Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “basis sets”

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 559 records · Page 31
All sourcesNASA NTRSDOE OSTI
NASA NTRS1987

Positive ions of the first- and second-row transition metal hydrides

Theoretical dissociation energies for the first- and second-row transition metal hydride positive ions are critically compared against recent experimental values obtained from ion beam reactive scattering methods. Theoretical spectroscopic parameters and dipole moments are presented for the ground and several low-lying excited states. The calculations employ large Gaussian basis sets and account for electron correlation using the single-reference single- and double-excitation configuration interaction and coupled-pair-functional methods. The Darwin and mass-velocity contributions to the relativistic energy are included in the all-electron calculations on the first-row systems using first-order perturbation theory, and in the second-row systems using the Hay and Wadt relativistic effective core potentials. The theoretical D(0) values for the second-row transition metal hydride positive ions should provide a critical measure of the experimental values, which are not as refined as many of those in the first transition row.

Pettersson, Lars G. M.↗
NASA NTRS1987

A high-precision ab initio determination of the equilibrium geometry and force field of HOC(+)

The results of an ab initio molecular orbital investigation of the isoformyl cation, HOC(+), shape are reported. The effects of expanding the basis set to near the Hartree-Fock limit and of electron correlation were examined, and the results indicate that near the Hartree-Fock limit the HOC(+) is linear. An analytic potential function is presented, from which the calculated rotational energies are only 0.03 percent different from the experimental values. This represents a nearly two orders of magnitude reduction in error from earlier work.

Defrees, D. J.↗
NASA NTRS1987

Effective core potential parameters for first- and second-row atoms

An improved effective core potential (ECP) technique is described and used to give ECP parameters for the atoms of the first two rows of the periodic table. A given basis set is parametrized which allows for a direct comparison with all-electron calculations. Extensive test calculations on first- and second-row molecules using the ECP have been performed, giving excellent agreement with the all-electron results at the SCF, CASSCF, and CI levels of treatment. Correlating and diffuse functions may be added without modifying the ECP parameters. The present ECP descriptions result in CPU time reductions of the order of 50 percent in addition to reduced disk storage.

Pettersson, Lars G. M.↗
NASA NTRS1987

Small Al clusters. II - Structure and binding in Al(n) (n = 2-6, 13)

The structure and stability of aluminum clusters containing up to six atoms have been studied using correlated wave functions and extended basis sets. The lowest energy structure is planar for Al4 and Al5, but three dimensional for Al6. The icosahedral, hcp, fcc, and two planar structures of Al13 were considered at the SCF level. The lowest energy structure is the icosahedron, but the planar structures are fairly low lying even in this case. A simplified description using two- and three-body interaction potentials is found to agree well with the ab initio structures and binding energies.

Pettersson, Lars G. M.↗
NASA NTRS1987

Schwinger multichannel study of the 2Pi(g) shape resonance in N2

The results of a study on electron-target correlations in the 2Pi(g) shape resonance of elastic e-N2 scattering, using the Schwinger multichannel formulation, are reported. The effects of basis set, orbital representation, and closed-channel-configurations are delineated. The different roles of radial and angular correlations are compared.

Huo, Winifred M.↗
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

Theoretical study of the N2(+) Meinel system

Atomic natural orbital Gaussian basis sets and large complete-active-space self-consistent field/multireference configuration-interaction wave functions are used to determine the potential curves for the X 2Sigma(+) sub g and A 2Pi sub u states of N2(+). The dependence of the electronic transition moment between the two states on internuclear distance is accurately determined, and is shown to differ significantly from previous determinations. These theoretically determined lifetimes agree with experimental time-of-flight data within stated experimental error bars.

Langhoff, Stephen R.↗
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.↗