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At least 181 records · Page 10

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NASA NTRS1983

The dissociation energy of Cu2 - Do we want to perform multi-reference singles and doubles CIs on many-electron systems?

Reference is made to a study by Hay and Dunning (1976), who showed that, for most problems, it is not necessary to perform full FOCI (first order configuration interaction); instead, only that subset of configuration state functions (CSFs) that differ by only one or two spin orbitals from any of a list of reference configurations need be used. This is referred to as POLCI. Calculations of the D(e) of Cu2 using both SDCI (singles and doubles configuration interaction) and POLCI models are presented. It is found that the size-consistency problems associated with SDCI cause an error in D(e), whereas the POLCI results are in excellent agreement with experiment. It is proposed that the orbitals be classified as inactive and active and that the inactive-inactive correlation be eliminated to reduce the size-consistency error. In addition, it is recommended that SDCI treatments be applied with caution to systems having a large number of electrons.

Bauschlicher, C. W., Jr.↗

NASA NTRS1995

Ulysses observations of electron and proton components in a magnetic cloud and related wave activity

In addition to a smooth rotation of the magnetic field vector, magnetic clouds have a low proton temperature T(sub p). Their expansion in the solar wind leads to depletion and therefore the ion component cools down. It has been shown recently that the electron component in magnetic clouds behaves differently: when the cloud expands, electron temperature Te anti correlates with density and therefore Te increases in the cloud, creating favorable conditions for the rise of ion-acoustic waves. For the magnetic cloud observed by Ulysses on June 10 - 12, 1993 at 4.64 AU at S 32.5 deg, we present observations for both electron and proton components and related plasma wave activity. Our results confirm the anti correlation between T(sub e) and electron density and also exhibit a high ratio of T(sub e)/T(sub P) in the cloud. Since Landau damping is not effective for T(sub e)/T(sub p) much greater than 1, Doppler shifted ion acoustic waves are expected in the cloud. Calculation of ion acoustic wave frequencies in the cloud and comparison with observed wave activity confirm this expectation. As in our previous work, we show that the electron component in the cloud obeys a polytropic law with gamma is less than 1 (gamma approximately equals 0.3-0.4). The dynamics of the magnetic cloud are determined to a large degree by the dominating electron pressure.

Osherovich, V. A.↗

NASA NTRS1987

Accurate ab initio calculations for the ground states of N2, O2 and F2

Spectroscopic constants and dissociation energies for the ground states of N2, O2, and F2 determined at the CAS SCF MRCI correlation level are in excellent agreement with experiment when very large primitive valence and polarization one-particle Gaussian basis sets are employed. The dissociation energy (De) for N2 is larger than experiment unless the 2s electrons are correlated. The basis set requirement for an accurate determination of De is found to increase with the degree of multiple-bond character in the molecule.

Langhoff, Stephen R.↗

NASA NTRS2003

Electron-H Elastic Scattering

Precision calculations for e^{-}-H and e^{-}-He^{+} for S-wave scattering in the elastic region have been carried out using the optical potential approach. This formalism is now extended to e^{-}-H P-wave scattering in the elastic region. The scattering equations are solved by the non-iterative method. Phase shifts are calculated using Hylleraas-type correlation functions up to 84 terms. Results are rigorous lower bounds to the exact phase shifts and they are compared to those obtained in previous calculations.

Bhatia, A. K.↗

NASA NTRS1990

Tunneling calculations for GaAs-Al(x)Ga(1-x)As graded band-gap sawtooth superlattices

The transmission resonance spectra and tunneling current-voltage characteristics for direct conduction band electrons in sawtooth GaAs-Al(x)Ga(1-x)As superlattices are computed. Only direct-gap interfaces are considered. It is found that sawtooth superlattices exhibit resonant tunneling similar to that in step superlattices, manifested by correlation of peaks and regions of negative differential resistance in the current-voltage curves with transmission resonances. The Stark shift of the resonances of step-barrier superlattices is a linear function of the field, whereas in sawtooth superlattices under strong fields the shift is not a simple function of the field. This follows from the different ways in which the two structures deform under uniform electric fields: the sawtooth deforms into a staircase, at which field strength all barriers to tunneling are eradicated. The step-barrier superlattice always presents some barrier to tunneling, no matter how high the electric field strength.

