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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 1,747 records · Page 97
All sourcesNASA NTRSDOE OSTI
DOE OSTI2013

Rotational spectroscopy of pyridazine and its isotopologs from 235–360 GHz: Equilibrium structure and vibrational satellites

The rotational spectrum of pyridazine (o-C{sub 4}H{sub 4}N{sub 2}), the ortho disubstituted nitrogen analog of benzene, has been measured and analyzed in the gas phase. For the ground vibrational state of the normal isotopolog, over 2000 individual rotational transitions have been identified between 238 and 360 GHz and have been fit to 13 parameters of a 6th-order centrifugal distortion Hamiltonian. All transitions in this frequency region can now be predicted from this model to near experimental accuracy, i.e., well enough for the purpose of any future radio-astronomical search for this species. Three isotopologs, [3-{sup 13}C]-C{sub 4}H{sub 4}N{sub 2}, [4-{sup 13}C]-C{sub 4}H{sub 4}N{sub 2}, and [1-{sup 15}N]-C{sub 4}H{sub 4}N{sub 2}, have been detected in natural abundance, and several hundred lines have been measured for each of these species and fit to 6th-order Hamiltonians. Ten additional isotopologs were synthesized with enhanced deuterium substitution and analyzed to allow for a complete structure determination. The equilibrium structure (R{sub e}) of pyridazine was obtained by correcting the experimental rotational constants for the effects of vibration-rotation coupling using interaction constants predicted from CCSD(T) calculations with an ANO0 basis set and further correcting for the effect of electron mass. The final R{sub e} structural parameters are determined with excellent accuracy, as evidenced by their ability to predict 28 independent moments of inertia (I{sub a} and I{sub b} for 14 isotopologs) very well from 9 structural parameters. The rotational spectra of the six lowest-energy fundamental vibrational satellites of the main isotopolog have been detected. The rotational spectra of the five lowest-energy vibrational satellites have been assigned and fit to yield accurate rotational and distortion constants, while the fit and assignment for the sixth is less complete. The resultant vibration-rotation interaction (α) constants are found to be in excellent agreement with ones predicted from coupled-cluster calculations, which proved to be the key to unambiguous assignment of the satellite spectra to specific vibration modes.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Exploring the limit of accuracy for density functionals based on the generalized gradient approximation: Local, global hybrid, and range-separated hybrid functionals with and without dispersion corrections

The limit of accuracy for semi-empirical generalized gradient approximation (GGA) density functionals is explored by parameterizing a variety of local, global hybrid, and range-separated hybrid functionals. The training methodology employed differs from conventional approaches in 2 main ways: (1) Instead of uniformly truncating the exchange, same-spin correlation, and opposite-spin correlation functional inhomogeneity correction factors, all possible fits up to fourth order are considered, and (2) Instead of selecting the optimal functionals based solely on their training set performance, the fits are validated on an independent test set and ranked based on their overall performance on the training and test sets. The 3 different methods of accounting for exchange are trained both with and without dispersion corrections (DFT-D2 and VV10), resulting in a total of 491 508 candidate functionals. For each of the 9 functional classes considered, the results illustrate the trade-off between improved training set performance and diminished transferability. Since all 491 508 functionals are uniformly trained and tested, this methodology allows the relative strengths of each type of functional to be consistently compared and contrasted. The range-separated hybrid GGA functional paired with the VV10 nonlocal correlation functional emerges as the most accurate form for the present training and test sets, which span thermochemical energy differences, reaction barriers, and intermolecular interactions involving lighter main group elements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

First-principle calculation and assignment for vibrational spectra of Ba(Mg{sub 1/3}Nb{sub 2/3})O{sub 3} microwave dielectric ceramic

