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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 541 records · Page 30
All sourcesNASA NTRSDOE OSTI
NASA NTRS1984

Radiative lifetimes of the second negative system of O2(+)

The dipole moment of the A2Pi(u)-X2Pi(g) transition of O2(+) is calculated as a function of internuclear distance using ab initio methods. The band absorption oscillator strengths and band transition probabilities of the second negative system are derived and the resulting lifetimes are compared with experimental data. The high-lying v double prime levels of the ground state may decay into low-lying v prime levels of the excited state. The corresponding radiative lifetimes are calculated.

Wetmore, R. W.↗
NASA NTRS2004

Vibrational Spectroscopy of Ions and Radicals Present in the Interstellar Medium and in Planetary Atmospheres: A Theoretical Study

Anharmonic vibrational frequencies and intensities are calculated for OH(H2O)n and H(H2O)n radicals (that form on icy particles of the interstellar medium), HCO radical (the main intermediate in the synthesis of organic molecules in space), NH2(-) and C2H(-) anions, H5(+) cation, and other systems relevant to interstellar chemistry. In addition to pure ions and radicals, their complexes with water are studied to assess the effects of water environment on infrared spectra. The calculations are performed using the correlation-corrected vibrational self-consistent field (CC-VSCF) method with ab initio potential surfaces at the MP2 and CCSD(T) levels. Fundamental, overtone, and combination excitations are computed. The results are in good agreement with available experimental data and provide reliable predictions for vibrational excitations not yet measured in laboratory experiments. The data should be useful for interpretation of astronomically observed spectra and identification of ions and radicals present in the interstellar medium and in planetary atmospheres.

Chaban, Galina M.↗
DOE OSTI2024

An Ab initio based OH initiated oxidation kinetics of glycerol carbonate: A promising biofuel component

The global energy demand is steadily increasing because of the population explosion and economic growth. Fossil fuels supply around 85 % of global primary energy demand. On one hand, fulfilling the increasing energy demands is a big challenge for the next few decades. On the other hand, the continued burning of fossil fuels leads to higher CO2 emissions, severely impacting global warming. Therefore, the policymakers vow to shift from conventional fuels to renewable resources for economic, environmental, and future energy security reasons. In this context, biofuels from lignocellulosic biomass and/or carbon-neutral fuels produced in the sustainable carbon cycle can close the carbon cycle and reach net zero-carbon emission. Recently, glycerol carbonate has been proposed as a promising fuel or fuel additive for future sustainability. Therefore, we investigated the hydrogen abstraction reactions of glycerol carbonate (GC) by OH radicals using high-level ab initio and variational transition state theory calculations. We mapped out the potential energy surface using the CCSD(T)/cc-pV(D, T)Z//MP2/cc-pVTZ level of theory. Here we used the ab initio parameters to obtain the site-specific rate coefficients by employing the variational transition state theory. We observed that every hydrogen atom in GC displays a unique reactivity with OH radicals. We derived branching ratio of each channel that are difficult to access experimentally. The overall rate coefficients exhibit a strong non-Arrhenius behaviour, which can be represented as: $k^{CVT/SCT}_{ov}$ (T) = 3.39 x 10 -20 x T 2.659 x e$\frac{-750.0 Jmol^{-1}}{RT}$ $\frac{cm^{3}}{molecule s}$ This is the first reported rate data for the glycerol carbonate and OH radicals reaction.

09 BIOMASS FUELS↗
DOE OSTI2016

Mode-selective chemistry on metal surfaces: The dissociative chemisorption of CH{sub 4} on Pt(111)

A quantum approach based on an expansion in vibrationally adiabatic eigenstates is used to explore CH{sub 4} dissociation on Pt(111). Computed sticking probabilities for molecules in the ground, 1v{sub 3} and 2v{sub 3}, states are in very good agreement with the available experimental data, reproducing the variation in reactivity with collision energy and vibrational state. As was found in similar studies on Ni(100) and Ni(111), exciting the 1v{sub 1} symmetric stretch of CH{sub 4} is more effective at promoting the dissociative chemisorption of CH{sub 4} than exciting the 1v{sub 3} antisymmetric stretch. This behavior is explained in terms of symmetry, mode-softening, and nonadiabatic transitions between vibrationally adiabatic states. We find that the efficacies of the bending modes for promoting reaction are reasonably large, and similar to the 1v{sub 3} state. The vibrational efficacies for promoting reaction on Ni(111) are larger than for reaction on Pt(111), due to the larger nonadiabatic couplings. Our computed sticking probabilities are in good agreement with results from recent ab initio molecular dynamics and reactive force field studies.

