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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 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2023

High-pressure CO 2 dissociation with nanosecond pulsed discharges

Herein we investigate the conversion of CO 2 into CO and O 2 with nanosecond repetitively pulsed (NRP) discharges in a high-pressure batch reactor. Stable discharges are obtained at up to 12 bar. By-products are measured with gas chromatography. The energy efficiency is determined for a range of processing times, pulse energy, and fill pressures. It is only weakly sensitive to the plasma operating parameters, i.e the extent of CO 2 conversion is almost linearly-dependent on the specific energy invested. A conversion rate as high as 14% is achieved with an energy efficiency of 23%. For long processing times, saturation in the yield and a drop in efficiency are observed, due to the increasing role of three-body recombination reactions, as described by zero-dimensional detailed kinetic modeling. The modeling reveals the presence of three-stage kinetics between NRP pulses, controlled by electron-impact CO 2 dissociation, vibrational relaxation, and neutral elementary kinetics. Transport effects are shown to be important for CO 2 conversion at high pressures. For fill pressures beyond 10 bar, CO 2 may locally transit into supercritical states. The supercritical plasma kinetics may bypass atomic oxygen pathways and directly convert CO 2 into O 2 . This work provides a detailed analysis of plasma-based high-pressure CO 2 conversion, which is of great relevance to future large-scale sustainable carbon capture, utilization, and storage.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
NASA NTRS1994

Computation of nonequilibrium viscous flows in arc-jet wind tunnel nozzles

The axisymmetric Navier-Stokes equations are numerically solved for air flows in converging-diverging conical nozzles. A nonequilibrium formulation with a two-temperature thermochemical model has been employed for vibrationally excited, partially dissociated and ionized air. Evaluations of the formulation is made through comparisons of the computed flow quantities with the experimental data obtained in expanding arc-jet nozzle flows. Two sets of experimental data obtained in conical nozzles with geometric exit-to-throat area ratios of 625 and 8100 cover reservoir pressures ranging from 5 to 95 atm and enthalpies from 5 to 10 MJ/kg. The computed results are in good agreement with local mass flux, Pitot pressure, and static wall pressure measurements at the nozzle exit. For low pressure reservoir conditions, comparisons of computations with the experimental data indicate that the wall catalycity is very important in predicting species mole fraction at the nozzle exit since gas phase chemistry is frozen. The current computations overpredict the atomic oxygen concentrations which in turn results in underprediction of the vibrational temperature.

Gokcen, Tahir↗
DOE OSTI2025

Assessment of thermally driven local structural phase changes in 1⁢𝑇′−MoTe 2

The role of layer disorder is important in establishing the topological phases of MoTe 2 . A rich tapestry of atomic ordering influences the structural phase transitions (SPTs), but there is little understanding of the mechanistic details of the phase transition. An atomistic level study was conducted to investigate the local structure of the 1⁢𝑇′ and 𝑇 𝑑 phases of MoTe 2 by using the pair distribution function (PDF) technique. While the average structure exhibits an SPT and coexistence of phases as a function of temperature, the local structure showed the suppression of SPT. The sample retained its monoclinic structure at all temperatures in short-range order. A sharp PDF peak observed at short distances indicated a strong atom-atom correlation between the Mo and Te atoms within the Mo octahedra. In addition, a large-box modeling of the PDF data indicated a preferential motion of Te atoms towards 𝑐 axis at all temperatures. Structural defects, such as stacking faults, likely result in the coexistence of phases in the average structure and suppress the local SPT of MoTe 2 . These results are stepping stones to understand the long-debated origins of structural, vibrational, and electronic properties of MoTe 2 and similar transition metal dichalcogenides.

2-dimensional systems↗
DOE OSTI2026

Bond Dissociation Energies of the Actinide Halides AnX, An = Ac–Lr and X = F–I, Utilizing Relativistic Composite Coupled Cluster Approaches

Bond dissociation energies (BDEs) have been calculated for the set of actinide halides AnX with An=Ac, Pa, and Np-Lr and X=F-I. Two composite thermochemistry methods based on the Feller-Peterson-Dixon (FPD) approach have been utilized, one involving spinor-based relativistic CCSD(T) calculations where spin-orbit (SO) was included at the orbital level and another using scalar relativistic CCSD(T) with a posteriori SO contributions based on 2-component multireference configuration interaction calculations. The method that was chosen for a given actinide halide was based on which representation yielded the best single determinant reference determinant for the coupled cluster calculation. The spinor-based method was chosen for all cases except for AmX, CmX, and BkX. Both composite approaches included contributions accounting for basis set truncation, outer-core correlation, the Gaunt interaction, and QED. The scalar FPD results, as well as the spinor-based calculations for AcF, also included higher order electron correlation up through CCSDT(Q). In addition to BDEs, CCSD(T) equilibrium bond lengths, harmonic frequencies, and vibrational anharmonicity constants are reported for all species. Last, the FPD BDEs for the fluorides were used to confirm the trend across the actinide series previously predicted by Gibson using bonding models based atomic promotion energies that provide a single 6d electron for bonding. In particular the local minimum in the BDEs at AmF is confirmed in the present calculations. Furthermore, the BDEs for LrX are predicted to be slightly larger than those of AcX, making them the largest in the actinide halide series.

