Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “CI”

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.

Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.

At least 325 records · Page 18
All sourcesNASA NTRSDOE OSTI
NASA NTRS1988

Theoretical characterization of the minimum energy path for the reaction H + O2 to HO2(asterisk) to HO + O

The potential energy surface for the H + O2 to HO2(asterisk) to HO + O reaction has been investigated in the region of the minimum energy path using CASSCF/contracted CI (CCI) calculations with a large basis set. The results show no barrier for the addition of an H atom to O2, in agreement with previous studies. A crossing between the surface for electrostatic (OH dipole-O quadrupole) interaction and that for the formation of an O-O chemical bond, at r(infinity) of about 5.5 a(0), results in a small (about 0.5 kcal/mol) barrier.

Walch, Stephen P.↗
NASA NTRS1988

On the bond distance in methane

The equilibrium bond distance in methane has been optimized using coupled-pair functional and contracted CI wave functions, and a Gaussian basis that includes g-type functions on carbon and d-type functions on hydrogen. The resulting bond distance, when corrected for core-valance correlation effects, agrees with the experimental value of 2.052 a(0) to within the experimental uncertainty of 0.002 a(0). The main source of error in the best previous studies, which showed discrepancies with experiment of 0.007 a(0) is shown to be basis set incompleteness. In particular, it is important that the basis set be close to saturation, at least for the lower angular quantum numbers.

Bowen-Jenkins, Philippa↗
NASA NTRS1988

Full configuration-interaction benchmark calculations for AlH

Full CI and CASSCF/SOCI theoretical computations are presented for the X 1Sigma(+), A 1Pi, and C 1Sigma(+) states of AlH. The aim is to establish benchmark data to calibrate methods which describe valence-Rydberg transitions in other molecules. The results are presented in extensive tables and graphs and compared with published theoretical and experimental values, and the conditions under which CASSCF/SOCI calculations accurately reproduce the FCI results are defined.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1988

Theoretical study of the nitrogen atom hyperfine coupling constant

The nitrogen-atom isotropic hyperfine coupling constant A(iso) is studied as a function of improvements in both the one-particle and n-particle basis sets. The study underscores the importance of diffuse basis functions. For example, the (9s 5p) primitive set of Huzinaga (1965) augmented with an even-tempered diffuse s function yields values for A(iso) that are virtually identical to an energy-optimized (23s 12p) even-tempered set. The A(iso) constant is found to converge relatively quickly with increasing l quantum numbers: d, f, and g functions are estimated to contribute 2.5 + or - 0.2, 0.4 + or - 0.1, and 0.05 + or - 0.05 MHz, respectively. Full CI calibration calculations indicate that very high levels of correlation treatment are required for quantitative results. In addition, a strong coupling is observed between the one-particle and n-particle requirements. The best result, 10.4 MHz, is in excellent agreement with the accurate experimental value of 10.4509 MHz.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1988

The lowest ionization potentials of Al2

Potential curves for the lowest two electronic states (X 2 sigma g + and A 2 pi u) of Al2(+) were computed using complete active space SCF/multireference CI wave functions and large Gaussian basis sets. The lowest observable vertical ionization potential (to Al2(+) X 2 sigma g +) of the Al2 X 3 pi u ground state is calculated to occur around 6.1 eV, in excellent agreement with the experimental range of 6.0 to 6.42 eV obtained in recent cluster ionization studies by Cox and co-workers. The second vertical ionization potential (to Al2(+) A 2 pi u) occurs near 6.4 eV, also within the experimental range. The adiabatic IP of 5.90 eV is in good agreement with the value of 5.8 to 6.1 eV deduced by Hanley and co-workers from the difference in thresholds between collision induced dissociation processes of Al3(+). The computed IP values are somewhat larger than those deduced from branching ratios in cluster fragmentation experiments by Jarrold and co-workers. The observation of an ionization threshold below 6.42 eV is shown to be incompatible with an Al2 ground electronic state assignment of 3 sigma g -, but the separation between the two lowest states of Al2 is so small that it is likely that both are populated in the experiments, so that this does not provide unambiguous support for the recent theoretical assignment of the ground state as 3 pi u.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1988

A comparison of Halley dust with meteorites, interplanetary dust and interstellar grains

The variability of the mineral forming elements in the submicron Halley grains provides a powerful basis for comparison of Halley with the different classes of meteoritic materials that have been studied in the lab. The degree of variability in the Halley samples is larger than that seen in chondrites implying that Halley is more heterogeneous at the submicron scale. A critical distinction is that Halley contains abundant pure Mg silicates at the size scale while the carbon rich meteorites do not. The submicron dispersion composition seen in Halley is dramatically different from the narrowly constrained compositions seen in CI and CM (type 1 and 2) carbonaceous chondrites. These meteorites are carbon rich but are dominated by a hydrated silicate with a very narrow range of Mg/Si ratio. The Halley results are also unlike the composition variations seen in most of interplanetary dust types that are dominated by hydrated materials. The only known class of meteoritic material that appear to closely resemble the Halley data is a class of cosmic dust composed entirely of anhydrous minerals. The composition implies that Halley is dominated by olivine, pyroxene, iron sulfide, glass and amorphous carbonaceous matter.