Forrest, Kathrine↗

NASA NTRS2002

Theoretical Study of Infrared and Raman Spectra of Hydrated Magnesium Sulfate Salts

Harmonic and anharmonic vibrational frequencies, as well as infrared and Raman intensities, are calculated for MgSO4.nH20 (n=1-3). Electronic structure theory at the second order Moller-Plesset perturbation theory (MP2) level with a triple-zeta + polarization (TZP) basis set is used to determine the geometry, properties, and vibrational spectra of pure and hydrated MgSO4 salts. The direct vibrational self-consistent field (VSCF) method and its correlation corrected (CC-VSCF) extension are used to determine anharmonic corrections to vibrational frequencies and intensities for the pure MgSO4 and its complex with one water molecule. Very significant differences are found between vibrational of water molecules in complexes with MgSO4 and pure water. Some of the O-H stretching frequencies are shifted to the red very significantly (by up to 1500-2000/cm) upon complexation with magnesium sulfate. They should be observed between 1700 and 3000/cm in a region very different from the corresponding O-H stretch frequency region of pure water (3700-3800/cm). In addition, the SO2 stretching vibrations are found at lower frequency regions than the water vibrations. They can serve as unique identifiers for the presence of sulfate salts. The predicted infrared and Raman spectra should be of valuable help in the design of future missions and analysis of observed data from the ice surface of Jupiter's moon Europa that possibly contains hydrated MgSO4 salts.

Chaban, Galina M.↗

NASA NTRS1995

Investigation of a Diagnostic for Perturbation Theory: Comparison to the T(sub 1) Diagnostic of Coupled-Cluster Theory

A diagnostic for perturbation theory calculations, S(sub 2), is defined and numerical results are compared to the established T(sub 1) diagnostic from coupled-cluster theory. S(sub 2) is the lowest order non-zero contribution to a perturbation expansion of T(sub 1). S(sub 2) is a reasonable estimate of the importance of non-dynamical electron correlation, although not as reliable as T(sub 1). S(sub 2) values less than or equal to 0.012 suggest that low orders of perturbation theory should yield reasonable results; S(sub 2) values between 0.012-0.015 suggest that caution is required in interpreting results from low orders of perturbation theory; S(sub 2) values greater than or equal to 0.015 indicate that low orders of perturbation theory are not reliable for accurate results. Although not required mathematically, S(sub 2) is always less than T(sub 1) for the examples studied here.

Lee, Timothy J.↗

NASA NTRS2006

Ion Thruster Discharge Performance Per Magnetic Field Topography

DC-ION is a detailed computational model for predicting the plasma characteristics of rain-cusp ion thrusters. The advanced magnetic field meshing algorithm used by DC-ION allows precise treatment of the secondary electron flow. This capability allows self-consistent estimates of plasma potential that improves the overall consistency of the results of the discharge model described in Reference [refJPC05mod1]. Plasma potential estimates allow the model to predict the onset of plasma instabilities, and important shortcoming of the previous model for optimizing the design of discharge chambers. A magnetic field mesh simplifies the plasma flow calculations, for both the ions and the secondary electrons, and significantly reduces numerical diffusion that can occur with meshes not aligned with the magnetic field. Comparing the results of this model to experimental data shows that the behavior of the primary electrons, and the precise manner of their confinement, dictates the fundamental efficiency of ring-cusp. This correlation is evident in simulations of the conventionally sized NSTAR thruster (30 cm diameter) and the miniature MiXI thruster (3 cm diameter).

plasma processes↗

NASA NTRS1992

Concerted hydrogen atom exchange between three HF molecules

We have investigated the termolecular reaction involving concerted hydrogen exchange between three HF molecules, with particular emphasis on the effects of correlation at the various stationary points along the reaction. Using an extended basis, we have located the geometries of the stable hydrogen-bonded trimer, which is of C(sub 3h) symmetry, and the transition state for hydrogen exchange, which is of D(sub 3h) symmetry. The energies of the exchange reation were then evaluated at the correlated level, using a large atomic natural orbital basis and correlating all valence electrons. Several correlation treatments were used, namely, configration interaction with single and double excitations, coupled-pair functional, and coupled-cluster methods. We are thus able to measure the effect of accounting for size-extensivity. Zero-point corrections to the correlated level energetics were determined using analytic second derivative techniques at the SCF level. Our best calculations, which include the effects of connected triple excitations in the coupled-cluster procedure, indicate that the trimer is bound by 9 +/- 1 kcal/mol relative to three separate monomers, in excellent agreement with previous estimates. The barrier to concerted hydrogen exchange is 15 kcal/mol above the trimer, or only 4.7 kcal/mol above three separated monomers. Thus the barrier to hydrogen exchange between HF molecules via this termolecular process is very low.

