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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 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Implementation of real‐time TDDFT for periodic systems in the open‐source PySCF software package

Abstract We present a new implementation of real‐time time‐dependent density functional theory (RT‐TDDFT) for calculating excited‐state dynamics of periodic systems in the open‐source Python‐based PySCF software package. Our implementation uses Gaussian basis functions in a velocity gauge formalism and can be applied to periodic surfaces, condensed‐phase, and molecular systems. As representative benchmark applications, we present optical absorption calculations of various molecular and bulk systems and a real‐time simulation of field‐induced dynamics of a (ZnO) 4 molecular cluster on a periodic graphene sheet. We present representative calculations on optical response of solids to infinitesimal external fields as well as real‐time charge‐transfer dynamics induced by strong pulsed laser fields. Due to the widespread use of the Python language, our RT‐TDDFT implementation can be easily modified and provides a new capability in the PySCF code for real‐time excited‐state calculations of chemical and material systems.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Functionalized Magnetic Nanoparticles for Technetium Sequestration from Groundwater

Technetium 99 (Tc) is among the most common environmental contaminants at DOE sites and one of the most common risk drivers in low- and high-level waste disposal sites. The majority of Tc is generated from anthropogenic sources, such as nuclear power plants, global weapons, nuclear storage facilities and medical applications. Through these sources, Tc contamination has been unintentionally introduced in to the environment. The most common chemical form of Tc is Tc(VII)O{sub 4}{sup -}. Due to its high solubility and mobility, Tc can enter the food chain and cause adverse health effects to humans. Currently, ion exchange resins and reduction processes are the most common approaches for Tc immobilization. Although these techniques have shown to be effective, they also possess major drawbacks, such as high cost, low adsorption capacity, and complex creation and maintenance. Therefore, development of more efficient and simple technologies for the remediation of Tc-contaminated systems are needed. Functionalized magnetic nanoparticles have been used to remove organic and inorganic contaminants from water resources. These nanoparticles have attracted extensive attention as an adsorbent material due to their large surface area, high efficiency, low-cost, easy functionalization and separation with a magnet. This study seek to develop functionalized magnetic iron oxide nanoparticles for the efficient removal of Tc and other heavy metal contaminants from water resources under ambient conditions. Objectives: Synthesize magnetic iron oxide nanoparticles and functionalize their surface with Cetyltrimethylammonium Bromide (CTAB) and tetraethyl-orthosilicate (TEOS). Characterize the synthesized nanoparticles using scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDS), Dynamic Light Scattering (DLS) and Zeta PALS. Perform adsorption studies to evaluate their adsorption behavior and capacity for (a) Technetium using Rhenium (ReO{sub 4}{sup -}) as a surrogate and (b) heavy metals, e.g. Cu{sup 2+}. Conclusions: Magnetic iron oxide nanoparticles were successfully functionalized with CTAB and TEOS. The functionalization of the iron oxide nanoparticles affects their surface charge and their hydrodynamic diameter. The addition of CTAB or TEOS decreased the hydrodynamic diameter of the nanoparticles due to repulsive and steric forces. The SEM micrographs show spherical nanoparticles of different sizes. The EDX analysis shows the presence of iron and oxygen from the iron oxide crystalline structure, and the different constituents of the CTAB and TEOS molecules. Proof-of-concept shows the successful adsorption of rhenium (ReO{sub 4}{sup -}) and copper Cu{sup 2+}) onto CTAB-Fe{sub 2}O{sub 3} and TEOS-Fe{sub 2}O{sub 3} respectively.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗
DOE OSTI2020