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

Ab initio calculation of muon capture on 24 Mg

In this work we study ordinary muon capture (OMC) on 24 Mg from a first-principles perspective. Starting from a particular two- and three-nucleon interaction derived from chiral effective field theory, we use the valence-space in-medium similarity renormalization group (VS-IMSRG) framework to construct effective Hamiltonians and muon-capture operators, which nonperturbatively account for many-body physics outside the valence space. Here, the obtained nuclear matrix elements are compared against those from the phenomenological shell model. The impact of including the correlations from the nuclear shell model (NSM) as well as including the induced twobody part is studied in detail. Furthermore, the effects of realistic bound-muon wave function on the operators is studied. Finally, predictions for capture rates to the lowest excited states in 24 Na are given and compared with available data. It is found that the spectroscopic properties of 24 Mg and its OMC daughter 24 Na are fairly well described by both the NSM and VS-IMSRG, and that the effect of the hadronic two-body currents significantly reduces the OMC rates. Both models have some difficulties in matching the measured OMC rates, especially for the 2 + final states. This calls for further studies in other light nuclei with available OMC data.

20 ≤ A ≤ 38↗
DOE OSTI2018

Spectral Analysis of 3-(Adamantan-1-yl)-4-Ethyl-1-[(4-Phenylpiperazin-1-yl) Methyl]-1H-1,2,4-Triazole-5(4H)-Thione

Vibrational IR (3200–650 cm{sup –1}) and Raman spectra (3200–150 cm{sup –1}) of adamantane-containing 3-(adamantan-1-yl)-4-ethyl-1-[(4-phenylpiperazin-1-yl)methyl]-1H-1,2,4-triazole-5(4H)-thione, which is promising for drug design, were examined. The UV/Vis spectrum (450–200 nm) of the compound in EtOH was measured. Full geometry optimization using density functional theory (DFT) in the B3LYP/cc-pVDZ approximation allowed the equilibrium configuration of the molecule to be determined and IR and Raman spectra to be calculated. Based on these, the experimental vibrational IR and Raman spectra were interpreted and the biological activity indices were predicted. The UV/Vis spectrum of the title compound was simulated at the time-dependent DFT/CAM-B3LYP/cc-pVDZ level with and without solvent effects and at the ab initio multi-reference perturbation theory XMCQDPT2 level. The UV/Vis spectrum that was simulated using the multi-reference XMCQDPT2 approximation agreed very successfully with the experimental data, in contrast to the single-reference DFT method. This was probably a consequence of intramolecular charge transfer.

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

A thermodynamic model to predict the aqueous solubility of hydrocarbon mixtures at two-phase hydrate-liquid water equilibrium

In order to understand the fate and transport of hydrocarbons and hydrocarbon mixtures in the deep sea and underlying sediments it requires an accurate determination of the two-phase hydrate (H)-liquid water (L w ) thermodynamic equilibrium in the absence of a free gas phase. In addition to controlling hydrate formation directly from the aqueous phase, the H-L w equilibrium provides the aqueous solubility of dissolving hydrate. The aqueous solubility of hydrocarbon mixture at H-L w equilibrium was calculated based on the van der Waals and Platteeuw statistical thermodynamic model and the Holder model. Langmuir constants were calculated from cell potential parameters obtained from ab initio intermolecular potentials and thus the model contains no fitting parameters. The model accurately predicts pure methane, ethane, and propane experimental H-L w equilibrium solubility data, including new data provided here for methane. Here, we present hydrocarbon solubilities in water and seawater at H-L w equilibrium at deep sea conditions for both methane and a thermogenic mixture based on the methane–ethane–propane ratio from the 2010 Macondo oil spill. We also present model predictions of the proportion of occupied large and small cages at H-L w equilibrium for both systems, as well as hydrocarbon ratios in the hydrate phase for the thermogenic mixture.

