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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 307 records · Page 17
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

Molecular hydrodynamic theory of the velocity autocorrelation function

The velocity autocorrelation function (VACF) encapsulates extensive information about a fluid’s molecular-structural and hydrodynamic properties. We address the following fundamental question: How well can a purely hydrodynamic description recover the molecular features of a fluid as exhibited by the VACF? To this end, we formulate a bona fide hydrodynamic theory of the tagged-particle VACF for simple fluids. Our approach is distinguished from previous efforts in two key ways: collective hydrodynamic modes and tagged-particle self-motion are modeled by linear hydrodynamic equations; the fluid’s spatial velocity power spectrum is identified as a necessary initial condition for the momentum current correlation. This formulation leads to a natural physical interpretation of the VACF as a superposition of products of quasinormal hydrodynamic modes weighted commensurately with the spatial velocity power spectrum, the latter of which appears to physically bridge continuum hydrodynamical behavior and discrete-particle kinetics. The methodology yields VACF calculations quantitatively on par with existing approaches for liquid noble gases and alkali metals. Furthermore, we obtain a new, hydrodynamic form of the self-intermediate scattering function whose description has been extended to low densities where the Schmidt number is of order unity; various calculations are performed for gaseous and supercritical argon to support the general validity of the theory. Excellent quantitative agreement is obtained with recent MD calculations for a dense supercritical Lennard-Jones fluid.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2023

Converging high-level coupled-cluster energetics via adaptive selection of excitation manifolds driven by moment expansions

A novel approach to rapidly converging high-level coupled-cluster (CC) energetics in an automated fashion is proposed. The key idea is an adaptive selection of excitation manifolds defining higher--than--two-body components of the cluster operator inspired by CC(P;Q) moment expansions. Further, the usefulness of the resulting methodology is illustrated by molecular examples where the goal is to recover the electronic energies obtained using the CC method with a full treatment of singly, doubly, and triply excited clusters (CCSDT) when the noniterative triples corrections to CCSD fail.

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

M06-SX screened-exchange density functional for chemistry and solid-state physics

Significance Density functionals with Hartree–Fock exchange have been widely used for a wide range of chemical applications, but the nonlocal character of exchange makes long-range exchange computationally expensive for solid-state calculations with periodic boundary conditions, and full exchange is nonphysical for condensed-phase systems. Here, we present a screened-exchange (SX) density functional, M06-SX, that is especially designed to have good accuracy for both solid-state physics and chemical applications with less computational cost than full Hartree–Fock exchange. The M06-SX functional gives accuracy comparable to functionals with full Hartree–Fock exchange for predicting chemical properties of molecules, while also being practical with good accuracy for plane wave calculations on band gaps and lattice constants of solids.

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

New reactions of diazene and related species for modelling combustion of amine fuels

Potential energy surfaces for reactions involving N 2 H 2 isomers of diazene (diimide) have been explored using density functional theory, with energies based on coupled-cluster theory. A focus is on processes that create or consume these species, and isomerisation between the E (trans) and Z (cis) forms of HNNH. Furthermore, these include isomerisation and dissociation pathways for HNNH, addition of H atoms to form N 2 H 3 , abstraction by H atoms yielding short-lived NNH, and abstraction reactions of H with N 2 H 3 . Transition state and capture theories are applied for high-pressure-limiting behaviour, while low-pressure and falloff regions are characterised via the methods of Troe and coworkers. Rate constants and thermochemistry are provided to improve models of diamine chemistry, relevant to the combustion of NH 3 especially at high concentrations, high pressures or under reducing conditions. Results indicate that amine radical recombination mainly yields the E HNNH isomer, while H-abstraction from N 2 H 3 results in E HNNH and H 2 NN. However, at elevated temperature E → Z isomerisation becomes competitive, and Z HNNH, being more reactive, acts to enhance the diazene consumption rate.

10 SYNTHETIC FUELS↗
DOE OSTI2024

Synthesis and investigation into explosive sensitivity for a series of new picramide explosives

Tailoring the molecular properties that govern energetic material sensitivity is essential to improve safety and help develop new energetic materials. Despite this need, understanding the complex chemistry and physics of explosive initiation and propagation is still a challenge. Recent work by our group has reinforced the view that explosive sensitivity under sub-shock conditions is connected to the strength of the weakest covalent bond in the molecule, that is, its “trigger linkage.” These correlations have been observed with different classes of energetic molecules and indicate that “trigger linkage” bond breaking, and heat of explosion are good indicators for the sensitivity trends. Herein we report the synthesis of aliphatic energetic materials with ethane, propane and neopentane backbones. Experimental and computational studies show that the trigger linkage model, based on results from quantum molecular dynamics simulations, correctly predicts trends observed in the impact sensitivity of the molecules. However, while the model predicts the impact sensitivities of the ethane series, the neopentane series has higher impact sensitivities than predicted, which is presumably influenced by crystal packing effects.