Hydration Mechanisms in Nanoparticle Interaction and Surface Energetics

Work on the project advanced molecular level understanding, prediction and control of nanoscale hydration in salt solutions under electric stimuli or ionic patterning. Permeation of nanoporous electrodes at preset voltage underlies the function of ultracapacitors. Transitory regulation of wetting in nanoporous media by electric field spans an array of applications in materials, energy storage, and separation sciences. The physically related modulation of nanoparticle solubility by surface charges can significantly extend the range of the nanomaterial applications, improve processing techniques, and potentially alleviate environmental concerns. Pore/solution equilibria, and activated kinetics of liquid gating by nanoconfined electrolytes are challenging problems at the forefront of experimental and theoretical research. Addressing these problems from a molecular perspective required the development of state-of-the-art simulation algorithms in statistical mechanics to capture complex processes in open systems under electric control. Parallel studies of wetting and dispersibility of polar and ionizing particles aim to uncover predictive relations between electrowetting, chemical functionalization, and geometry of nanomaterial particles. By nonequilibrium dynamic modeling, we elucidated electrolyte flow in nanochanels and associated electrokinetic energy conversion. Research on the program provided training opportunities for the next generation of scientists in computational chemistry. Insights, and methods from the project implicate broad segment of researchers in energy and nanosciences, materials and surface chemistry.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2023

Shadow molecular dynamics and atomic cluster expansions for flexible charge models

A shadow molecular dynamics scheme for flexible charge models is presented, where the shadow Born-Oppenheimer potential is derived from a coarse-grained approximation of range-separated density functional theory. The interatomic potential, including the atomic electronegativities and the charge-independent short-range part of the potential and force terms, are modeled by the linear atomic cluster expansion (ACE), which provides a computationally efficient alternative to many machine learning methods. The shadow molecular dynamics scheme is based on extended Lagrangian (XL) Born-Oppenheimer molecular dynamics (BOMD) [Eur. Phys. J. B 94, 164 (2021)]. XL-BOMD provides a stable dynamics, while avoiding the costly computational overhead associated with solving an all-to-all system of equations, which normally is required to determine the relaxed electronic ground state prior to each force evaluation. To demonstrate the proposed shadow molecular dynamics scheme for flexible charge models using the atomic cluster expansion, we emulate the dynamics generated from self-consistent charge density functional tight-binding (SCC-DFTB) theory using a second-order charge equilibration (QEq) model. The charge-independent potentials and electronegativities of the QEq model are trained for a supercell of uranium oxide (UO2) and a molecular system of liquid water. The combined ACE + XL-QEq dynamics are stable over a wide range of temperatures both for the oxide and the molecular systems, and provide a precise sampling of the Born-Oppenheimer potential energy surfaces. Accurate ground Coulomb energies are produced by the ACE-based electronegativity model during an NVE simulation of UO 2 , predicted to be within 1 meV of those from SCC-DFTB on average during comparable simulations.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2022

Squeezing Out Interfacial Solvation: The Role of Hydrogen-Bonding in the Structural and Orientational Freedom of Molecular Self-Assembly

We report bioinspired membrane molecules with improved physical properties and enhanced stability can serve as functional models for conventional lipid or amphiphilic species. Importantly, these molecules can also provide new insights into emergent phenomena that manifest during self-assembly at interfaces. Here, we elucidate the structural response and mechanistic steps underlying the self-assembly of the amphiphilic, charged oligodimethylsiloxane imidazolium cation (ODMS-MIM+) at the air–aqueous interface using Langmuir trough methods with coincident surface-specific vibrational sum-frequency generation (SFG) spectroscopy. We find evidence for a new compression-induced desolvation step that precedes commonly known disordered-to-ordered phase transitions to form nanoscopic assemblies. The experimental data was supported by atomistic molecular dynamics (MD) simulations to provide a detailed mechanistic picture underlying the assembly and the role of water in these phase transitions. The sensitivity of the hydrophobic ODMS tail conformations to compression-owing to distinct water–ODMS interactions and tail–tail solvation properties-offers new strategies for the design of interfaces that can be further used to develop soft-matter electronics and low-dimensional materials using physical and chemical controls.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2020

Charging-driven coarsening and melting of a colloidal nanoparticle monolayer at an ionic liquid–vacuum interface

