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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 343 records · Page 19
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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

Theoretical study of the A prime 5Sigma(+)g and C double prime 5Pi u states of N2 - Implications for the N2 afterglow

Theoretical spectroscopic constants are reported for the A prime 5Sigma(+)g and C double prime 5Pi u states of N2 based on CASSCF/MRCI calculations using large ANO Gaussian basis sets. The calculated A prime Sigma(+)g potential differs qualitatively from previous calculations in that the inner well is significantly deeper (De = 3450/cm). This deeper well provides considerable support for the suggestion of Berkowitz et al. (1956) that A prime 5Sigma(+)g is the primary precursor state involved in the yellow Lewis-Rayleigh afterglow of N2.

Partridge, Harry↗
NASA NTRS1987

How important is correlation in the description of the Ni-H2O interaction

Using very large basis sets, which can accurately describe the polarizability of Ni and H2O and the dipole moment of H2O, the dipole-induced-dipole interaction is shown to be more than 50 percent of the about 4.8 kcal/mole bonding. Dispersion is found to account for the remainder of the bonding; this is significantly less than in previous estimates. The superposition error at the SCF level is essentially zero, and only 0.5 kcal/mole at the SDCI level, and the binding energy has been corrected for this error.

Bauschlicher, Charles W., Jr.↗
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

Theoretical confirmation of a 4-Delta ground state for FeH

Large CAS SCF/multireference configuration interaction (MRCI) and modified coupled pair functional (MCPF) calculations are carried out for the 4-Delta and 6-Delta states of FeH using very large Gaussian basis sets. At the MCPF level, 3s and 3p correlation preferentially lowers the 4-Delta state by 0.10 eV. Adding this inner-shell correlation effect to our best CAS SCF/MRCI+Q valence treatment results in a 4-Delta-6 Delta separation of 0.16 eV. This supports the interpretation of the photodetachment spectra of Stevens et al. (1983) that places the 6-Delta state about 0.25 eV above the 4-Delta ground state.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1988

Intermolecular potential for thermal H2O-He collisions

Theoretical potentials for rotational excitation of H2O by He were constructed via several methods, all of which start with a large basis set SCF interaction. The semiempirical Hartree-Fock with damped dispersion model adds a damped long-range attraction with parameters adjusted to fit experimental total differential cross sections. Purely ab initio potentials add correlation energies obtained via perturbation theory (MP2 and MP4) or a variational method (ICF1). Scattering calculations were performed on all surfaces to compare wih available beam scattering and pressure broadening data and to assess sensitivity of state-to-state rates to uncertainties in the potential. From comparison with the limited experimental data, the ICF1 surface appears to be marginally better than the MP4 surface. Thermal rates calculated from this surface should be accurate to better than 50 percent, at least for the larger, more important rates.

Palma, Amedeo↗
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 NTRS1987

Theoretical study of the dissociation energy and the red and violet band systems of CN

The dissociation energy (D sub O) of CN is determined to be 7.65 + or - 0.06 eV. This corresponds to delta H sub f (CN) = 105.3 + or - 1.5 kcal/mole, in excellent agreement with Engleman and Rouse (1975), but considerably larger than the recent value deduced from shock-tube studies by Colket (1984). The result is obtained not only from extensive ab initio MRCI calculations using a very large Gaussian basis set, but also from extrapolation of the directly computed value by comparison of computed and experimental results fo NO, C2, and N2. As an additional calibration of the methods, the D sub O value for CN was computed from the corresponding value for CN(-) using the experimental electron affinity data. The lifetime of the nu prime = 0 level of the violet (B 2 sigma + yields X 2 sigma +) system was computed to be 62.4 ns, in good agreement with both experiment and previous calculations. Lifetimes for the red (A 2 pi yields X 2 sigma +) system decrease with increasing nu prime, which is consistent both with the recent experiment and calculations. While the computed lifetimes are significantly longer that those obtained from the experiment, they are shorter than those deduced from an analysis of the solar spectrum. However the D sub O and f (sub OO) are consistent with Lambert's model for the solar spectrum.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1988

Full configuration-interaction study of the ionic-neutral curve crossing in LiF

Full configuration-interaction (FCI) calculations are used to assess the relative ability of methods for truncating the n-particle expansion in describing the ionic-neutral curve crossing between the two lowest Sigma(+) states of LiF. While the FCI calculations yield a smooth dipole moment function, MRCI calculations based on CASSCF orbitals optimized for the lowest state at all r values yield a discontinuous dipole moment function. However, when the orbitals are optimized using a state-averaged CASSCF procedure, with equal weights for the ionic and neutral solutions, both the CASSCF and MRCI dipole moment functions are smooth and in reasonable agreement with the FCI. No single-reference-based method is found to work satisfactorily. Potential curves for the lowest two Sigma(+) states are determined in both the adiabatic and diabatic representations using a large atomic natural orbit Gaussian basis set and a state-averaged CASSCF/MRCI treatment of electron correlation.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1988