1:2 B-site cation ordered Ba(Mg{sub 1/3}Nb{sub 2/3})O{sub 3} ceramic was synthesized using conventional solid-state reaction at 1600 °C for 12 h. The structure parameters were obtained through Rietveld refinement of X-ray diffraction data. The Raman peak frequencies were obtained by Lorenz fitting on Raman spectrum. Four-parameter semiquantum model was used to fit the infrared (IR) reflectivity spectrum, and the fitted parameters were used to calculate the dielectric permittivity ε and dielectric loss tanδ. A total of 9 active Raman and 16 active IR modes were obtained using first-principle calculations based on density functional theory with local density approximation. All of the vibrational modes were assigned and represented by linear combinations of the symmetry coordinates deduced using group theory analysis. The Raman mode with the highest frequency A{sub 1g}{sup (4)} (789 cm{sup −1}) can be described as the breathing vibration of NbO{sub 6}. The IR modes E{sub u}{sup (1)} (149 cm{sup −1}) and A{sub 2u}{sup (2)} (212 cm{sup −1}), which can be described as the twisting vibrations of Ba–MgO{sub 6}/Ba–NbO{sub 6} on the a–b plane and the stretching vibrations of Ba–MgO{sub 6}/Ba–NbO{sub 6} along the c direction, respectively, are the dominant contributing modes to ε and tanδ. The dielectric property parameters obtained using IR spectrum fittings, first-principal calculations, and microwave measurements were compared.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Correlation between surface phonon mode and luminescence in nanocrystalline CdS thin films: An effect of ion beam irradiation

The influence of swift heavy ion irradiation (SHII) on surface phonon mode (SPM) and green emission in nanocrystalline CdS thin films grown by chemical bath deposition is studied. The SHII of nanocrystalline CdS thin films is carried out using 70 MeV Ni ions. The micro Raman analysis shows that asymmetry and broadening in fundamental longitudinal optical (LO) phonon mode increases systematically with increasing ion fluence. To analyze the role of phonon confinement, spatial correlation model (SCM) is fitted to the experimental data. The observed deviation of SCM to the experimental data is further investigated by fitting the micro Raman spectra using two Lorentzian line shapes. It is found that two Lorentzian functions (LFs) provide better fitting than SCM fitting and facilitate to identify the contribution of SPM in the observed distortion of LO mode. The behavior of SPM as a function of ion fluence is studied to correlate the observed asymmetry (Γ{sub a}/Γ{sub b}) and full width at half maximum of LO phonon mode and to understand the SHII induced enhancement of SPM. The ion beam induced interstitial and surface state defects in thin films, as observed by photoluminescence (PL) spectroscopy studies, may be the underlying reason for enhancement in SPM. PL studies also show enhancement in green luminescence with increase in ion fluence. PL analysis reveals that the variation in population density of surface state defects after SHII is similar to that of SPM. The correlation between SPM and luminescence and their dependence on ion irradiation fluence is explained with the help of thermal spike model.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2014

Universal scaling of potential energy functions describing intermolecular interactions. II. The halide-water and alkali metal-water interactions

The scaled versions of the newly introduced [S. S. Xantheas and J. C. Werhahn, J. Chem. Phys.141, 064117 (2014)] generalized forms of some popular potential energy functions (PEFs) describing intermolecular interactions – Mie, Lennard-Jones, Morse, and Buckingham exponential-6 – have been used to fit the ab initio relaxed approach paths and fixed approach paths for the halide-water, X - (H 2 O), X = F, Cl, Br, I, and alkali metal-water, M + (H 2 O), M = Li, Na, K, Rb, Cs, interactions. The generalized forms of those PEFs have an additional parameter with respect to the original forms and produce fits to the ab initio data that are between one and two orders of magnitude better in the χ 2 than the original PEFs. They were found to describe both the long-range, minimum and repulsive wall of the respective potential energy surfaces quite accurately. Overall the 4-parameter extended Morse (eM) and generalized Buckingham exponential-6 (gBe-6) potentials were found to best fit the ab initio data for these two classes of ion-water interactions. Finally, the fitted values of the parameter of the (eM) and (gBe-6) PEFs that control the repulsive wall of the potential correlate remarkably well with the ionic radii of the halide and alkali metal ions.

Werhahn, Jasper C.↗
DOE OSTI2014

Analytic representations of bath correlation functions for ohmic and superohmic spectral densities using simple poles

We present a scheme to express a bath correlation function (BCF) corresponding to a given spectral density (SD) as a sum of damped harmonic oscillations. Such a representation is needed, for example, in many open quantum system approaches. To this end we introduce a class of fit functions that enables us to model ohmic as well as superohmic behavior. We show that these functions allow for an analytic calculation of the BCF using pole expansions of the temperature dependent hyperbolic cotangent. We demonstrate how to use these functions to fit spectral densities exemplarily for cases encountered in the description of photosynthetic light harvesting complexes. Finally, we compare absorption spectra obtained for different fits with exact spectra and show that it is crucial to take properly into account the behavior at small frequencies when fitting a given SD.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Weighted-density functionals for cavity formation and dispersion energies in continuum solvation models