Brownlee, D. E.↗
NASA NTRS1988

Planetary Fabry-Perot spectroscopy

Application of high spectral resolution, Earth-based Fabry-Perot spectroscopy to the study of planetary atmospheres, for which current topics are outer planet HD and H2 spectra (atmospheric structure, D/H ratio), Mars CO2, CO, O2, and H2O spectra (atomspheric photochemistry), Venus H2O and HDO, associated laboratory spectroscopy (especially H2 overtone bands, HDO) was accomplished. Monochromatic charge coupled device (CCD) imaging photometry of the Jovian nebula, with images taken in rapid sequence among the diagnostic spectral lines of ionized sulfur species, provided self-supporting snapshots of the Jupiter/Io plasma conditions (spatially resolved electron and ion densities and temperatures), covering the post-Voyager period from 1981 and leading up to the Galileo tour in the early 1990s. High spectral resolution Fabry-Perot/charge coupled device (CCD) imaging of comets (OI, CI, and H2O(+) velocity maps and spatial distriubtions), and Io's charge exchanged neutral jet was studied.

Trauger, J. T.↗
NASA NTRS1988

Recent advances in electronic structure theory and their influence on the accuracy of ab initio potential energy surfaces

Recent advances in electronic structure theory and the availability of high speed vector processors have substantially increased the accuracy of ab initio potential energy surfaces. The recently developed atomic natural orbital approach for basis set contraction has reduced both the basis set incompleteness and superposition errors in molecular calculations. Furthermore, full CI calculations can often be used to calibrate a CASSCF/MRCI approach that quantitatively accounts for the valence correlation energy. These computational advances also provide a vehicle for systematically improving the calculations and for estimating the residual error in the calculations. Calculations on selected diatomic and triatomic systems will be used to illustrate the accuracy that currently can be achieved for molecular systems. In particular, the F+H2 yields HF+H potential energy hypersurface is used to illustrate the impact of these computational advances on the calculation of potential energy surfaces.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1988

ALH85085 - A unique volatile-poor carbonaceous chondrite with possible implications for nebular fractionation processes

The characteristics and possible origin of the chondrite ALH85085 are discussed. It is found that the metal silicate, and sulfide compositions of ALH85085 are similar to those in CM-CO and Al Rais-Renazzo chondrites. High siderophile abundances and volatile depletion are observed. It is found that ALH85085 agglomerated when temperatures in the nebula were near 1000 K, in the same region where Renazzo, Al Rais, and the CI chondrites formed. It is suggested that ALH85085 was annealed and lightly shocked after agglomeration. C1 and other clasts were subsequently incorporated during late-stage brecciation.

Grossman, Jeffrey N.↗
NASA NTRS1989

Theoretical characterization of the minimum energy path for hydrogen atom addition to N2 - Implications for the unimolecular lifetime of HN2

Results are reported from CASSCF externally contracted CI ab initio computations of the minimum-energy path for the addition of H to N2. The theoretical basis and numerical implementation of the computations are outlined, and the results are presented in extensive tables and graphs and characterized in detail. The zero-point-corrected barrier for HN2 dissociation is estimated as 8.5 kcal/mol, and the lifetime of the lowest-lying quasi-bound vibrational state of HN2 is found to be between 88 psec and 5.8 nsec (making experimental observation of this species very difficult).

Walch, Stephen P.↗
NASA NTRS1989

Aqueous alteration on the hydrous asteroids - Results of EQ3/6 computer simulations

The two models of carbonaceous chondrite precursor material presently formulated to study the process of aqueous alteration in hydrous asteroids are based, in the first case, on the anhydrous mineralogy of CM chondrites, while the second is based on that of the CV chondrites. It is noted that the alteration mineralogy of the CM chondrites and their parent asteroids may be produced by starting with the anhydrous mineralogy of the same CM chondrites, at temperatures in the 1-25 C range, with a wide variety of rock/fluid ratios. The mineralogy of the important CI chondrites is reproducible through the alteration of either CM or CV anhydrous material, at temperatures in the 50-150 C.

Zolensky, Michael E.↗
NASA NTRS1989

The composition of comets

The present discussion of recent studies concerning cometary composition gives attention to the results obtained by in situ measurements of Comet Halley's dust composition by Vega 1's impact mass spectrometer, which discovered a mineral fraction that appears to be CI chondritic, as well as an organic fraction consisting of highly unsaturated hydrocarbons. The mineral fraction of comets appears to form a core that is embedded in essentially organic material; the spectroscopic invisibility of carbon is due to its presence in the cometary dust. The mass of most dust particles is found to be in the 10 to the -12th to 10 to the -14th g range. A considerable fraction of the dust grains serves as an extended source of gas in the inner coma.