Theoretical study of the NO gamma system

A systematic study of the NO gamma system with level of correlation treatment was carried out using large Gaussian basis sets to determine the potential curves for the X2Pi and A2Sigma(+) states of NO. It is shown that the A2Sigma-X2Pi electronic transition moment (gamma system) increases monotonically with decreasing internuclear distance and that the increase in the moment as r decreases is correlated with the increasing degree of diffuse character in the X2Pi state. The results of a study of the X2Pi and A2Sigma(+) dipole moment functions showed that the X2Pi vibrationally averaged dipole moments and the (1-0) and (2-0) vibration-rotation band intensities agree well with experimental data.

Langhoff, Stephen R.↗
NASA NTRS1988

Oscillator strengths for Si II

New accurate results are presented for absorption oscillator strengths of Si II resonance lines. In these ab initio calculations, an extensive basis set of 67 electronic configuration are employed, including fine-structure states and relativistic effects in the Breit-Pauli approximation. For the strong Si II lines, good agreement is found with previous LS-coupling f-values of Dufton et al. (1983). Oscillator strengths of selected weaker lines disagree in some cases with empirically determined f-values by Shull, Snow, and York (1981) and by Van Buren (1986). The theoretical results are combined with curve-of-growth analyses of Copernicus and IUE data to yield a list of recommended Si II oscillator strengths consistent with the errors in both theoretical and observational analyses. These f-values have been used (Van Steenberg and Shull) for a Galactic survey of interstellar silicon abundances with the International Ultraviolet Explorer satellite.

Luo, Ding↗
NASA NTRS1988

On the dissociation energies and bonding in NiCO(+) and TiCO(+)

Ab initio calculations on the NiCO(+) and TiCO(+) molecules are carried out using large Gaussian basis sets and extensive treatment of electron correlation. The NiCO(+) molecule is found to have a 2Sigma(+) ground state with a 2Delta state only 2.1 kcal/mole higher in energy. The Ni(+)-CO structure is about 11 and 28 kcal/mole more stable than the Ni(+)-OC and the T-shaped structures, respectively.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1988

On the interpretation of the photoelectron spectrum of NiCO(-)

Ab initio calculations have been carried out for the X1Sigma(+), a3Delta, b3Delta(+), and c3Pi states of NiCO, using a large Gaussian basis set and an MCPF treatment of electron correlation. The calculated dissociation energies, De (kcal/mol), are 30.1, 11.5, 10.1, and 4.3 respectively. An analysis of the relative cross sections for photodetachment indicates the the lower energy feature in the photoelectron spectrum of NiCO(-) results primarily from bound-free transitions to the c3Pi state, with some contribution from bound-bound transitions to both the b3Sigma(+) and c3Pi states.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1989

Ordering of the O-O stretching vibrational frequencies in ozone

The ordering of nu1 and nu3 for O3 is incorrectly predicted by most theoretical methods, including some very high level methods. The first systematic electron correlation method based on one-reference configuration to solve this problem is the coupled cluster single and double excitation method. However, a relatively large basis set, triple zeta plus double polarization is required. Comparison with other theoretical methods is made.

Scuseria, Gustavo E.↗
NASA NTRS1989

Theoretical studies of the transition metal-carbonyl systems MCO and M(CO)2, M = Ti, Sc, and V

Large Gaussian basis sets and an electron correlation treatment are used in ab initio calculations on the transition metal-carbonyl systems MCO and N(CO)2 for M = Ti, Sc, and V. The results show that high-spin ground states are favored for the monocarbonyl molecules, and that for the dicarbonyl molecules there is a competition between high, intermediate, and low spin states which are very close in energy. Dissociation energies of 0.62 eV for Ti-CO and 1.02 for Ti(CO)2 are found, relative to the ground state Ti atomic asymptote and CO 1Sigma(+). The binding energy per carbonyl for the three metal atoms is shown to be significantly lower for the dicarbonyl than for the the monocarbonyl molecules.

Barnes, Leslie A.↗
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

Bonding in zerovalent Ni compounds - NiN2 and Ni(N2)4 compared with NiCO and Ni(CO)4

Calculations are carried out on NiN2, which may be considered a prototypical metal surface-ligand system. A large Gaussian basis set and an MCPF treatment of electron correlation are used. Consideration is also given to the 2Sigma(+) states of NiN2(-), NiCO(-), and NiN2(+), the low-lying 2Delta and 2Pi states of NiN2(+), and the 1A1 states of Ni(CO)4 and Ni(N2)4.

Bauschlicher, Charles W., Jr.↗