Continuum solvation models enable efficient first principles calculations of chemical reactions in solution, but require extensive parametrization and fitting for each solvent and class of solute systems. Here, we examine the assumptions of continuum solvation models in detail and replace empirical terms with physical models in order to construct a minimally-empirical solvation model. Specifically, we derive solvent radii from the nonlocal dielectric response of the solvent from ab initio calculations, construct a closed-form and parameter-free weighted-density approximation for the free energy of the cavity formation, and employ a pair-potential approximation for the dispersion energy. We show that the resulting model with a single solvent-independent parameter: the electron density threshold (n{sub c}), and a single solvent-dependent parameter: the dispersion scale factor (s{sub 6}), reproduces solvation energies of organic molecules in water, chloroform, and carbon tetrachloride with RMS errors of 1.1, 0.6 and 0.5 kcal/mol, respectively. We additionally show that fitting the solvent-dependent s{sub 6} parameter to the solvation energy of a single non-polar molecule does not substantially increase these errors. Parametrization of this model for other solvents, therefore, requires minimal effort and is possible without extensive databases of experimental solvation free energies.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

On readout of vibrational qubits using quantum beats

Readout of the final states of qubits is a crucial step towards implementing quantum computation in experiment. Although not scalable to large numbers of qubits per molecule, computational studies show that molecular vibrations could provide a significant (factor 2–5 in the literature) increase in the number of qubits compared to two-level systems. In this theoretical work, we explore the process of readout from vibrational qubits in thiophosgene molecule, SCCl{sub 2}, using quantum beat oscillations. The quantum beats are measured by first exciting the superposition of the qubit-encoding vibrational states to the electronically excited readout state with variable time-delay pulses. The resulting oscillation of population of the readout state is then detected as a function of time delay. In principle, fitting the quantum beat signal by an analytical expression should allow extracting the values of probability amplitudes and the relative phases of the vibrational qubit states. However, we found that if this procedure is implemented using the standard analytic expression for quantum beats, a non-negligible phase error is obtained. We discuss the origin and properties of this phase error, and propose a new analytical expression to correct the phase error. The corrected expression fits the quantum beat signal very accurately, which may permit reading out the final state of vibrational qubits in experiments by combining the analytic fitting expression with numerical modelling of the readout process. The new expression is also useful as a simple model for fitting any quantum beat experiments where more accurate phase information is desired.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Spicing up continuum solvation models with SaLSA: The spherically averaged liquid susceptibility ansatz

Continuum solvation models enable electronic structure calculations of systems in liquid environments, but because of the large number of empirical parameters, they are limited to the class of systems in their fit set (typically organic molecules). Here, we derive a solvation model with no empirical parameters for the dielectric response by taking the linear response limit of a classical density functional for molecular liquids. This model directly incorporates the nonlocal dielectric response of the liquid using an angular momentum expansion, and with a single fit parameter for dispersion contributions it predicts solvation energies of neutral molecules with a RMS error of 1.3 kcal/mol in water and 0.8 kcal/mol in chloroform and carbon tetrachloride. We show that this model is more accurate for strongly polar and charged systems than previous solvation models because of the parameter-free electric response, and demonstrate its suitability for ab initio solvation, including self-consistent solvation in quantum Monte Carlo calculations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Mapping the genome of meta-generalized gradient approximation density functionals: The search for B97M-V

A meta-generalized gradient approximation density functional paired with the VV10 nonlocal correlation functional is presented. The functional form is selected from more than 10{sup 10} choices carved out of a functional space of almost 10{sup 40} possibilities. Raw data come from training a vast number of candidate functional forms on a comprehensive training set of 1095 data points and testing the resulting fits on a comprehensive primary test set of 1153 data points. Functional forms are ranked based on their ability to reproduce the data in both the training and primary test sets with minimum empiricism, and filtered based on a set of physical constraints and an often-overlooked condition of satisfactory numerical precision with medium-sized integration grids. The resulting optimal functional form has 4 linear exchange parameters, 4 linear same-spin correlation parameters, and 4 linear opposite-spin correlation parameters, for a total of 12 fitted parameters. The final density functional, B97M-V, is further assessed on a secondary test set of 212 data points, applied to several large systems including the coronene dimer and water clusters, tested for the accurate prediction of intramolecular and intermolecular geometries, verified to have a readily attainable basis set limit, and checked for grid sensitivity. Compared to existing density functionals, B97M-V is remarkably accurate for non-bonded interactions and very satisfactory for thermochemical quantities such as atomization energies, but inherits the demonstrable limitations of existing local density functionals for barrier heights.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

