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NASA NTRS2019

K-line X-ray fluorescence from highly charged iron ions under dense astrophysical plasma conditions

In the present work, we report an investigation of plasma environment effects on the atomic parameters associated with the K-vacancy states in highly charged iron ions within the astrophysical context of accretion disks around black holes. More particularly, the sensitivity of K-line X-ray fluorescence parameters (wavelengths, radiative transition probabilities, and Auger rates) in Fe XVII–Fe XXV ions has been estimated for plasma conditions characterized by an electron temperature ranging from 105 to 107K and an electron density ranging from 1018 to1022 cm−3. In order to do this, relativistic multiconfiguration Dirac-Fock atomic structure calculations have been carried out by considering a time averaged Debye-Hückel potential for both the electron–nucleus and electron–electron interactions.

Jérôme Deprince↗

NASA NTRS1974

High-temperature mass spectrometry - Vaporization of group 4-B metal carbides

The high temperature vaporization of the metal-carbon systems TiC, ZrC, HfC, and ThC was studied by the Knudsen effusion - mass spectrometric method. For each system the metal dicarbide and tetracarbide molecular species were identified in the gas phase. Relative ion currents of the carbides and metals were measured as a function of temperature. Second- and third-law methods were used to determine enthalpies. Maximum values were established for the dissociation energies of the metal monocarbide molecules TiC, ZrC, HfC, and ThC. Thermodynamic functions used in the calculations are discussed in terms of assumed molecular structures and electronic contributions to the partition functions. The trends shown by the dissociation energies of the carbides of Group 4B are compared with those of neighboring groups and discussed in relation to the corresponding oxides and chemical bonding. The high temperature molecular beam inlet system and double focusing mass spectrometer are described.

Stearns, C. A.↗

NASA NTRS1984

Theoretical research program to study transition metal trimers and embedded clusters

Small transition metal clusters were studied at a high level of approximation, including all the valence electrons in the calculation and extensive electron correlation, in order to understand the electronic structure of these small metal clusters. By comparison of dimers, trimers, and possibly higher clusters, the information obtained was used to provide insights into the electronic structure of bulk transition metals. Small metal clusters are currently of considerable experimental interest and some information is becomming available both from matrix electron spin resonance studies and from gas phase spectroscopy. Collaboration between theorists and experimentalists is thus expected to be especially profitable at this time since there is some experimental information which can serve to guide the theoretical work.

Walch, S. P.↗

NASA NTRS1988

Non-Maxwellian distribution functions in flaring coronal loops - Comparison of Landau-Fokker-Planck and BGK solutions

The high-velocity tail of the electron distribution has been calculated by solving the high-velocity form of the Landau equation for a thermal structure representative of a flaring coronal loop. These calculations show an enhancement of the tail population above Maxwellian for electrons moving down the temperature gradient. The results obtained are used to test the reliability of the BGK approximation. The comparison shows that the BGK technique can estimate contributions to the heat flux from the high-energy tail to within an order of magnitude.

Ljepojevic, N. N.↗

NASA NTRS1993

Projectile compositions and modal frequencies on the chemistry of micrometeoroids LDEF experiment

The Chemistry of Micrometeoroids Experiment (LDEF instrument A0187-1) exposed witness plates of high-purity gold (greater than 99.99 percent Au) and commercial aluminum (greater than 99 percent Al) with the objective of analyzing the residues of cosmic-dust and orbital-debris particles associated with hypervelocity impact craters. The gold substrates were located approximately 8 deg off LDEF's trailing edge (Bay A03), while the aluminum surfaces resided in Bay A11, approximately 52 deg from LDEF's leading edge. SEM-EDX techniques were employed to analyze the residues associated with 199 impacts on the gold and 415 impacts on the aluminum surfaces. The residues that could be analyzed represent natural or man-made materials. The natural particles dominate at all particle sizes less than 5 micron. It is possible to subdivide both particle populations into subclasses. Chondritic compositions dominate the natural impactors (71 percent), followed by monomineralic, mafic-silicate compositions (26 percent), and by Fe-Ni rich sulfides (approximately 3 percent). Approximately 30 percent of all craters on the gold collectors were caused by man-made debris such as aluminum, paint flakes, and other disintegrated, structural and electronic components. Equations-of-state and associated calculations of shock stresses for typical LDEF impacts into the gold and aluminum substrates suggest that substantial vaporization may have occurred during many of the impacts and is the reason why approximately 50 percent of all craters did not contain sufficient residue to permit analysis by the SEM-EDX technique. After converting the crater diameters into projectile sizes using encounter speeds typical for the trailing-edge and forward-facing (Row 11) directions, and accounting for normalized exposure conditions of the CME collectors, we derived the absolute and relative fluxes of specific projectile classes. The natural impactors encounter all LDEF pointing directions with comparable, modal frequencies suggesting compositional (and dynamic) homogeneity of the interplanetary-dust environment in near-Earth orbit.