58 GEOSCIENCES↗
DOE OSTI2017

Phonon thermal transport in 2H, 4H and 6H silicon carbide from first principles

Here, silicon carbide (SiC) is a wide band gap semiconductor with a variety of industrial applications. Among its many useful properties is its high thermal conductivity, which makes it advantageous for thermal management applications. In this paper we present ab initio calculations of the in-plane and cross-plane thermal conductivities, κ in and κ out , of three common hexagonal polytypes of SiC: 2H, 4H and 6H. The phonon Boltzmann transport equation is solved iteratively using as input interatomic force constants determined from density functional theory. Both κ in and κ out decrease with increasing n in nH SiC because of additional low-lying optic phonon branches. These optic branches are characterized by low phonon group velocities, and they increase the phase space for phonon-phonon scattering of acoustic modes. Also, for all n, κ in is found to be larger than κ out in the temperature range considered. At electron concentrations present in experimental samples, scattering of phonons by electrons is shown to be negligible except well below room temperature where it can lead to a significant reduction of the lattice thermal conductivity. This work highlights the power of ab initio approaches in giving quantitative, predictive descriptions of thermal transport in materials. It helps explain the qualitative disagreement that exists among different sets of measured thermal conductivity data and provides information of the relative quality of samples from which measured data was obtained.

36 MATERIALS SCIENCE↗
DOE OSTI2018

High-throughput density-functional perturbation theory phonons for inorganic materials

The knowledge of the vibrational properties of a material is of key importance to understand physical phenomena such as thermal conductivity, superconductivity, and ferroelectricity among others. However, detailed experimental phonon spectra are available only for a limited number of materials, which hinders the large-scale analysis of vibrational properties and their derived quantities. In this work, we perform ab initio calculations of the full phonon dispersion and vibrational density of states for 1521 semiconductor compounds in the harmonic approximation based on density functional perturbation theory. The data is collected along with derived dielectric and thermodynamic properties. As a result, we present the procedure used to obtain the results, the details of the provided database and a validation based on the comparison with experimental data.

36 MATERIALS SCIENCE↗
DOE OSTI2015

Forbidden optical transition in Ti-like Xe, Ba, and Ir

We present measurements of the (3d{sup 4}){sup 5}D{sub 2}−{sup 5}D{sub 3} transitions in the Ti-like ions Xe{sup 32+}, Ba{sup 34+}, and Ir{sup 55+} produced and trapped in the Heidelberg electron beam ion trap. The obtained wavelengths have a precision at the few ppm-level and are thereby the most precise measurements of these transitions up to date. For Z=60−75 semi-empirical calculations have shown excellent agreement, however our measurements combined with data from other works shows that outside this range predictions quickly deviate. The value obtained for Ir{sup 55+} 357.434(2) nm confirms the linear mismatch to ab initio calculations for Z > 70, as hypothesized in Utter et al., Phys. Rev. A 67, 012508 (2003)

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2015

Electron-impact vibrational excitation of cyclopropane

We report a very detailed test of the ab initio discrete momentum representation (DMR) method of calculating vibrational excitation of polyatomic molecules by electron impact, by comparison of its results with an extensive set of experimental data, covering the entire range of scattering angles from 10{sup ∘} to 180{sup ∘} and electron energies from 0.4 to 20 eV. The DMR calculations were carried out by solving the two-channel Lippmann-Schwinger equation in the momentum space, and the interaction between the scattered electron and the target molecule was described by exact static-exchange potential corrected by a density functional theory (DFT) correlation-polarization interaction that models target’s response to the field of incoming electron. The theory is found to quantitatively reproduce the measured spectra for all normal modes, even at the difficult conditions of extreme angles and at low energies, and thus provides full understanding of the excitation mechanism. It is shown that the overlap of individual vibrational bands caused by limited experimental resolution and rotational excitation must be properly taken into account for correct comparison of experiment and theory. By doing so, an apparent discrepancy between published experimental data could be reconciled. A substantial cross section is found for excitation of the non-symmetric HCH twisting mode ν{sub 4} of A{sub 1}{sup ″} symmetry by the 5.5 eV A{sub 2}{sup ′} resonance, surprisingly because the currently accepted selection rules predict this process to be forbidden. The DMR theory shows that the excitation is caused by an incoming electron in an f-wave of A{sub 2}{sup ′} symmetry which causes excitation of the non-symmetric HCH twisting mode ν{sub 4} of the A{sub 1}{sup ″} symmetry and departs in p- and f-waves of A{sub 2}{sup ″} symmetry.