Actinides↗
NASA NTRS1986

Evidence for nonlocal thermodynamic equilibrium in the nu3 mode of mesospheric ozone

Laboratory kinetic studies suggest that an appreciable fraction of the ozone produced by recombination of atomic oxygen is vibrationally excited in the nu3 mode. Further, laboratory data are available for the physical quenching of nu3, its radiative relaxation, and its radiative excitation by resonant absorption. It is shown that these chemical and physical processes are likely to result in substantial departures from local thermodynamic equilibrium for the nu3 mode of ozone in the mesosphere and therefore have important effects on infrared mesospheric ozone measurments by emission in the 9.6-micron band. Implications of these effects on data from the Limb Infrared Monitor of the Stratosphere (Remsberg et al, 1984), particularly their night/day ratio, are discussed.

Solomon, S.↗
DOE OSTI2025

Completely Multipolar Model for Many-Body Water–Ion and Ion–Ion Interactions

This work constructs an advanced force field, the Completely Multipolar Model (CMM), to quantitatively reproduce each term of an energy decomposition analysis (EDA) for aqueous solvated alkali metal cations and halide anions and their ion pairings. We find that all individual EDA terms remain well-approximated in the CMM for ion-water and ion-ion interactions, except for polarization, which shows errors due to the partial covalency of ion interactions near their equilibrium. We quantify the onset of the dative bonding regime by examining the change in molecular polarizability and Mayer bond indices as a function of distance, showing that partial covalency manifests by breaking the symmetry of atomic polarizabilities while strongly damping them at short-range. This motivates an environment-dependent atomic polarizability parameter that depends on the strength of the local electric field experienced by the ions to account for strong damping, with anisotropy introduced by atomic multipoles. The resulting CMM model for ions provides accurate dimer surfaces and three-body polarization and charge transfer compared to EDA, and shows excellent performance on various ion benchmarks including vibrational frequencies and cluster geometries.

Heindel, Joseph P↗
DOE OSTI2021

Attosecond Intramolecular Scattering and Vibronic Delays

We study the temporal and vibrational signature of the universal nuclear recoil associated with the electron emission and intramolecular scattering that accompanies the photoelectric effect. We illustrate these phenomena in the photoionization of the CO molecule from the C-1s orbital using an analytical model that reproduces the entangled character of the nuclear and electronic motion in this process. We show that the photoelectron emission delay can be decomposed into its localization and resonant-confinement components. Photoionization by a broadband x-ray pulse results in a coherent vibrational ionic state delayed compared to the classical sudden-photoemission limit.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2025

Generalized approach for rapid entropy calculation of liquids and solids

We build a comprehensive methodology for the fast computation of entropy across both solid and liquid phases. The proposed method utilizes a single trajectory of molecular dynamics (MD) to facilitate the calculation of entropy, which is composed of three components. The electronic entropy is determined through the temporal average acquired from density functional theory MD simulations. The vibrational entropy, typically the predominant contributor to the total entropy, even within the liquid state, is evaluated by computing the phonon density of states via the velocity autocorrelation function. The most arduous component to quantify, the configurational entropy, is assessed by probability analysis of the local structural arrangement and atomic distribution. We illustrate, through a variety of examples, that this method is both a versatile and valid technique for characterizing the thermodynamic states of both solids and liquids. Furthermore, this method is employed to expedite the calculation of melting temperatures, demonstrating its practical utility in computational thermodynamics.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Violation of the T –1 Relationship in the Lattice Thermal Conductivity of Mg 3 Sb 2 with Locally Asymmetric Vibrations

Most crystalline materials follow the guidelines of T –1 temperature-dependent lattice thermal conductivity (κ L ) at elevated temperatures. Here, we observe a weak temperature dependence of κ L in Mg 3 Sb 2 , T –0.48 from theory and T –0.57 from measurements, based on a comprehensive study combining ab initio molecular dynamics calculations and experimental measurements on single crystal Mg 3 Sb 2 . These results can be understood in terms of the so-called “phonon renormalization” effects due to the strong temperature dependence of the interatomic force constants (IFCs). The increasing temperature leads to the frequency upshifting for those low-frequency phonons dominating heat transport, and more importantly, the phonon-phonon interactions are weakened. In-depth analysis reveals that the phenomenon is closely related to the temperature-induced asymmetric movements of Mg atoms within MgSb 4 tetrahedron. With increasing temperature, these Mg atoms tend to locate at the areas with relatively low force in the force profile, leading to reduced effective 3 rd -order IFCs. The locally asymmetrical atomic movements at elevated temperatures can be further treated as an indicator of temperature-induced variations of IFCs and thus relatively strong phonon renormalization. The present work sheds light on the fundamental origins of anomalous temperature dependence of κ L in thermoelectrics.