Dynamics of neutrals and ions in an ultrafast laser produced Zn plasma

Optical time of flight dynamics of neutrals and ions in an ultrafast laser produced zinc plasma generated by irradiating a solid zinc target using 100 fs laser pulses is investigated. An acceleration of ions is observed which arises from internal Coulomb forces acting between charged species in the plasma. Some of the fast ions recombine with electrons in the plasma and generate fast neutrals. Plasma plume imaging performed at various ambient pressures indicates adiabatic expansion at lower pressures and plume front deceleration at higher pressures: at lower pressures the plume front-time (R-t) plot displays a linear expansion, shock wave model fits to the data at 5 Torr and at higher pressures the data fits better to the drag model. Furthermore, around an intermediate pressure of 10 Torr, the R-t plot fits to the shock wave model at earlier stages of plasma expansion, while it fits to the drag model at the later stages. These investigations provide relevant information on the acceleration of ions and neutrals in an expanding zinc plasma plume produced by ultrafast laser pulses.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2015

Intrinsic magnetic properties of L1{sub 0} FeNi obtained from meteorite NWA 6259

FeNi having the tetragonal L1{sub 0} crystal structure is a promising new rare-earth-free permanent magnet material. Laboratory synthesis is challenging, however, tetragonal L1{sub 0} FeNi—the mineral “tetrataenite”—has been characterized using specimens found in nickel-iron meteorites. Most notably, the meteorite NWA 6259 recovered from Northwest Africa is 95 vol. % tetrataenite with a composition of 43 at. % Ni. Hysteresis loops were measured as a function of sample orientation on a specimen cut from NWA 6259 in order to rigorously deduce the intrinsic hard magnetic properties of its L1{sub 0} phase. Electron backscatter diffraction showed that NWA 6259 is strongly textured, containing L1{sub 0} grains oriented along any one of the three equivalent cubic directions of the parent fcc structure. The magnetic structure was modeled as a superposition of the three orthonormal uniaxial variants. By simultaneously fitting first-quadrant magnetization data for 13 different orientations of the sample with respect to the applied field direction, the intrinsic magnetic properties were estimated to be saturation magnetization 4πM{sub s} = 14.7 kG and anisotropy field H{sub a} = 14.4 kOe. The anisotropy constant K = 0.84 MJ/m{sup 3} is somewhat smaller than the value K = 1.3 MJ/m{sup 3} obtained by earlier researchers from nominally equiatomic FeNi prepared by neutron irradiation accompanied by annealing in a magnetic field, suggesting that higher Ni content (fewer Fe antisite defects) may improve the anisotropy. The fit also indicated that NWA 6259 contains one dominant variant (62% by volume), the remainder of the sample being a second variant, and the third variant being absent altogether.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Effect of the interface resistance in non-local Hanle measurements

We use lateral spin valves with varying interface resistance to measure non-local Hanle effect in order to extract the spin-diffusion length of the non-magnetic channel. A general expression that describes spin injection and transport, taking into account the influence of the interface resistance, is used to fit our results. Whereas the fitted spin-diffusion length value is in agreement with the one obtained from standard non-local measurements in the case of a finite interface resistance, in the case of transparent contacts a clear disagreement is observed. The use of a corrected expression, recently proposed to account for the anisotropy of the spin absorption at the ferromagnetic electrodes, still yields a deviation of the fitted spin-diffusion length which increases for shorter channel distances. This deviation shows how sensitive the non-local Hanle fittings are, evidencing the complexity of obtaining spin transport information from such type of measurements.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2015

Time dependent changes in Schottky barrier mapping of the W/Si(001) interface utilizing ballistic electron emission microscopy

The W/Si(001) Schottky barrier height is mapped to nanoscale dimensions using ballistic electron emission microscopy (BEEM) over a period of 21 days to observe changes in the interface electrostatics. Initially, the average spectrum is fit to a Schottky barrier height of 0.71 eV, and the map is uniform with 98% of the spectra able to be fit. After 21 days, the average spectrum is fit to a Schottky barrier height of 0.62 eV, and the spatial map changes dramatically with only 27% of the spectra able to be fit. Transmission electron microscopy shows the formation of an ultra-thin tungsten silicide at the interface, which increases in thickness over the 21 days. This increase is attributed to an increase in electron scattering and the changes are observed in the BEEM measurements. Interestingly, little to no change is observed in the I-V measurements throughout the 21 day period.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2015