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

Plasma-assisted catalysis for ammonia synthesis in a dielectric barrier discharge reactor: key surface reaction steps and potential causes of low energy yield

Ammonia synthesis experiments were carried out in a coaxial dielectric barrier discharge (DBD) reactor packed with several different supports and metal catalysts. There was a marked increase in the reaction rate, over that obtained in an empty DBD plasma reactor, upon introduction of a packed bed of γ-Al 2 O 3 , Ru/γ-Al 2 O 3 , or SiO 2 particles. The difference in the reaction rates over γ-Al 2 O 3 and Ru/γ-Al 2 O 3 was minimal. Complementary zero-dimensional plasma kinetic model analysis was also performed using inputs from experimental data. This kinetic analysis allowed for gas phase reactions, Eley–Rideal (E–R) reactions, and direct adsorption of radical species on the γ-Al 2 O 3 surface. On the metal surface, dissociative adsorption of N 2 and H 2 , and Langmuir–Hinshelwood reactions were also included. This analysis revealed that, under the conditions of our experiments, ammonia synthesis proceeds principally by the formation of reactive radicals in the gas phase, which then adsorb and participate in E–R reactions on both the metal and support material surfaces. Furthermore, this finding illustrates a challenge for substantially increasing the energy yield for plasma-assisted ammonia synthesis in typical DBD reactors containing packed catalyst beads.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2026

The ballad of LLM agents: philosophical reasoning for chemistry

Large language models (LLMs) show remarkable potential for scientific reasoning but often produce unreliable or scientifically unactionable outputs when faced with multi-step logic, domain grounding, and interpretability challenges, especially in complex fields like chemistry and materials science. Here, we introduce a framework of philosophical reasoning agents, inspired by canonical thinkers such as Socrates, Descartes, Kant, and Hume, to guide LLM behavior via structured prompt engineering. These agents embody distinct reasoning paradigms (dialectical inquiry, deductive logic, rule-based judgment, and empirical validation) and are evaluated across multiple chemistry subdomains, physical, analytical, general, inorganic, and organic chemistry, using the ChemBench benchmark. Our agentic prompting approach yields substantial accuracy gains on open-ended numerical chemistry questions, with gains of +11.5 percentage points for GPT-4o with Hume, +4.5 percentage points for GPT-5 with Kant, and +21.8 percentage points for GPT-5.1 with Socrates at the strict 1% error threshold, relative to the corresponding base models. Beyond accuracy, we observe benchmark-level model–agent performance patterns, suggesting that different prompting styles interact differently with each base model. These findings demonstrate that embedding philosophy-of-science principles into multi-agent frameworks can improve and produce interpretable, adaptive, and domain-aligned scientific LLMs.

Harb, Hassan [Argonne National Laboratory (ANL), A↗
DOE OSTI2020

Nematic ordering of hard rods under strong confinement in a dense array of nanoposts

The effect of confinement on the behavior of liquid crystals is interesting from a fundamental and practical standpoint. In this work, we report Monte Carlo simulations of hard rods in an array of hard nanoposts, where the surface-to-surface separations between nanoposts are comparable to or less than the length of hard rods. This particular system shows promise as a means of generating large-scale organization of the nematic liquid by introducing an entropic external field set by the alignment of nanoposts. The simulations show that nematic ordering of hard rods is enhanced in the nanopost arrays compared with that in bulk, in the sense that the nematic order is significant even at low concentrations at which hard rods remain isotropic in bulk, and the enhancement becomes more significant as the passage width between two nearest nanoposts decreases. An analysis of local distribution of hard-rod orientations at low concentrations with weak nematic ordering reveals that hard rods are preferentially aligned along nanoposts in the narrowing regions between two curved surfaces of nearest nanoposts; hard rods are less ordered in the passages and in the centers of interpost spaces. Finally, it is concluded that at low concentrations the confinement in a dense array of nanoposts induces the localized nematic order first in the narrowing regions and, as the concentration further increases, the nematic order spreads over the whole region. The formation of a well-ordered phase at low concentrations of hard rods in a dense array of nanoposts can provide a new route to the low-concentration preparation of nematic liquid crystals that can be used as anisotropic dispersion media.

