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At least 847 records · Page 47
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NASA NTRS1988

Symmetry and equivalence restrictions in electronic structure calculations

A simple method for obtaining MCSCF orbitals and CI natural orbitals adapted to degenerate point groups, with full symmetry and equivalnece restrictions, is described. Among several advantages accruing from this method are the ability to perform atomic SCF calculations on states for which the SCF energy expression cannot be written in terms of Coulomb and exchange integrals over real orbitals, and the generation of symmetry-adapted atomic natural orbitals for use in a recently proposed method for basis set contraction.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1987

On the bond distance in methane

The equilibrium bond distance in methane was 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-valence 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 NTRS1987

An initio calculations on C2, Si2, and SiC

Full-configuration-interaction (FCI) calculations have been performed for the Z 1Sigma(g)(+), a 3Pi(u), and b 3Sigma(g)(-) states of C2 and the X 3Sigma(g)(-) and A 3Pi(u) states of Si2 in valence double-zeta plus polarization one-particle basis sets. By carrying out the CASSCF multireference singles plus doubles CI (MRCI) procedure in a very large Gaussian basis set and correcting for errors with the FCI, the triplet-triplet separation in C2 is reproduced to within 47/cm. Analogous calculations on Si2 definitively determine the ground state to be 3Sigma(g)(-); the 3Pi(u) state is only 440 + or - 100/cm higher in energy. For the SiC molecule, which has never been observed spectroscopically but is believed to be an important component in carbon stars and to be present in interstellar space, the A 3Sigma(-) state is nearly 4000/cm above the X 3Pi ground state.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1988

Theoretical studies of the potential surface for the F + H2 - HF + H reaction

Several aspects of the F + H2 - HF + H potential energy hypersurface are considered. The classical barrier height is studied as a function of improvements to both the one-particle and n-particle treatments, approaching the one-particle basis set limit. The externally contracted CI (CCI) method is used to compute bending potentials in the collinear saddle point region. The calculated CCI surface is used to locate the bottleneck on the vibrationally adiabatic potential curve, and the reaction threshold is deduced from a one-dimensinal tunneling calculation. The true classical barrier height is estimated by adjusting the CCI barrier height for the difference in the calculated and experimental thresholds.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1988

A computational study of the TiO2 molecule

A computational investigation of the ground 1A1 and lowest energy B2 states of the titanium dioxide molecule has been carried out. The treatment utilized SCF calculations in an extended basis followed by a CI treatment for each geometry. The ground state geometry agrees well with experiment, while the agreement between the computed vibrational frequency nu1 and the experimental value for a matrix isolated TiO2 is less satisfactory. Population analysis for the ground state indicates less than one excess electron on each oxygen atom. The first excited state has a linear geometry and the singlet and triplet are essentially degenerate.

Ramana, M. V.↗
NASA NTRS1988

A simple interpretation of the Fe2(-) photoelectron spectrum

A simple interpretation of the Fe2(-) photoelectron spectrum is proposed based on detachment of 4s(sigma)-asterisk(u) electrons from a (4s sigma/g/)2 (4s sigma-asterisk/u/) (3d) 13 anion. This interpretation implies a (4s sigma/g/)2 (4s sigma-asterisk/u/)1 (3d)13 ground state configuration for Fe2, rather than the (4s sigma/g/)2 (3d)14 configuration that has generally been assumed. The results of preliminary valence CI calculations provide strong support for the proposed Fe2 and Fe2(-) configurations.

Leopold, Doreen G.↗
NASA NTRS1988

Theoretical study of the first and second negative systems of N2(+)

Extended Gaussian basis sets and large CASSCF/multireference CI wave functions are used in theoretical determination of the potential curves for the X 2Sigma(+)g, B 2Sigma(+)g, C 2Sigma(+)u, (1) 2Delta(u), (2) 2Delta(u), 4Pi(u), and 2Sigma(-)u states of N2(+). The results, including the radial dependence of the electronic transition moments, the Einstein coefficients, the radiative lifetimes, and the crossing points between selected states, are presented in extensive tables and graphs and discussed in detail.

Langhoff, Stephen R.↗
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.↗