In this work, we induce and investigate the coarsening and melting dynamics of an initially static nanoparticle colloidal monolayer at an ionic liquid–vacuum interface, driven by a focused, scanning electron beam. Coarsening occurs through grain interface migration and larger-scale motions such as grain rotations, often facilitated by sliding dislocations. The progressive decrease in area fraction that drives melting of the monolayer is explained using an electrowetting model whereby particles at the interface are solvated once their accumulating charge recruits sufficient counterions to subsume the particle. Subject to stochastic particle removal from the monolayer, melting is recapitulated in simulations with a Lennard-Jones potential. This new driving mechanism for colloidal systems, whose dynamical timescales we show can be controlled with the accelerating voltage, opens the possibility to manipulate particle interactions dynamically without need to vary particle intrinsic properties or surface treatments. Furthermore, the decrease in particle size availed by electron imaging presents opportunities to observe force and time scales in a lesser-explored regime intermediate between typical colloidal and molecular systems.

36 MATERIALS SCIENCE↗
DOE OSTI2021

Features of ion generation by a picosecond laser in the range of 10 11 –10 13 W cm -2 power densities

Picosecond lasers (ps-lasers) have significant advantages for the generation of low charge state ions compared to nanosecond lasers because the influence of heat conductivity on a solid target is almost negligible in the case of ps-laser ablation for laser pulse durations less than 10 ps. However, there is no comprehensive data on ion yields for different elements and target irradiation conditions for laser power densities at the target surface around and below 10 13 W cm –2 , which is of interest to our study of such plasmas as a source of low charge state ions for various applications, particularly for external injection of those ions into an Electron Beam Ion Source (EBIS). We investigated ion generation from Al, Ti, Cu, Nb and Ta target elements by a ps-laser with power densities in the range of 10 11 –10 13 W cm –2 at the target surface. A ps-laser with 1.27 mJ maximum energy within an 8 ps pulse and repetition rate up to 400 Hz has been used to generate a laser-ablated plasma. Dependencies of ion current versus time, total charge of registered ions as well as ion kinetic energy distributions are characterized using a Faraday cup. Significant difference in ion current dynamics between first, second and following shots onto the same target spot was found for all five target elements. The total charge of ions registered by the Faraday cup increases linearly with increasing laser pulse energy and is almost independent of the target element and number of shots onto the same target spot for all five target elements studied. The results obtained give us a basis for specification and design of the source of low charge state ions for external injection into EBIS.

43 PARTICLE ACCELERATORS↗
DOE OSTI2021

Study of Ion Generation by a ps-laser for External Injection into Electron Beam Ion Source

We investigated ion generation from Al, Ti, Cu, Nb and Ta target elements by a picosecond-laser in the range of 10 11 – 10 13 W/cm 2 power densities at the target surface. A ps-laser with 1.27 mJ maximum energy within a 8 ps pulse and repetition rate up to 400 Hz has been used to generate a laser-ablated plasma. Dependencies of ion current vs time, total charge of registered ions as well as ion kinetic energy distributions are characterized using a Faraday cup. Significant difference in ion current dynamics between first, second and following shots onto the same target spot was found for all five target elements. The total charge of ions registered by the Faraday cup increase linearly with increasing laser pulse energy and are almost independent on the target element and number of shots onto the same target spot for all five target elements studied. Target craters have been examined using a commercially available microscope (Nikon Eclipse LV150) and crater cross section areas were found to be in the range of 0.0076 – 0.0172 mm 2 within the first five shots onto the same target spot for different target elements. A linear dependence of crater cross section square on laser pulse energy has been observed for the Ta target. Ion energy distributions for all target elements have a plateau or a slight peak in the energy range of 10 - 100 eV and long low-intensity energy tail up to tens of keV.