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

Effective traplike activated dynamics in a continuous landscape

In this work, we use a simple model to extend network models for activated dynamics to a continuous landscape with a well-defined notion of distance and a direct connection to many-body systems. The model consists of a tracer in a high-dimensional funnel landscape with no disorder. We find a nonequilibrium low-temperature phase with aging dynamics that is effectively equivalent to that of models with built-in disorder, such as the trap model, step model and random energy model. Finally, we compare entropy with energy-driven activation, and we remark that the former is more robust to the choice of the dynamics since it does not depend on whether one uses local or global updates.

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

Tuning Stoichiometry to Promote Formation of Binary Colloidal Superlattices

The self-assembly of binary nanoparticle superlattices from colloidal mixtures is a promising method for the fabrication of complex colloidal cocrystal structures. However, binary mixtures often form amorphous or metastable phases instead of the thermodynamically stable phase. Here we show that in binary mixtures of differently sized spherical particles, an excess of the smaller component can promote—and, in some cases, may be necessary for—the self-assembly of a binary cocrystal. Using computer simulations, we identify two mechanisms responsible for this phenomenon. First, excess small particles act like plasticizers and enable systems to reach a greater supersaturation before kinetic arrest occurs. Second, they can disfavor competing structures that may interfere with the growth of the target structure. We find the phase behavior of simulated mixtures of nearly hard spheres closely matches published experimental results. We demonstrate the generality of our findings for mixtures of particles of arbitrary shape by presenting a binary mixture of hard shapes that only self-assembles with an excess of the smaller component.

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

Actinide N-Donor Thermodynamics: Expanding the f-element Covalency Dialogue. Final report

Resolving the chemistry and physics of f-electrons is one of the grand challenges of science for energy technology. A central component of this challenge is describing covalency in actinide-ligand interactions. Crystallography, x-ray spectroscopy and computational techniques have provided reasonable, and in some cases remarkable, support for covalency in actinide-ligand interactions. Courtesy the quality of the results obtained, a significant portion of the covalency dialogue has been forwarded through solid-state and computational studies of the more stable actinides (Th, U, Pu, Np). However; recent reports have questioned whether covalency in actinide interactions increases or decreases across the series. Examination of less-stable trans-actinides (Am, Cm, Bk, Cf and Es) by the aforementioned approaches can be rapidly limited due to material availability, radiological hazards and experimental data to validate computational models. Furthermore, limited thermodynamic data exists to confirm covalency in actinide solution phase interactions that are highly relevant to the remediation and reprocessing of used nuclear fuel. The best-defined interactions of actinides with soft donors in aqueous solutions involve (poly)aminopolycarboxylate (APC) ligands. The chelate effect and binding affinity with the acetic acid APCs subgroups encourages amine interactions with the actinide metal center. In the absence of these factors, amine interactions with actinides are too weak to overcome the protective hydration shell of the dissolved ion. The ability for APCs to force actinide interactions with soft nitrogen donors (as defined by Pearson’s Hard Soft Acid Base theory) encourages the application of these ligands in a variety of processes for actinide recovery from nearly chemically identical lanthanides. The ability to functionalize the amine center of the ligand in a variety of capacities (adding additional amine groups, exchanging the conventional acetate group for an acetate group, etcetera), allows for the APC ligand to serve as a thermodynamic probe for actinide-nitrogen interactions. Perhaps the single most significant breakthrough during the previous funding cycle was the observation that covalency for the transplutonium part of the actinide series can be increasingly influenced with energy degeneracy driven covalency as the actinides become heavier. This was observed most predominantly with dipicolinic acid, but extensions of f-orbital degeneracy were found to affect aliphatic aminopolycarboxylate-actinide complexes through einsteinium.

