of vortical structures is proposed as a key mechanism for coherent structure breakdown, mixing, turbulence production, and aerodynamic noise generation. A simple analysis of the viscous vorticity equation using symmetry of configurations of vortical structures before and after the interaction gives realistic predictions.
Hussain, A. K. F.↗
Tunable Metal–Organic Frameworks Based on 8-Connected Metal Trimers for High Ethane Uptake
Metal trimers [M 3 (O/OH)](OOCR) 6 are among the most important structural building blocks. From these trimers, a great success has been achieved in the design of 6- or 9-connected framework materials with various topological features and outstanding gas-sorption properties. In comparison, 8-connected trimer-based MOFs are rare. Given multiple competitive pathways for the formation of 6- or 9-connected frameworks, it remains challenging to identify synthetic or structural parameters that can be used to direct self-assembly process towards trimer-based 8-connected materials. Here, we reveal a viable strategy called angle bending modulation for creating a prototypical MOF type based on 8-connected M 3 (OH)(OOCR) 5 (Py-R) 3 trimers, M = Zn, Co, Fe). As a proof of concept, we synthesized six members in this family using three types of ligands (CPM-80, -81, and -82). These materials do not possess open-metal sites and show excellent uptake capacity for various hydrocarbon gas molecules and inverse C 2 H 6 /C 2 H 4 selectivity. CPM-81-Co, made from 2,5-furandicarboxylate and isonicotinate, features selectivity of 1.80 with high uptake capacity for ethane (123 cm 3 /g -1 ) and ethylene (113 cm 3 /g -1 ) at 298 K and 1 bar.
36 MATERIALS SCIENCE↗
Probing the potential of type V Deep eutectic solvents as sustainable electrolytes
The increasing interest within the scientific community in environmentally friendly solvents has led to a focus on Deep Eutectic Solvents (DES), which have natural components. DES are viewed as alternatives to traditional organic solvents and have the potential to be used as electrolytes. For the first time, transport properties of four Type V Deep Eutectic Salt Solutions (DESS) were accessed to investigate the potential of this technology, selecting precursors ranked as excellent in Eco-Scale metrics. The DESS were composed of terpene and trioctylphosphine oxide (TOPO), and varying concentrations of lithium bis(trifluoromethane)sulfonimide (LiTFSI), and their properties were assessed through self-diffusion, viscosity, density, and conductivity measurements. While Type V DESS are capable of dissolving significant amounts of LiTFSI (up to 30 % molar), their ionic conductivity is low, with values ranging from 3.6·10 –3 to 9.3·10 –2 mS·cm –1 at 25 °C, thus limiting their suitability as electrolytes, for instance, for lithium-ions batteries applications. Similar diffusion coefficients for Li + and TFSI – ions suggest the formation of long-lived ion pairs moving as a neutral species. As a result, future research aims to introduce additives to disrupt contact ion pairs and enhance transport properties, leveraging the sustainable appeal of DES and their use in advanced energy storage technologies.
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NIAC Phase 1 Final Study Report on Titan Aerial Daughtercraft
Saturns giant moon Titan has become one of the most fascinating bodies in the Solar System. Even though it is a billion miles from Earth, data from the Cassini mission reveals that Titan has a very diverse, Earth-like surface, with mountains, fluvial channels, lakes, evaporite basins, plains, dunes, and seas [Lopes 2010] (Figure 1). But unlike Earth, Titans surface likely is composed of organic chemistry products derived from complex atmospheric photochemistry [Lorenz 2008]. In addition, Titan has an active meteorological system with observed storms and precipitation-induced surface darkening suggesting a hydrocarbon cycle analogous to Earths water cycle [Turtle 2011].Titan is the richest laboratory in the solar system for studying prebiotic chemistry, which makes studying its chemistry from the surface and in the atmosphere one of the most important objectives in planetary science [Decadal 2011]. The diversity of surface features on Titan related to organic solids and liquids makes long-range mobility with surface access important [Decadal 2011]. This has not been possible to date, because mission concepts have had either no mobility (landers), no surface access (balloons and airplanes), or low maturity, high risk, and/or high development costs for this environment (e,g. large, self-sufficient, long-duration helicopters). Enabling in situ mobility could revolutionize Titan exploration, similarly to the way rovers revolutionized Mars exploration. Recent progress on several fronts has suggested that small-scale rotorcraft deployed as daughtercraft from a lander or balloon mothercraft may be an effective, affordable approach to expanding Titan surface