43 PARTICLE ACCELERATORS↗
DOE OSTI2023

Shivalik Plasma Device-I, a glow discharge device to study the collective dynamics of dusty plasma

Using a uniquely configured glow discharge-based Shivalik Plasma Device-I, we demonstrate a variety of collective phenomena in dusty plasma away from the glow discharge region. The cylindrical glass device produces plasma using parallel disc-shaped electrodes with a smaller anode size than the cathode. The dust microparticles are initially sprinkled over the grounded cathode. These particles acquire a significant negative charge upon plasma formation, resulting in their levitation due to the balance between the Coulomb force and gravity. The new device supports the levitation of a big-sized (10 × 8 × 5 cm 3 ) three-dimensional dust cloud over the glass surface. It contrasts the dusty plasma formations in-between electrodes reported earlier. As the discharge voltage varies from high to low, the dust cloud travels from over the glass surface to between the electrodes. A complex interplay of dust void over the cathode, a sharp density gradient, and gravity lead to self-excitation of collective dust phenomena. It includes dust density waves (phase velocity, v ph ~4 cm/s), dust cloud oscillation (frequency, f = 5 Hz), sheared flow (flow velocity, v f ~ 1 cm/s), and multiple-sized dust vortices. These dust vortices provided an excellent platform for studying turbulent mixing phenomena. The power spectrum analysis agreed with two-dimensional Kolmogorov power-law scaling. This is an ideal dusty plasma apparatus where we can create or move the dust cloud to a location of choice from the glass surface to in-between the electrodes and excite one among many collective dust dynamics.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2021

Improvements to the macroscopic-microscopic approach of nuclear fission

The well-established macroscopic-microscopic (mac-mic) description of nuclear fission enables the prediction of fission-fragment yields for a broad range of fissioning systems. In this work, we present several key enhancements to this approach. We improve upon the microscopic sector of nuclear potential-energy surfaces by magnifying the resolution of the Lipkin-Nogami equations and strengthening the Strutinsky procedure, thus reducing spurious effects from the continuum. We further present a novel deterministic method for calculating fission dynamics under the assumption of strongly damped nucleonic motion. Our technique directly determines the evolution of the scissioned shape distribution according to the number of random-walk steps rather than the statistical accumulation of fission events. We show that our new technique is equivalent to the Metropolis random walk pioneered over the past decade by Randrup and colleagues. It further improves upon it because we remove the need for altering the nuclear landscape via a biased potential. With our final improvement, we calculate fission fragments mass and charge distributions using particle number projection, which affords the simultaneous calculation of both mass- and charge-yield distributions. Fission fragments are thus calculated from the quantum-mechanical A -body states of the potential-energy surface rather than from the collective mass asymmetry variable α g of the finite-range liquid-drop model used in past work. We highlight the success of our enhancements by predicting the odd-even staggering and the charge polarization for the neutron-induced fission of 233 U and 235 U .

73 NUCLEAR PHYSICS AND RADIATION PHYSICS↗
DOE OSTI2022

Capacitance of Carbon Nanotube/Graphene Composite Electrodes with [BMIM + ][BF$_4^–$]/Acetonitrile: Fixed Voltage Molecular Dynamics Simulations

The capacitance of nanoporous carbon electrode materials is dictated by the physical interactions with electrolyte ions and molecules at the accessible interior electrode surface. While significant progress has been made in designing and synthesizing carbon materials with well-defined and relatively homogeneous nanoporosity, the majority of materials remain heterogeneous, and the resulting properties reflect an average over this distribution. In this regard, computer simulations can be a valuable tool to predict or validate structure/property relationships by systematically investigating well-defined, model electrode morphologies. In this work, we utilize fixed-voltage molecular dynamics simulations to predict structure/capacitance relationships for five different model morphologies of carbon nanotube/graphene (CNT/G) composite electrodes with 1-butyl-3-methylimidazolium tetrafluoroborate/acetonitrile electrolyte. The CNT/G electrode models are inspired by experimental “layer-by-layer” syntheses and strike a balance between realism and computational tractability. Comparison between different model electrode architectures elucidates important structure/property relationships. We find that CNT/graphene contact points serve as “hot spots” with significantly enhanced charge separation relative to the rest of the electrode. Furthermore, we demonstrate a specific nanoconfinement motif that provides substantial 3–4$\times$ enhancement of local capacitance, resulting in a ~40% increase of the total electrode differential capacitance. Because the accessible surface area of the model CNT/G electrodes is precisely determined, a comparison of per-area capacitance across systems is unambiguous. Our results thus complement a prior computational demonstration of capacitance enhancement in nanoconfinement while elucidating additional interaction motifs at CNT/G electrochemical interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2022