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

High-Accuracy Module Emulators from Physically-Constrained AI Algorithms

Focal Area(s): How do we use AI tools to integrate observations, simulated data and physical and chemical fundamentals (Focal Area 3) into model components (Focal Area 2) that have high accuracy and stability and low computational burden to improve Earth System Predictability? Science Challenge: Earth system modeling of the hydrological cycle involves compute-intensive modules representing complex chemical and physical process. Recently, AI tools that are far less compute intensive have been developed that emulate these modules, but many of these efforts are not yet sufficiently accurate or even stable. We know a lot about the physics and chemistry of earth system processes. The Science Challenge is developing AI tools that not only incorporate observations and simulated data, but also incorporate the physics and chemistry of the process, while still maintaining the compute efficiency.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2023

A review of the shear rheology of carbon black suspensions

The microstructural link to the rheology of carbon black suspensions has recently become clear as a result of advances in computational and experimental methods. This understanding reveals the important role of the restructuring, build-up, and break-up of carbon black agglomerates in simple shear, rationalized by a dimensionless balance of the hydrodynamic forces acting to break the agglomerates apart against the cohesive forces holding them together (i.e., the Mason number). The Mason number not only can predict the origin of reversible thixotropy seen in carbon black suspensions observed at higher shear intensities, but can also be used to rationalize the evolution of microstructure at lower shear intensities. This review focuses on carbon black suspension behavior, but the insights derived from carbon black suspensions are broadly applicable to a diverse class of soft matter including colloidal gels relevant to a variety of applications.

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

The Scattering of Phonons by Infinitely Long Quantum Dislocations Segments and the Generation of Thermal Transport Anisotropy in a Solid Threaded by Many Parallel Dislocations

A canonical quantization procedure is applied to the interaction of elastic waves—phonons—with infinitely long dislocations that can oscillate about an equilibrium, straight line, configuration. The interaction is implemented through the well-known Peach–Koehler force. For small dislocation excursions away from the equilibrium position, the quantum theory can be solved to all orders in the coupling constant. We study in detail the quantum excitations of the dislocation line and its interactions with phonons. The consequences for the drag on a dislocation caused by the phonon wind are pointed out. We compute the cross-section for phonons incident on the dislocation lines for an arbitrary angle of incidence. The consequences for thermal transport are explored, and we compare our results, involving a dynamic dislocation, with those of Klemens and Carruthers, involving a static dislocation. In our case, the relaxation time is inversely proportional to frequency, rather than directly proportional to frequency. As a consequence, the thermal transport anisotropy generated on a material by the presence of a highly-oriented array of dislocations is considerably more sensitive to the frequency of each propagating mode, and, therefore, to the temperature of the material.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2024

Interpreting accelerated tests on perovskite modules using photooxidation of MAPbI 3 as an example

Solar panels (modules) based on metal halide perovskites are following a fast track to commercialization. Unlike more established solar cell materials, there are not yet decades-long field observations to increase consumer confidence. The "physics and chemistry of failure" approach is used in other industries and estimates product degradation based on laboratory accelerated tests integrated with an understanding of degradation mechanisms. This work uses that approach to quantify the relationship between accelerated tests and projected product behavior for metal halide perovskite modules. Degradation involving photooxidation of methylammonium lead iodide is used to illustrate the method. Acceleration factors in common accelerated tests are found to be low. Conclusions emphasize that the accelerated tests on photovoltaics should not be interpreted as equivalent across module types or as a green light for commercialization unless supported by the appropriate field data or physics and chemistry of failure analysis.

14 SOLAR ENERGY↗
DOE OSTI2022

Dehydration of gas-phase benzyl amine alcohols studied at atmospheric pressure

Gas-phase ion chemistry is a useful approach for the investigation of physical organic chemistry and the study of reactivity, structure, and thermochemical properties of ionic and neutral organic substrates. Herein, one-step dehydration of gas-phase benzyl amine alcohols to give benzazetidines was discovered without the use of catalysts. Mechanistic investigations of the gas-phase dehydration reactions were explored to study the possible influence of charged microdroplet acceleration during electrospray ionization (ESI) and collisions occurring during ion transfer through the atmospheric pressure interface (API) of the mass spectrometer. The product ion distribution was observed to be less sensitive to droplet effects (spray distance and voltage), and temperature of transfer capillary in the API. However, the product ion distribution exhibit high sensitivity to different S-lens radio frequency (RF) voltage of the API, providing evidence that the dehydration reaction is driven by collisions during ion transfer in the API. With this insight, we developed atmospheric pressure thermal dissociation platform that allowed thermal-induced collisions outside of the mass spectrometer when the benzyl amine alcohols are carried through a heated coiled tube. Up to 98% dissociation efficiency was achieved with the coiled tube heated to a temperature of 200 °C, yielding only the desired benzazetidine product. Finally, by performing the atmospheric pressure thermal dissociation experiment outside of the mass spectrometer, we believe it will be straightforward to collect the dehydration product.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