Komornicki, Andrew↗

NASA NTRS1997

AB Initio Study of the Structure and Spectroscopic Properties of Halogenated Thioperoxy Radicals

Thioperoxy (XSO or XOS) radicals exist in a variety of chemical environments, and they have as a consequence drawn some interest. HSO, an important species in the chemistry of the troposphere, has been examined both experimentally. The halogenated (X = F, Cl or Br) peroxy species and isovalent thioperoxy species have been studied less, but they too are potentially interesting because oxidized sulfur species and halogen sources are present in the atmosphere. Learning the fate of XSO and XOS radicals is important to understanding the atmospheric oxidation chemistry of sulfur compounds. Of these, FSO and ClSO are particularly interesting because they have been directly detected spectroscopically. Recent studies in our laboratory on the photochemistry of thionyl halides (X2SO; where X = F or Cl) have suggested new ways to generate XSO species. The laser-induced photodissociation of thionyl fluoride, F2SO, at 193 nm and thionyl chloride, ClSO, at 248 nm is characterized by a radical mechanism, X2SO -> XSO + X. The structure of FSO has been characterized experimentally by Endo et cd. employing microwave spectroscopy. Using the unrestricted Hartree-Fock (UHF) self-consistent field (SCF) method, Sakai and Morokuma computed the electronic structure of the ground (sup 2)A" and the first excited (sup 2)A' states of FSO. Electron correlation was not taken into account in their study. In a laser photodissociation experiment, Huber et al. identified ClSO mass spectromctrically. ClSO has also been detected in low temperature matrices by EPR and in the gas phase by far IR laser magnetic resonance. Although the structure of FSO is known in detail, the only study, experimental or theoretical, of CISO has been an ab initio HFSCF study by Hinchliffe. Electron correlation corrections were also excluded from this study. In order to better understand the isomerization and dissociation dynamics of the radical species, we have performed ab initio correlated studies of the potential energy surfaces (PES) of ClSO and its isomer ClOS at the QCISD(T)/6-31 G* level of theory. For FSO and FOS, more extensive QCISD/6-31 1G(2df) calculations have been possible, and the results are summarized here.

Munoz, Luis A.↗

NASA NTRS2003

Anharmonic Vibrational Spectroscopy of the F-(H20)n, complexes, n=1,2

We report anharmonic vibrational spectra (fundamentals, first overtones) for the F-(H(sub 2)O) and F-(H(sub 2)O)2 clusters computed at the MP2 and CCSD(T) levels of theory with basis sets of triple zeta quality. Anharmonic corrections were estimated via the correlation-corrected vibrational self-consistent field (CC-VSCF) method. The CC-VSCF anharmonic spectra obtained on the potential energy surfaces evaluated at the CCSD(T) level of theory are the first ones reported at a correlated level beyond MP2. We have found that the average basis set effect (TZP vs. aug-cc-pVTZ) is on the order of 30-40 cm(exp -1), whereas the effects of different levels of electron correlation [MP2 vs. CCSD(T)] are smaller, 20-30 cm(exp -1). However, the basis set effect is much larger in the case of the H-bonded O-H stretch of the F-(H(sub 2)O) cluster amounting to 100 cm(exp -1) for the fundamentals and 200 cm (exp -1) for the first overtones. Our calculations are in agreement with the limited available set of experimental data for the F-(H(sub 2)O) and F-(H(sub 2)O)2 systems and provide additional information that can guide further experimental studies.

Chaban, Galina M.↗

NASA NTRS1998

Molecular Static Third-Order Polarizabilities of Carbon-Cage Fullerene and Their Correlation with Three Geometric Properties: Symmetry, Aromaticity, and Size

The static third-order polarizabilities (gamma) of C60, C70, five isomers of C78 and two isomers of C84 were analyzed in terms of three properties, from a geometric point of view: symmetry, aromaticity and size. The polarizability values were based on the finite field approximation using a semiempirical Hamiltonian (AM1) and applied to molecular structures obtained from density functional theory calculations. Symmetry was characterized by the molecular group order. The selection of 6-member rings as aromatic was determined from an analysis of bond lengths. Maximum interatomic distance and surface area were the parameters considered with respect to size. Based on triple linear regression analysis, it was found that the static linear polarizability (alpha) and gamma in these molecules respond differently to geometrical properties: alpha depends almost exclusively on surface area while gamma is affected by a combination of number of aromatic rings, length and group order, in decreasing importance. In the case of alpha, valence electron contributions provide the same information as all-electron estimates. For gamma, the best correlation coefficients are obtained when all-electron estimates are used and when the dependent parameter is ln(gamma) instead of gamma.