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

Liquid Be, Ca and Ba. An orbital-free ab-initio molecular dynamics study

Several static and dynamic properties of liquid beryllium (l-Be), liquid calcium (l-Ca) and liquid barium (l-Ba) near their triple point have been evaluated by the orbital-free ab initio molecular dynamics method (OF-AIMD), where the interaction between valence electrons and ions is described by means of local pseudopotentials. These local pseudopotentials used were constructed through a force-matching process with those obtained from a Kohn-Sham ab initio molecular dynamics study (KS-AIMD) of a reduced system with non-local pseudopotentials. The calculated static structures show good agreement with the available experimental data, including an asymmetric second peak in the structure factor which has been linked to the existence of a marked icosahedral short-range order in the liquid. As for the dynamic properties, we obtain collective density excitations whose associated dispersion relations exhibit a positive dispersion.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2017

Ab initio simulations of the dynamic ion structure factor of warm dense lithium

Here, we present molecular dynamics simulations based on finite-temperature density functional theory that determine self-consistently the dynamic ion structure factor and the electronic form factor in lithium. Our comprehensive data set allows for the calculation of the dispersion relation for collective excitations, the calculation of the sound velocity, and the determination of the ion feature from the total electronic form factor and the ion structure factor. The results are compared with available experimental x-ray and neutron scattering data. Good agreement is found for both the liquid metal and warm dense matter domain. Finally, we study the impact of possible target inhomogeneities on x-ray scattering spectra.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Spin-orbit coupled systems in the atomic limit: rhenates, osmates, iridates

Motivated by RIXS experiments on a wide range of complex heavy oxides, including rhenates, osmates, and iridates, we discuss the theory of RIXS for site-localized t 2 g orbital systems with strong spin-orbit coupling. For such systems, we present exact diagonalization results for the spectrum at different electron fillings, showing that it accesses “single-particle” and “multiparticle” excitations. This leads to a simple picture for the energies and intensities of the RIXS spectra in Mott insulators such as double perovskites which feature highly localized electrons, and yields estimates of the spin-orbit coupling and Hund's coupling in correlated 5d oxides. We present new higher resolution RIXS data at the Re L 3 edge in Ba 2 YReO 6 which finds a previously unresolved peak splitting, providing further confirmation of our theoretical predictions. Using ab initio electronic structure calculations on Ba 2 MReO 6 (with M=Re, Os, Ir) we show that while the atomic limit yields a reasonable effective Hamiltonian description of the experimental observations, effects such as t 2 g –e g interactions and hybridization with oxygen are important. Our ab initio estimate for the strength of the intersite exchange coupling shows that, compared to the d 3 systems, the exchange is one or two orders of magnitude weaker in the d 2 and d 4 materials, which may partly explain the suppression of long-range magnetic order in the latter compounds. As a way to interpolate between the site-localized picture and our electronic structure band calculations, we discuss the spin-orbital levels of the MO 6 cluster. In conclusion, this suggests a possible role for intracluster excitons in Ba 2 YIrO 6 which may lead to a weak breakdown of the atomic J eff = 0 picture and to small magnetic moments.

74 ATOMIC AND MOLECULAR PHYSICS↗
DOE OSTI2020

Strong QCD from Hadron Structure Experiments

The topical workshop Strong QCD from Hadron Structure Experiments took place at Jefferson Lab from November 6–9, 2019. Impressive progress in relating hadron structure observables to the strong QCD mechanisms has been achieved from the ab initio QCD description of hadron structure in a diverse array of methods in order to expose emergent phenomena via quasi-particle formation. The wealth of experimental data and the advances in hadron structure theory make it possible to gain insight into strong interaction dynamics in the regime of large quark–gluon coupling (the strong QCD regime), which will address the most challenging problems of the Standard Model on the nature of the dominant part of hadron mass, quark–gluon confinement, and the emergence of the ground and excited state hadrons, as well as atomic nuclei, from QCD. This workshop aimed to develop plans and to facilitate the future synergistic efforts between experimentalists, phenomenologists, and theorists working on studies of hadron spectroscopy and structure with the goal to connect the properties of hadrons and atomic nuclei available from data to the strong QCD dynamics underlying their emergence from QCD. These results pave the way for a future breakthrough extension in the studies of QCD with an Electron–Ion Collider in the U.S.