Nonadiabatic Molecular Dynamics Simulations Based on Time-Dependent Density Functional Tight-Binding Method

Nonadiabatic excited-state molecular dynamics underpin many photophysical and photochemical phenomena, such as exciton dynamics, charge separation and transport. In this work, we present an efficient nonadiabatic molecular dynamic (NAMD) simulation method based on time-dependent density functional tight-binding (TDDFTB) theory. Specifically, the adiabatic electronic structure, an essential NAMD input, is described at the TDDFTB level. Here, the nonadiabatic effects originating from the coupled motions of electrons and nuclei are treated by the trajectory surface hopping algorithm. To improve the computational efficiency, nonadiabatic couplings between excited states within the TDDFTB method are derived and implemented using an analytical approach. Further, the time-dependent nonadiabatic coupling scalars are calculated based on the overlap between molecular orbitals rather than the Slater determinants to speed up the simulations. In addition, the electronic decoherence scheme and a state reassigned unavoided crossings algorithm, which has been implemented in the NEXMD software, are used to improve the accuracy of the simulated dynamics and handle trivial unavoided crossings. Finally, the photoinduced nonadiabatic dynamics of a benzene molecule are simulated to demonstrate our implementation. The results for excited state NAMD simulations of benzene molecule based on TDDFTB method compare well that obtained with numerically expensive time-dependent density functional theory. The proposed methodology provides an attractive theoretical simulation tool for predicting the photophysical and photochemical properties of complex materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2025

Ir(hkl) Surface Electrochemistry in a Nonadsorbing Acidic Medium

The fundamental properties of electrochemical materials depend on the multiple and often complex interactions between electrode surface sites and electrolyte species at the electrochemical interface. Despite Iridium use in electrolyzer systems, much of its surface electrochemistry remains underexplored. This study investigates the surface electrochemistry of Ir(111), Ir(100), and Ir(110) surfaces in acidic media. Using cyclic voltammetry and CO charge displacement experiments, we establish the charge states and adsorbate coverages as a function of the electrode potential, revealing the presence of hydrogen and hydroxyl co-adsorption at low potentials on (111), and almost no coverage of H ad on (110) facet. In situ Shell Isolated Nanoparticle Enhanced Raman Spectroscopy experiments provide direct evidence of the formation of key adsorbate species, such as hydrogen, hydroxyl, and oxygen, but most importantly, their interactions with interfacial water, confirmed by Density Functional Theory calculations. Our findings highlight the role of co-adsorption and interspecies interactions, with microkinetic adsorption voltammetry simulations corroborating the influence of lateral interactions on adsorption dynamics, particularly for Ir(100) where the OHad formation occurs as a sharp adsorption/desorption current. Our results underscores the importance of interfacial water and hydrogen bonding networks in shaping the electrochemical behavior on Ir surfaces, refining our baseline understanding of the Ir surface electrochemistry necessary for the development of advanced Ir-based electrochemical materials.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2021

Real-time Characterization of the Fine Structure and Dynamics of an Electrical Double Layer at Electrode-electrolyte Interfaces

The chemisorption of species from supporting electrolytes on electrode surfaces is ubiquitous in electrochemical systems and affects the dynamics and mechanism of various electrochemical reactions. The understanding of chemical structure and property of the resulting electrical double layer is vital but limited. In this work, we operando probed the electrochemical interface between a gold electrode surface and a common supporting electrolyte, phosphate buffer, using our newly developed in situ liquid secondary ion mass spectrometry. We surprisingly found that on the positively charged gold electrode surface sodium cations were anchored in the stern layer in a partially dehydrated form by formation of compact ion pairs with the accumulated phosphate anions. The resulting strong and dense adsorption phase was further revealed to retard the electro-oxidation reaction of ascorbate. This finding addressed one major gap in the fundamental science of electrode-electrolyte interfaces that where and how the cations reside in the double layer to impose effects on electrochemical reactions, providing insights into engineering of better electrode-electrolyte interfaces in electrochemical processes.