A temperature-dependent coarse-grained model for the thermoresponsive polymer poly(N-isopropylacrylamide)

A coarse-grained (CG) model is developed for the thermoresponsive polymer poly(N-isopropylacrylamide) (PNIPAM), using a hybrid top-down and bottom-up approach. Nonbonded parameters are fit to experimental thermodynamic data following the procedures of the SDK (Shinoda, DeVane, and Klein) CG force field, with minor adjustments to provide better agreement with radial distribution functions from atomistic simulations. Bonded parameters are fit to probability distributions from atomistic simulations using multi-centered Gaussian-based potentials. The temperature-dependent potentials derived for the PNIPAM CG model in this work properly capture the coil–globule transition of PNIPAM single chains and yield a chain-length dependence consistent with atomistic simulations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

First-principles investigations on ionization and thermal conductivity of polystyrene for inertial confinement fusion applications

Using quantum molecular-dynamics (QMD) methods based on the density functional theory, we have performed first-principles investigations of the ionization and thermal conductivity of polystyrene (CH) over a wide range of plasma conditions (ρ = 0.5 to 100 g/cm{sup 3} and T = 15 625 to 500 000 K). The ionization data from orbital-free molecular-dynamics calculations have been fitted with a “Saha-type” model as a function of the CH plasma density and temperature, which gives an increasing ionization as the CH density increases even at low temperatures (T < 50 eV). The orbital-free molecular dynamics method is only used to gauge the average ionization behavior of CH under the average-atom model in conjunction with the pressure-matching mixing rule. The thermal conductivities (κ{sub QMD}) of CH, derived directly from the Kohn–Sham molecular-dynamics calculations, are then analytically fitted with a generalized Coulomb logarithm [(lnΛ){sub QMD}] over a wide range of plasma conditions. When compared with the traditional ionization and thermal conductivity models used in radiation–hydrodynamics codes for inertial confinement fusion simulations, the QMD results show a large difference in the low-temperature regime in which strong coupling and electron degeneracy play an essential role in determining plasma properties. Hydrodynamic simulations of cryogenic deuterium–tritium targets with CH ablators on OMEGA and the National Ignition Facility using the QMD-derived ionization and thermal conductivity of CH have predicted ∼20% variation in target performance in terms of hot-spot pressure and neutron yield (gain) with respect to traditional model simulations.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗
DOE OSTI2016

Vibrational energies for HFCO using a neural network sum of exponentials potential energy surface

A six-dimensional potential energy surface (PES) for formyl fluoride (HFCO) is fit in a sum-of-products form using neural network exponential fitting functions. The ab initio data upon which the fit is based were computed at the explicitly correlated coupled cluster with single, double, and perturbative triple excitations [CCSD(T)-F12]/cc-pVTZ-F12 level of theory. The PES fit is accurate (RMSE = 10 cm{sup −1}) up to 10 000 cm{sup −1} above the zero point energy and covers most of the experimentally measured IR data. The PES is validated by computing vibrational energies for both HFCO and deuterated formyl fluoride (DFCO) using block improved relaxation with the multi-configuration time dependent Hartree approach. The frequencies of the fundamental modes, and all other vibrational states up to 5000 cm{sup −1} above the zero-point energy, are more accurate than those obtained from the previous MP2-based PES. The vibrational frequencies obtained on the PES are compared to anharmonic frequencies at the MP2/aug-cc-pVTZ and CCSD(T)/aug-cc-pVTZ levels of theory obtained using second-order vibrational perturbation theory. The new PES will be useful for quantum dynamics simulations for both HFCO and DFCO, e.g., studies of intramolecular vibrational redistribution leading to unimolecular dissociation and its laser control.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2016

Calibration of scintillation-light filters for neutron time-of-flight spectrometers at the National Ignition Facility

Sixty-four neutral density filters constructed of metal plates with 88 apertures of varying diameter have been radiographed with a soft x-ray source and CCD camera at National Security Technologies, Livermore. An analysis of the radiographs fits the radial dependence of the apertures’ image intensities to sigmoid functions, which can describe the rapidly decreasing intensity towards the apertures’ edges. The fitted image intensities determine the relative attenuation value of each filter. Absolute attenuation values of several imaged filters, measured in situ during calibration experiments, normalize the relative quantities which are now used in analyses of neutron spectrometer data at the National Ignition Facility.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