Brodsky, S. J.↗
DOE OSTI2016

Quantum-state dependence of product branching ratios in vacuum ultraviolet photodissociation of N{sub 2}

The branching ratios for the N({sup 4}S) + N({sup 2}D), N({sup 4}S) + N({sup 2}P), and N({sup 2}D) + N({sup 2}D) channels are measured for the photodissociation of N{sub 2}(X{sup 1}Σ{sub g}{sup +};v{sup ′′}=0,J{sup ′′}) in the vacuum ultraviolet (VUV) region of 100,808–122,159 cm{sup −1} using the VUV–VUV pump-probe approach combined with velocity-map-imaging-photoion detection. No evidence of forming the ground-state N({sup 4}S) + N({sup 4}S) products is found. No potential barrier is observed for the N({sup 2}D) + N({sup 2}D) channel, but the N({sup 4}S) + N({sup 2}P) channel has a small potential barrier of ≈740 cm{sup −1}. The branching ratios are found to depend on the symmetry of predissociative N{sub 2} states instead of the total VUV excitation energy, indicating that N{sub 2} photodissociation is nonstatistical. When the branching ratios for N({sup 4}S) + N({sup 2}D) and N({sup 4}S) + N({sup 2}P) products are plotted as a function of the VUV excitation energy for the valence N{sub 2} {sup 1}Π{sub u} and {sup 1}Σ{sub u}{sup +} states, oscillations in these ratios are observed demonstrating how these channels are competing with each other. These data can be used to select both the velocity and internal states of the atomic products by picking the quantum state that is excited. High-level ab initio potential energy curves of the excited N{sub 2} states are calculated to provide insight into the mechanisms for the observed branching ratios. The calculations predict that the formation of both N({sup 4}S) + N({sup 2}D) and N({sup 4}S) + N({sup 2}P) channels involves potential energy barriers, in agreement with experimental observations. A discussion of the application of the present results to astronomy, planetary sciences, and comets is given.

79 ASTRONOMY AND ASTROPHYSICS↗
NASA NTRS1985

Calculation of pressure-broadened linewidths for CO in Ar

Calculations of the pressure-broadening cross sections of CO in Ar have been made within the infinite-order sudden (IOS) and coupled states (CS) quantum scattering approximations. Two intermolecular potentials were used, a pairwise additive atom-atom potential which has been employed previously in semiclassical (modified Anderson theory) studies of this system and one calculated ab initio within an electron gas formalism. Predictions from the two potentials generally agree within about 25 percent and bracket experimental values (except for some recent high temperature data obtained in shock tube experiments). The CS approximation appears to be quite accurate although computationally expensive. The much cheaper IOS approximation is accurate for the J = 0-1 line but does not properly predict the dependence on line number. The quantum results are also compared with earlier semiclassical values.

Green, S.↗
NASA NTRS1998

Simulated infrared emission spectra of highly excited polyatomic molecules: a detailed model of the PAH-UIR hypothesis

A detailed description of the polycyclic aromatic hydrocarbon (PAH)/unidentified infrared band (UIR) mechanism is presented in which experimental spectral bandshape functions are used to simulate IR emission spectra for individual molecules. These spectra are additively superimposed to produce a conglomerate spectrum representative of a family of PAH molecules. Ab initio vibrational frequencies and intensities for nine PAHs (neutral and cationic) as large as ovalene are used in conjunction with measured bandshape and temperature-dependent redshift data to simulate the UIR bands. The calculated spectra of cations provide a closer match to the UIRs than do those of the neutrals. However, the PAH cations used in the simulations fail to reproduce the details of the UIR emission spectra. The discrepancies are potentially alleviated if both larger PAHs and a greater number of PAHs were included in the simulation.

Non-NASA Center↗