36 MATERIALS SCIENCE↗
DOE OSTI2022

Reversible motions and disordered structure of soft particles in amorphous solids

In amorphous solids, soft vibrational modes derived from normal mode analysis can be utilized to identify the soft particles that are prone to irreversible rearrangements. However, the normal mode analysis approach cannot explain why the spatial distributions of clustered soft particles do not change over time. We define a softness parameter based on the vibrational density of states calculated directly from molecular dynamics simulations with both the harmonic vibrations and anharmonic relaxations being properly captured at finite temperatures. This parameter spontaneously correlates with the real space atomic motions and the dynamics heterogeneity. Using the softness parameter, we show that the softest particles are confined within rigid cages. These particles keep rearranging reversibly without long-range diffusion. The moderately soft particles rearrange irreversibly, and the hard particles mainly participate in vibrations without rearrangement. Here, we also show that the soft particles form locally disordered structures, while the hard particles present strong ordering. These findings confirm the defective nature of soft particles, and provide insights on the nature of softness as the ability to rearrange, but not necessarily irreversibly.

36 MATERIALS SCIENCE↗
DOE OSTI2023

Multidimensional Coherent Spectroscopy of Molecular Polaritons: Langevin Approach

We present a microscopic theory for nonlinear optical spectroscopy of N molecules in an optical cavity. Using the Heisenberg-Langevin equation, an analytical expression is derived for the time- and frequency-resolved signals accounting for arbitrary numbers of vibrational excitations. We identify clear signatures of the polariton-polaron interaction from multidimensional projections of the signal, e.g., pathways and timescales. Cooperative dynamics of cavity polaritons against intramolecular vibrations is revealed, along with a crosstalk between long-range coherence and vibronic coupling that may lead to localization effects. Our results further characterize the polaritonic coherence and the population transfer that is slower.

74 ATOMIC AND MOLECULAR PHYSICS↗
NASA NTRS1982

Compensation mechanism in liquid encapsulated Czochralski GaAs Importance of melt stoichiometry

It is shown that the key to reproducible growth of undoped semi-insulating GaAs by the liquid encapsulated Czochralski (LEC) technique is the control over the melt stoichiometry. Twelve crystals were grown from stoichiometric and nonstoichiometric melts. The material was characterized by secondary ion mass spectrometry, localized vibrational mode far infrared spectroscopy, Hall-effect measurements, optical absorption, and photoluminescence. A quantitative model for the compensation mechanism in the semi-insulating material was developed based on these measurements. The free carrier concentration is controlled by the balance between EL2 deep donors and carbon acceptors; furthermore, the incorporation of EL2 is controlled by the melt stoichiometry, increasing as the As atom fraction in the melt increases. As a result, semi-insulating material can be grown only from melts above a critical As composition. The practical significance of these results is discussed in terms of achieving high yield and reproducibility in the crystal growth process.

Holmes, D. E.↗
NASA NTRS1991

Theoretical characterization of the potential energy surface for the reversible reaction H + O2 yields HO2(asterisk) yields OH + O. III - Computed points to define a global potential energy surface

Computed energies and geometries are reported which, combined with previously published calculations, permit a global representation of the potential energy surface for the reaction H + O2 yields HO2(asterisk) yields OH + O. These new calculations characterize the potential energy surface (PES) for all H atom angles of approach to O2 and for the region of the inner repulsive wall. The region of the T-shaped H-O2 exchange saddle point is connected with the constrained energy minimum (CEM) path, and a new collinear H-O2 exchange saddle point is characterized which lies only 9 kcal/mol above the H + O2 asymptote. A vibrational analysis which utilizes local cubic and quartic polynomial representations of the PES along the CEM path has been carried out. Optimal geometries, energies, and harmonic frequencies are reported along with anharmonic analyses for the O2 and OH asymptotes and for the HO2 minimum region of the PES.