Bernhard, Ronald P.↗

NASA NTRS1989

Accurate quantum chemical calculations

An important goal of quantum chemical calculations is to provide an understanding of chemical bonding and molecular electronic structure. A second goal, the prediction of energy differences to chemical accuracy, has been much harder to attain. First, the computational resources required to achieve such accuracy are very large, and second, it is not straightforward to demonstrate that an apparently accurate result, in terms of agreement with experiment, does not result from a cancellation of errors. Recent advances in electronic structure methodology, coupled with the power of vector supercomputers, have made it possible to solve a number of electronic structure problems exactly using the full configuration interaction (FCI) method within a subspace of the complete Hilbert space. These exact results can be used to benchmark approximate techniques that are applicable to a wider range of chemical and physical problems. The methodology of many-electron quantum chemistry is reviewed. Methods are considered in detail for performing FCI calculations. The application of FCI methods to several three-electron problems in molecular physics are discussed. A number of benchmark applications of FCI wave functions are described. Atomic basis sets and the development of improved methods for handling very large basis sets are discussed: these are then applied to a number of chemical and spectroscopic problems; to transition metals; and to problems involving potential energy surfaces. Although the experiences described give considerable grounds for optimism about the general ability to perform accurate calculations, there are several problems that have proved less tractable, at least with current computer resources, and these and possible solutions are discussed.

Bauschlicher, Charles W., Jr.↗

NASA NTRS1981

Quantum chemical calculation of the equilibrium structures of small metal atom clusters

A decomposition of the molecular energy is presented that is motivated by the atom superposition and electron delocalization physical model of chemical binding. The energy appears in physically transparent form consisting of a classical electrostatic interaction, a zero order two electron exchange interaction, a relaxation energy, and the atomic energies. Detailed formulae are derived in zero and first order of approximation. The formulation extends beyond first order to any chosen level of approximation leading, in principle, to the exact energy. The structure of this energy decomposition lends itself to the fullest utilization of the solutions to the atomic sub problems to simplify the calculation of the molecular energy. If nonlinear relaxation effects remain minor, the molecular energy calculation requires at most the calculation of two center, two electron integrals. This scheme thus affords the prospects of substantially reducing the computational effort required for the calculation of molecular energies.

Kahn, L. R.↗

NASA NTRS1980

Calculations of lightning return stroke electric and magnetic fields above ground

A lightning return stroke model with which the two station electric and magnetic fields measured at ground level can be reproduced is used to compute fields at altitudes up to 10 km and at ranges from 20 m to 10 km. These calculations provide the first detailed estimates of the return strokes fields that are encountered by aircraft in flight. With the advent of modern aircraft utilizing low voltage digital electronics and reduced electromagnetic shielding by way of structures containing advanced composite materials, these calculations are of considerable practical interest. Further, since airborne electric and magnetic field measurements are presently being attempted, a comparison of the calculations presented with appropriate experimental data, when they are available, will constitute a test of the return stroke model.

Uman, M. A.↗

NASA NTRS1975

A combined representation method for use in band structure calculations. 1: Method

A representation was described whose basis levels combine the important physical aspects of a finite set of plane waves with those of a set of Bloch tight-binding levels. The chosen combination has a particularly simple dependence on the wave vector within the Brillouin Zone, and its use in reducing the standard one-electron band structure problem to the usual secular equation has the advantage that the lattice sums involved in the calculation of the matrix elements are actually independent of the wave vector. For systems with complicated crystal structures, for which the Korringa-Kohn-Rostoker (KKR), Augmented-Plane Wave (APW) and Orthogonalized-Plane Wave (OPW) methods are difficult to apply, the present method leads to results with satisfactory accuracy and convergence.