Zhang, Yanyan↗
DOE OSTI2025

Spontaneous Formation of Single-Crystalline Spherulites in a Chiral 2D Hybrid Perovskite

In two-dimensional (2D) chiral metal-halide perovskites (MHPs), chiral organic spacers induce structural chirality and chiroptical properties in the metal-halide sublattice. This structural chirality enables reversible crystalline-glass phase transitions in (S-NEA) 2 PbBr 4 , a prototypical chiral 2D MHP where NEA + represents 1-(1-naphthyl)ethylammonium. Here, in this study, we investigate two distinct spherulite states of (S-NEA) 2 PbBr 4 , exhibiting either radial-like or stripe-like banded patterns depending on the annealing conditions of the amorphous film. Despite similarities in optical absorption and photoluminescence, the stripe-like, banded spherulite exhibits higher crystallinity and improved optical transparency compared to those of radial-like spherulite. X-ray nanoprobe measurements reveal tilting-angle modulations in the octahedral plane of stripe-like spherulites, correlating with the film’s surface geometry. Transfer matrix calculations indicate that the optical contrast in stripe-like patterns, seen in bright-field optical microscopy, arises from optical interference effects, differing from the contrast mechanism observed in polymer spherulites. Ultrafast carrier dynamics experiments suggest that the stripe-like spherulites resemble single crystals more closely than radial-like spherulites, while electrical conductivity measurements show enhanced charge carrier transport in stripe-like spherulites. These findings offer insights into MHP spherulite states with a single composition but different morphologies, previously observed only in polymers, highlighting their potential for optoelectronic applications.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Elevating the Practical Application of Sodium-Ion Batteries through Advanced Characterization Studies on Cathodes

Sodium-ion batteries (SIBs) have emerged as promising alternatives to their lithium-ion counterparts due to the abundance of sodium resources and their potential for cost-effective energy storage solutions. The chemistry for SIBs has been investigated since the 1980s, but it went through a slow research and development process. Recently, there has been an acceleration in technology maturation due to a supply chain crisis originating from unequal resource distribution and sustainability and safety concerns regarding lithium-ion batteries. However, the practical application of SIBs has been hindered primarily by challenges related to cathode materials, specifically, surface and structural stabilities in different conditions. Through the integration of advanced techniques such as in situ spectroscopy, operando diffraction, and high-resolution microscopy, a comprehensive understanding of the cathode’s dynamic behavior and degradation mechanisms can be achieved. The identified structural modifications, phase transitions, and degradation pathways offer critical insights into the design of robust cathode materials with prolonged cycling stability, fast charging capability, high energy density, great low-temperature performance, and safety. This review underscores the pivotal role of cutting-edge characterization techniques in guiding the development of high-performance sodium-ion batteries, thereby fostering the realization of sustainable and efficient energy storage solutions for diverse technological applications.

25 ENERGY STORAGE↗
DOE OSTI2026

Dynamic modeling of heat pipe integrated thermal battery latent heat storage system experiment validation

A heat pipe integrated thermal battery system has been constructed to investigate a high-temperature latent heat thermal energy storage technology that takes advantage of near isothermal operation of latent heat storage and heat pipes to potentially enable high-energy isothermal heat storage. A dynamic model constructed in Modelica has been validated, showing errors between 2.5 °C–39.7 °C across 10-h to 47-h simulations against experiment results, showing good prediction capability of experiment output, especially against phase change time. Model calibrations showing vessel heat-up capability of 3 kW and heat pipes combining to provide 600 W each during experiment operation validate experiment circumstances including reduced material loading and reduced power capability. The experiment configuration uses an Al-Mg-Zn eutectic metal as the storage material, heated via heat tape wrapped around the vessel and guide tubes to bring the system to operation range (>400 °C) and to simulate charging heat exchange, respectively, with heat rejection occurring through the surfaces of the material and facilitated via guide tubes with less insulation wrapping. The model is available in the open-source repository HYBRID on Github.

25 - ENERGY STORAGE↗