Walch, Stephen P.↗
DOE OSTI2024

A theory of phonon-induced friction on molecular adsorbates

In this manuscript, we provide a general theory for how surface phonons couple to molecular adsorbates. Our theory maps the extended dynamics of a surface’s atomic vibrational motions to a generalized Langevin equation, and by doing so captures these dynamics in a single quantity: the non-Markovian friction. The different frequency components of this friction are the phonon modes of the surface slab weighted by their coupling to the adsorbate degrees of freedom. Using this formalism, we demonstrate that physisorbed species couple primarily to acoustic phonons while chemisorbed species couple to dispersionless local vibrations. We subsequently derive equations for phonon-adjusted reaction rates using transition state theory and demonstrate that these corrections improve agreement with experimental results for CO desorption rates from Pt(111).

Science & Technology - Other Topics↗
DOE OSTI2022

Localized Phonon Densities of States at Grain Boundaries in Silicon

Since it is now possible to record vibrational spectra at nanometer scales in the electron microscope, it is of interest to explore whether extended defects in crystals such as dislocations or grain boundaries will result in measurable changes of the phonon densities of states (dos) that are reflected in the spectra. Phonon densities of states were calculated for a set of high angle grain boundaries in silicon. The boundaries are modeled by supercells with up to 160 atoms, and the vibrational densities of states were calculated by taking the Fourier transform of the velocity–velocity autocorrelation function from molecular dynamics simulations with larger supercells doubled in all three directions. In selected cases, the results were checked on the original supercells by comparison with the densities of states obtained by diagonalizing the dynamical matrix calculated using density functional theory. Near the core of the grain boundary, the height of the optic phonon peak in the dos at 60 meV was suppressed relative to features due to acoustic phonons that are largely unchanged relative to their bulk values. This can be attributed to the variation in the strength of bonds in grain boundary core regions where there is a range of bond lengths.

Materials Science↗
NASA NTRS1992

Ab initio atomic recombination reaction energetics on model heat shield surfaces

Ab initio quantum mechanical calculations on small hydration complexes involving the nitrate anion are reported. The self-consistent field method with accurate basis sets has been applied to compute completely optimized equilibrium geometries, vibrational frequencies, thermochemical parameters, and stable site labilities of complexes involving 1, 2, and 3 waters. The most stable geometries in the first hydration shell involve in-plane waters bridging pairs of nitrate oxygens with two equal and bent hydrogen bonds. A second extremely labile local minimum involves out-of-plane waters with a single hydrogen bond and lies about 2 kcal/mol higher. The potential in the region of the second minimum is extremely flat and qualitatively sensitive to changes in the basis set; it does not correspond to a true equilibrium structure.

Senese, Fredrick↗
DOE OSTI2025

Characterization of Two Positional Isomers of the Cs + Gly Complex Using Two-Color, IR–IR Photobleaching of the Cryogenically Cooled Ions

Metal ion binding to amino acid residues is an important interaction motif that controls the tertiary structures of oligopeptides. Analyses of the vibrational band patterns displayed by the amino acid scaffolds are commonly used to characterize the local docking motifs. Here we carry out two-color, IR-IR photobleaching measurements to obtain isomer-selective vibrational spectra of the Cs + Gly ion-molecule complex isolated in a cryogenically cooled, radiofrequency ion trap. The distinct band patterns of two non-interconverting isomers are observed and traced to different bidentate binding motifs between Cs + and the glycine scaffold. In one isomer, the ion attaches to the oxygen atoms of the carboxyl group whereas in the other it docks to the amino nitrogen and the carbonyl oxygen. Attachment to the acid head group yields a very diffuse absorption associated the OH group engaged in a strong intramolecular H-bond that closes a 5 membered ring. Furthermore, the band assignments, rearrangement pathways and electrostatic distortion of the electron density distributions in the glycine scaffold by the proximal ion are explored with electronic structure calculations and anharmonic theory.

Infrared spectroscopy↗
NASA NTRS2011

A Laboratory and Theoretical Study of Silicon Hydroxide SiOH

The rotational spectrum of the triatomic free radical SiOH in its X 2A' ground electronic state has been observed in a supersonic molecular beam by Fourier transform microwave spectroscopy. The fundamental (10,1 yields 00,0) transition has been detected for normal SiOH and for three rare isotopic species: (30)SiOH, Si(18)OH, and SiOD. The same transition has also been observed in two of three excited vibrational states, v2 and v3, for the most abundant species. Precise spectroscopic constants, including those that describe the effective spin doubling and hydrogen hyperfine structure, have been derived for each isotopic species or vibrational state. To complement the laboratory work, theoretical calculations of the structure, dipole moment, and energies of the X 2A' and low-lying 1 2A'' states have also been undertaken at the coupled cluster level of theory. In agreement with theoretical predictions, we conclude from the hyperfine constants that SiOH is a best described as a pi-type radical, with the unpaired electron localized on a p orbital on the silicon atom. Assuming a bond angle of 118.5 deg, the Si-O bond length is 1.647(2) Angstroms and the O-H bond length is 0.969(4) Angstrom.

McCarthy, M. C.↗