Friedli, C.↗

NASA NTRS2022

A Regional Classification of Time Spectral Amplitudes in Total Electron Content: Southeastern United States During Solar Cycle 24

To investigate the meso-scale structure (100 s of km) of the ionosphere at mid-latitudes, the spectral properties in calculated total electron content (TEC) at a cluster of GPS receivers in and around Florida are analyzed. The ionosphere does not respond exactly the same to periodic solar driving at different locations around the planet, due to the complex electrodynamic interactions of the coupled magnetosphere-ionosphere system. Therefore, at each GPS receiver in the cluster we compare spatio-temporal variations of the spectral amplitudes for diurnal, solar rotation, and seasonal oscillations. The amplitudes for these dominant oscillations are organized with respect to magnetic latitude of the receiver. A low-latitude and high-latitude station are also included to put the mid-latitude ionospheric response into a global context. The amplitudes of diurnal, seasonal, and solar rotation signals are well ordered by magnetic latitude, superposed with meso-scale deviations between stations separated by ~100s of km. The results suggest that spatio-temporal variations of spectral amplitudes in the mid-latitude ionosphere are not dominated by a single process. This conclusion is based on our finding that at high latitude, the shape of the diurnal signal varies significantly less with solar activity compared to low- and mid-latitudes, and additionally, that the ratio of annual to semi-annual amplitudes fluctuates around 1 with time and from station-to-station only at mid-latitudes.

ionosphere↗

NASA NTRS2002

Theoretical Study of Tautomerization Reactions for the Ground and First Excited Electronic States of Adenine

Geometrical structures and energetic properties for different tautomers of adenine are calculated in this study, using multi-configurational wave functions. Both the ground and the lowest singlet excited state potential energy surfaces are studied. Four tautomeric forms are considered, and their energetic order is found to be different on the ground and the excited state potential energy surfaces. Minimum energy reaction paths are obtained for hydrogen atom transfer (tautomerization) reactions in the ground and the lowest excited electronic states. It is found that the barrier heights and the shapes of the reaction paths are different for the ground and the excited electronic states, suggesting that the probability of such tautomerization reaction is higher on the excited state potential energy surface. This tautomerization process should become possible in the presence of water or other polar solvent molecules and should play an important role in the photochemistry of adenine.

Salter, Latasha M.↗

NASA NTRS2013

Association Mechanisms of Unsaturated C2 Hydrocarbons with Their Cations: Acetylene and Ethylene

The ion-molecule association mechanism of acetylene and ethylene with their cations is investigated by ab initio quantum chemical methods to understand the structures, association energies, and the vibrational and electronic spectra of the products. Stable puckered cyclic isomers are found as the result of first forming less stable linear and bridge isomers. The puckered cyclic complexes are calculated to be strongly bound, by 87, 35 and 56 kcal/mol for acetylene-acetylene cation, ethylene-ethylene cation and acetylene-ethylene cation, respectively. These stable complexes may be intermediates that participate in further association reactions. There are no association barriers, and no significant inter-conversion barriers, so the initial linear and bridge encounter complexes are unlikely to be observable. However, the energy gap between the bridged and cyclic puckered isomers greatly differs from complex to complex: it is 44 kcal/mol in C4H4 +, but only 6 kcal/mol in C4H8 +. The accurate CCSD(T) calculations summarized above are also compared against less computationally expensive MP2 and density functional theory (DFT) calculations for structures, relative energies, and vibrational spectra. Calculated vibrational spectra are compared against available experiments for cyclobutadiene cation. Electronic spectra are also calculated using time-dependent DFT.