Moore, C. E.↗

NASA NTRS1977

Morphology and physical parameters of a solar flare

The chromospheric and coronal morphology of the flare of June 15, 1973, (1B/M3) in NOAA active region 131 (McMath 12379) is discussed, and results of quantitative analysis of Skylab soft X-ray observations of the event are presented. H-alpha and white-light observations reveal evidence of emerging flux near the site of the H-alpha flare onset. Preflare and early flare filament activity and its spatial and temporal correlation with the flare are discussed. Spatially resolved soft X-rays are compared with H-alpha and magnetic-field measurements. Full-disk high-temporal-resolution soft X-ray flux measurements and time profiles of the resultant temperature and density calculations are also presented which yield a peak temperature of about 14.2 million K and a peak electron density of approximately 3.5 deg 10 to the -10th power per cu cm and show a preflash-phase temperature rise to about 9 million K. The peak values should be compared with the respective values of approximately 25 million K and 4.5 by 10 to the -10th power per cu cm deduced from the spatially resolved data.

Smith, J. B., Jr.↗

NASA NTRS1994

Simultaneous measurements of waves and precipitating electrons near the equator in the outer radiation belt

An investigation of wave-particle interactions is made using several simultaneous electron and wave measurements performed at near-equatorial positions from the Combined Release and Radiation Effects Satellite (CRRES) satellite. Bursts of electron precipitation were observed, most frequently at local times near dawn. Examples of bursts are presented in which the fluxes of the precipitating electrons and the wave intensities are correlated with coefficients as high as 0.7. During bursts the frequencies of the enhanced waves spanned a wide range from 311 Hz to 3.11 kHz, and the energies of the enhanced electrons were in the range 1.7 keV to 288 keV. The changes of the precipitating fluxes were generally less pronounced at the lowest energies. On the basis of electron-cyclotron resonant calculations using the cold plasma densities and ambient magnetic fields taken from the CRRES measurements it was found that the wave frequencies and precipitating electron energies were generally consistent with those expected from electron resonance with parallel propagating whistler waves. The electron data of principal concern here were acquired in and about the loss cone with narrow angular resolution spectrometers covering the energy range 340 eV to 5 MeV. The wave data included electric field measurements spanning frequencies from 5 Hz to 400 kHz and magnetic field measurements from 5 Hz to 10 kHz.

Imhof, W. L.↗

NASA NTRS1975

Quantum chemical study of relative reactivities of a series of amines and nitriles - Relevance to prebiotic chemistry

Using the Iterative Extended Huckel Theory (IEHT) calculations of the electron distribution and orbital energies of a series of thirteen amines, nitriles and amino-nitriles relevant to prebiotic and cosmo-chemistry have been carried out. Ground state properties such as the energy and nature of the highest occupied (HOMO) and lowest empty (LEMO) molecular orbitals, net atomic charges and number of nonbonding electrons have been identified as criteria for correlating the relative nucleophilicity of amine and nitrile nitrogens and the electrophilicity of nitrile and other unsaturated carbon atoms. The results of such correlations can be partially verified by known chemical behavior of these compounds and are used to predict and understand their role in prebiotic organic synthesis.

Loew, G. H.↗

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 NTRS1986

Theoretical dissociation energies for the alkali and alkaline-earth monofluorides and monochlorides

Spectroscopic parameters are accurately determined for the alkali and alkaline-earth monofluorides and monochlorides by means of ab initio self-consistent field and correlated wave function calculations. Numerical Hartree-Fock calculations are performed on selected systems to ensure that the extended Slater basis sets employed are near the Hartree-Fock limit. Since the bonding is predominantly electrostatic in origin, a strong correlation exists between the dissociation energy (to ions) and the spectroscopic parameter r(e). By dissociating to the ionic limits, most of the differential correlation effects can be embedded in the accurate experimental electron affinities and ionization potentials.

Langhoff, S. R.↗