Jessberger, E. K.↗
NASA NTRS1989

Theoretical characterization of selected regions of the ground state potential surface of N2H2

The results of CASSCF/multireference contracted CI calculations with large atomic natural orbital basis sets are presented for selected regions of the N2H2 potential surface. The calculations focused on the addition of an H atom to HN2. This process involves four channels. Approach of the H atom along the HN bond leads to N2 + H2 with no barrier (H abstraction), while approach of the H atom to the other three positions leads to trans-HNNH, cis-HNNH, and NNH2, which are stable minima. These calculations provide the most accurate energetics for these three stable species obtained to date. Combining the results of these calculations with previous results for HN2 provides accurate thermochemical data on these important molecules.

Walch, Stephen P.↗
NASA NTRS1989

Lowest ionization potentials of Al2

Potential curves for the lowest two electronic states, X 2Sigma(+)g and A 2Pi(u), of Al2(+) were computed using complete active space SCF/multireference CI wave functions and large Gaussian basis sets. The lowest observable vertical ionization potential, to Al2(+) X 2Sigma(+)g, of the Al2 X 3 Pi(u) ground state is calculated to occur around 6.1 eV, in excellent agreement with the experimental range of 6.0 to 6.42 eV obtained in recent cluster ionization studies by Cox and co-workers. The second vertical ionization potential, to Al2(+) A 2Pi(u), occurs near 6.4 eV, also within the experimental range. The adiabatic IP of 5.90 eV is in good agreement with the value of 5.8 to 6.1 eV deduced by Hanley and co-workers from the difference in thresholds between collision induced dissociation processes of Al3(+). The computed IP values are somewhat larger than those deduced from branching ratios in cluster fragmentation experiments by Jarrold and co-workers. The observation of an ionization threshold below 6.42 eV is shown to be incompatible with an Al2 ground electronic state assignment of 3Sigma(-)g, but the separation between the two lowest states of Al2 is so small that it is likely that both are populated in the experiments, so that this does not provide unambiguous support for the recent theoretical assignment of the ground state as 3Pi(u).

Bauschlicher, Charles W., Jr.↗
NASA NTRS1989

Major element composition of stratospheric micrometeorites

Results are presented on an element-composition study conducted on 200 interplanetary dust particles (IDPs) collected with NASA's U2 and RB 47 aircraft at altitudes near 20 km. These IDPs could be classified into two major morphological types, i.e., the 'porous' and the 'smooth' particle types, which showed significant compositional differences. Namely, elemental abundances found in porous particles are closely matching those of the CI chondrites, while the smooth particle group displayed systematic Ca and Mg depletions and contained stoichiometric 'excess' oxygen, consistent with the presence of hydrous phases. This fact, together with the occurrence of carbonates, magnetite framboids, and layer silicates, provides evidence that at least a significant number of the smooth-type IDPs were processed by aqueous activity. It is hypothesized that extensive aqueous activity only occurs in asteroids (as opposed to comets) and that the smooth class of IDPs is of an asteroidal origin.

Schramm, L. S.↗
NASA NTRS1989

The permanent electric dipole moment of chromium monoxide

The permanent electric dipole moments for the X 5Pi and B 5pi states of gas-phase CrO have been experimentally determined using the sub-Doppler optical technique of intermodulated fluorescence spectroscopy in conjunction with the Stark effect. The measured values are 3.88 + or - 0.13 and 4.1 + or - 1.8 D for the X and B states, respectively. The theoretical values determined for the X state using multireference CI iterative-natural-orbital and finite-field calculations are in excellent agreement with the experimental value.

Steimle, Timothy C.↗
NASA NTRS1989

Theoretical characterization of the potential energy surface for H + O2 yields HO2(asterisk) yields HO + O. II - The potential for H atom exchange in HO2

The results of CASSCF multireference contracted CI calculations with large ANO basis sets are presented for the exchange region of the HO2 potential-energy surface. The saddle point for H atom exchange is about 13 kcal/mol below the energy of H + O2; therefore, this region of the surface should be accessible during H + O2 recombination and methathesis reactions.

Walch, Stephen P.↗
NASA NTRS1989

Chemical, isotopic and mineralogical evidence for the origin of matrix in ordinary chondrites

Results are presented of a combined chemical, isotopic, and mineralogical study of fine-grained opaque matrix material from a type-3 ordinary chondrite Allan Hills A77299. It was found that the matrix of this chondrite (in contrast to chondrules) shows no siderophile element depletions and is remarkably unfractionated relative to CI chondrites. It was also found that the matrix lump has a unique oxygen isotopic composition which lies below the terrestrial fractionation line and differs markedly from the composition of fine-grained matrix lumps and chondrule rims from Semarkona chondrules (Grossman and Wasson, 1987; Grossman et al., 1987); the mineralogy and textures of the matrix lump (which consists of rare angular grains of pyroxene and olivine embedded within a ground-mass of rounded fine-grained olivines), as well as its major element composition, are typical of matrix material of other type-3 chondrites studied. It is concluded that the matrix lump in these chondrites consists largely of material that formed by annealing of amorphous presolar dust or nebular condensates.

Brearley, Adrian J.↗