ethylene↗

NASA NTRS2002

Atomic Data for the K-Vacancy States of Fe XXIV

As part of a project to compute improved atomic data for the spectral modeling of iron K lines, we report extensive calculations and comparisons of atomic data for K-vacancy states in Fe XXIV. The data sets include: (i) energy levels, line wavelengths, radiative and Auger rates; (ii) inner-shell electron impact excitation rates and (iii) fine structure inner-shell photoionization cross sections. The calculations of energy levels and radiative and Auger rates have involved a detailed study of orbital representations, core relaxation, configuration interaction, relativistic corrections, cancellation effects and semi-empirical corrections. It is shown that a formal treatment of the Breit interaction is essential to render the important magnetic correlations that take part in the decay pathways of this ion. As a result, the accuracy of the present A-values is firmly ranked at better than 10% while that of the Auger rates at only 15%. The calculations of collisional excitation and photoionization cross sections take into account the effects of radiation and spectator Auger dampings. In the former, these effects cause significant attenuation of resonances leading to a good agreement with a simpler method where resonances are excluded. In the latter, resonances converging to the K threshold display symmetric profiles of constant width that causes edge smearing.

Bautista, M. A.↗

NASA NTRS2003

Atomic Data for the K-vacancy States of Fe XXIV

Bautista, M. A.↗

NASA NTRS2000

A Theoretical Investigation of the Infrared Spectroscopic Properties of Closed-Shell Polycyclic Aromatic Hydrocarbon Cations

Density functional theory has been employed to calculate the harmonic frequencies and intensities of a range of PAH cations which explore both size and electronic structure effects on the infrared spectroscopic of these species. The sample extends the size range of PAH species considered to more than 50 carbon atoms and includes several representatives from each of two heretofore unexplored categories of PAH cations: (1) fully benzenoid PAH cations whose carbon skeleton is composed of an odd number of carbon atoms and (2) protonated PAH cations. Unlike the radical electronic structures of the PAH cations that have been the subject of previous theoretical and experimental work, the species in these two classes have a closed-shell electronic configuration. The calculated spectra of circumcoronene, C54H18, in both neutral and (radical) cationic form are also reported and compared to those of the other species. Closed-shell species are inherently less reactive than radical (or open-shell) cations and are known to play a role in combustion chemistry. Since interstellar PAHs are typically exposed to abundant atomic hydrogen and are thought to originate under pseudo-combustion conditions in carbon-rich circumstellar shells, such species may represent an important component of the interstellar PAH population. Furthermore, species larger than 50 carbon atoms are more representative of the size of the typical interstellar PAH. Overall, as has been the case for previous studies of PAH radical cations, the general pattern of band positions and intensities are consistent with that of the interstellar infrared emission spectrum. In addition, the spectra of closed-shell and open-shell cations are found to converge with increasing molecular size and are found to be relatively similar for species containing about 50 carbon atoms.

Hudgins, Douglas M.↗

NASA NTRS1986

The evolution of the spatial structure of thick-target hard X-ray emission in solar flares

The spatial distribution of hard X-ray bremsstrahlung emission from an electron-heated target is examined, using a self-consistent calculation of the hydrodynamic response of the atmosphere to heating by the electrons to compute the density-height structure of the target atmosphere at various times. In this way the temporal evolution of the hard X-ray spatial structure at various photon energies is predicted. These results are compared with existing observations from the SMM Hard X-Ray Imaging Spectrometer to give a prognosis for the type of structure to be expected at the subarcsec resolution planned for future instrumentation.

Emslie, A. G.↗

NASA NTRS1990

Dense simple plasmas as high-temperature liquid simple metals

The thermodynamic properties of dense plasmas considered as high-temperature liquid metals are studied. An attempt is made to show that the neutral pseudoatom picture of liquid simple metals may be extended for describing plasmas in ranges of densities and temperatures where their electronic structure remains 'simple'. The primary features of the model when applied to plasmas include the temperature-dependent self-consistent calculation of the electron charge density and the determination of a density and temperature-dependent ionization state.

Perrot, F.↗

NASA NTRS1980

Modified Iterative Extended Hueckel. 1: Theory

Iterative Extended Huekel is modified by inclusion of explicit effective internuclear and electronic interactions. The one electron energies are shown to obey a variational principle because of the form of the effective electronic interactions. The modifications permit mimicking of aspects of valence bond theory with the additional feature that the energies associated with valence bond type structures are explicitly calculated. In turn, a hybrid molecular, orbital valence, bond scheme is introduced which incorporates variant total molecular electronic density distributions similar to the way that Iterative Extended Hueckel incorporates atoms.

Aronowitz, S.↗