access. This includes rapid progress on autonomous navigation capabilities of such aircraft for terrestrial applications and on miniaturization, driven by the consumer mobile electronics market, of high performance of sensors, processors, and other avionics components needed for such aircraft. Chemical analysis, for example with a mass spectrometer, will be important to any Titan surface mission. Anticipating that it may be more practical to host chemical analysis instruments on a mothership than a daughtercraft, we defined system and mission concepts that deploy a small rotorcraft, termed a Titan Aerial Daughtercraft (TAD), from a lander or balloon to perform high-resolution imaging and mapping, potentially land to acquire microscopic images or other in situ measurements, and acquire samples to return to analytical instruments on the mothership. In principle, the ability to recharge batteries in TAD from a radioisotope or other long-lived power source on the mothership could enable multiple sorties. For a lander-based mission, a variety of landing sites is conceivable, including near lake margins, in dry lake beds, or in regions of plains, dunes, or putative cryovolanic or impact melt features. Such missions may require landing with greater precision than in previous missions (Huygens) and mission studies; this could also enhance the ability of TAD to reach interesting terrain from the landing site. Precision descent may also benefit balloon missions, with or without a daughtercraft, by increasing the probability that the balloon will drift over desired terrain early in its mission. Given these potential benefits, the overall concept studied here includes brief consideration of precision descent for landing or balloon deployment, followed by one or more sorties by a rotorcraft deployed from the mothership, with the ability to return to the mothership.
Saturn↗
Amorphous 1-D nanowires of calcium phosphate/pyrophosphate: A demonstration of oriented self-growth of amorphous minerals
Amorphous inorganic solids are traditionally isotropic, thus, it is believed that they only grow in a non-preferential way without the assistance of regulators, leading to the morphologies of nanospheres or irregular aggregates of nanoparticles. However, in the presence of (ortho)phosphate (Pi) and pyrophosphate ions (PPi) which have synergistic roles in biomineralization, the highly elongated amorphous nanowires (denoted ACPPNs) form in a regulator-free aqueous solution (without templates, additives, organics, etc). Based on thorough characterization and tracking of the formation process (e.g., Cryo-TEM, spherical aberration correction high resolution TEM, solid state NMR, high energy resolution monochromated STEM-EELS), the microstructure and its preferential growth behavior are elucidated. In ACPPNs, amorphous calcium orthophosphate and amorphous calcium pyrophosphate are distributed at separated but close sites. The ACPPNs grow via either the preferential attachment of ~2 nm nanoclusters in a 1-dimension way, or the transformation of bigger nanoparticles, indicating an inherent driving force-governed process. Here, we propose that the anisotropy of ACPPNs microstructure, which is corroborated experimentally, causes their oriented growth. This study proves that, unlike the conventional view, amorphous minerals can form via oriented growth without external regulation, demonstrating a novel insight into the structures and growth behaviors of amorphous minerals.
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Supramolecular Support of Cuprophilic Network Bonding in 2-D Copper n -Alkanethiolates
Here, the development of heterogeneous materials, catalysts, and semiconductors is often reliant on precise control of self-assembly and crystal packing. Many new materials are initially synthesized as microcrystalline powders, making them incompatible with typical methods of structure determination, such as single-crystal X-ray diffraction. This resultant lack of structural information has made thorough investigation into the effect of metal substitution on crystal structure in metal-organic chalcogenolates (MOChas) challenging. Here, we use small molecule serial femtosecond crystallography (smSFX) to present the structures of four copper n-alkanethiolates: CuSC4, CuSC5, CuSC6, and CuSC7. Divergent patterns of alkyl chain packing are identified from microcrystalline powders via smSFX. An odd-even effect in crystal packing has been identified and attributed to different orientations of symmetry elements in the even- and odd-numbered chains. This results in minute changes in the azimuthal organization of the even-numbered chains and the network of cuprophilic interactions. Additionally, we present a synthesis of crystalline gold n-alkanethiolates to provide the first comparison between three d 10 coinage metals (Cu, Ag, and Au) and their resultant n-alkanethiolates.
Willson, Maggie C. [Univ. of Connecticut, Storrs, ↗