Engineering topics

Langhoff, Stephen R.

Publications and source records attributed to Langhoff, Stephen R..

At least 199 records · Page 11

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

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

On the electron affinities of the Ca, Sc, Ti and Y atoms

For the Ca, Sc, Ti and Y atoms calculations are performed for the ground states of the neutrals and the ground and several low-lying excited states of the negative ions. Overall the computed electron affinities are in good accord with experiment. The calculations show the rapid stabilization of the 3d orbital relative to the 4p as the nuclear charge increases. The 3F(0) and 3D(0) terms are found to be close in energy in Sc(-) and in Y(-). This confirms earlier speculation that some of the peaks in the photodetachment spectra of Y(-) originate from the bound excited 3F(0) term of Y(-).

Bauschlicher, Charles W., Jr.↗

NASA NTRS1987

Theoretical determination of the radiative lifetime of the A 2Sigma(+) state of OH

The present theoretical potentials and transition moment-based computation of the radiative lifetime of the A 2Sigma(+)(v-prime = 0, N-prime = 1) state of OH yields a value of 673 ns, in excellent agreement with two of the experimental values obtained through laser excitation fluorescence. The theoretical radiative lifetimes, which are expected to be lower bounds and accurate to 2 percent, are accurate enough to preclude both the slightly lower value determined by Hanle effect studies and the higher values obtained by the high frequency deflection technique.

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 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 NTRS1987

On the 1A1 - 3B1 separation in CH2 and SiH2

The 1A1 - 3B1 separation in CH2 and SiH2 has been computed using extended basis sets and CASSCF/SOCI wave functions. Using theoretical estimates for the effects of zero-point vibration yields T(0) values of 8.9 and -20.9 kcal/mol respectively, in excellent agreement with the experimental values of 9.02 and -21.0 kcal/mol. A corollary to the small zero-point vibrational contribution to the separation is that the symmetric stretching fundamental in CH2(3B1) must be near 3100/cm, much less than a recently suggested value of around 3400/cm. An accurate Te value for SiH2 establishes the ionization potential of the 1A1 state as 9.15 eV, the higher of two recent experimental values.

Bauschlicher, Charles W., Jr.↗

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

Theoretical study of the dipole moment function of OH(X 2Pi)

A complete theoretical electric dipole moment function mu(r) is computed for OH(X 2Pi) at the full configuration-interaction (FCI) level for DZP + diffuse Gaussian basis set. The energy and dipole moment are also determined with 2d functions on oxygen at seven r values. The following methods are compared to the FCI for both the oxygen 1d and 2d basis sets: single-reference singles-plus-doubles configuration interaction (SDCI), SDCI with Davidson's correction, the coupled pair functional approach (CPF) and a modified form of CPF, CASSCF, and CASSCF-MRSDCI, and the external contracted CI(CCI) method. The dipole moments are evaluated both as an expectation value and by finite-field methods. The results support the superiority of evaluating the dipole moment as an energy derivative rather than as an expectation value.

Langhoff, Stephen R.↗

NASA NTRS1987

Accurate ab initio calculations which demonstrate a 3Pi(u) ground state for Al2

The computational requirements for accurately describing the spectroscopic constants for all three candidates for the ground state of Al2 are determined. Full CI(FCI) calculations are used to calibrate approximate methods of including the electron correlation. CASSCF/MRCI calculations which accurately reproduce the FCI results in the valence DZ + 2d Gaussian basis are carried to chemical accuracy by using extensive one-particle basis sets. The effect of 2s and 2p correlation and relativistic effects are considered as well as the valence 3s and 3p correlation. Several excited states are also considered. It is shown that the computed vibrational frequency of the (2) 3Pi(g) state and the Franck-Condon factors for the (1) 3Pi(u) - (2) 3Pi(g) transition are consistent with the spectrum obtained by Douglas et al. (1983) and Abe and Kolb (1983). It is therefore concluded that the ground state is 3Pi(u).

Bauschlicher, Charles W., Jr.↗

NASA NTRS1987

Full CI benchmark calculations on N2, NO, and O2 - A comparison of methods for describing multiple bonds

Full configuration interaction (CI) calculations on the ground states of N2, NO, and O2 using a DZP Gaussian basis are compared with single-reference SDCI and coupled pair approaches (CPF), as well as with CASSCF multireference CI approaches. The CASSCF/MRCI technique is found to describe multiple bonds as well as single bonds. Although the coupled pair functional approach gave chemical accuracy (1 kcal/mol) for bonds involving hydrogen, larger errors occur in the CPF approach for the multiple bonded systems considered here. CI studies on the 1Sigma(g +) state of N2, including all single, double, triple, and quadruple excitations show that triple excitations are very important for the multiple bond case, and accounts for most of the deficiency in the coupled pair functional methods.

Bauschlicher, Charles W., Jr.↗

NASA NTRS1987

Mixed Cu-simple metal dimers and trimers - CuLi, CuLi2, CuNa, CuK, CuBe, CuBe2, Cu2Be, CuAl, and CuAl2

Theoretical studies of selected diatomic and triatomic molecules containing copper and the simple metals Li, Na, K, Be, and Al are presented, with emphasis on elucidating the nature of the bonding in mixed transition metal-simple metal systems. Large Gaussian basis sets are used in the diatomic calculations, and are used to calibrate the triatomic calculations, in which somewhat smaller Gaussian basis sets are employed. Electron correlation is incorporated using both the single-reference singles plus doubles configuration interaction and coupled pair functional methods. It is found that alkali atoms form very polar sigma bonds with copper, and that the ionicity increases with the inclusion of higher excitations because they improve the electron affinity of copper, which in turn allows a larger negative charge on copper. Aluminum is found to form stronger bonds than beryllium, since it does not have to undergo sp hybridization. Some of the trimers bond by forming three-center three-electron bonds. These multicenter bonds are quite strong even when compared to the two-electron bonds in the dimers or to other bonding mechanisms in the trimers.

Bauschlicher, Charles W., Jr.↗

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 NTRS1987

Theoretical D(0) for NH(X3Sigma-)

A value of 3.37 + or - 0.03 eV is recommended for the D(0) of the X3Sigma(-) state of NH. The value of 3.34 eV computed directly from CAS SCF/MRSD CI calculations in a (5s4p3d2f1g/4s3p2d) contracted Gaussian basis has been corrected for basis set incompleteness based on analogous calculations on CH and OH where D(0) is accurately known. Equivalent full CI calculations on the ground states of CH, NH and OH in a (4s3p2d/2s1p) basis provide strong support for the 0.03 eV extrapolation of the D(0) for NH.

Bauschlicher, Charles W., Jr.↗

NASA NTRS1987

Theoretical spectroscopic parameters for the low-lying states of the second-row transition metal hydrides

A systematic analysis of the low-lying states of all of the second-row transition metal (TM) hydrides except CdH is reported. The calculations included the dominant relativistic contributions through the use of the relativistic effective core potentials of Hay and Wadt (1985). Electron correlation was incorporated, using single-plus-double configuration interaction, the coupled pair functional (CPF) formalism of Ahlrichs et al. (1985), and the Chong and Langhoff (1986) modified version of the CPF method. The spectroscopic parameters D(e), r(e), and mu(e) determined for the low-lying states are compared with the available experimental data and previous theoretical results. In contrast to the first-row TM hydrides studied earlier (Chong et al., 1986), the spectroscopic constants for the second-row TM hydrides were found to be much less sensitive to the level of correlation treatment.

Langhoff, Stephen R.↗

NASA NTRS1987

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

The F + H2 yields HF + H potential energy hypersurface was studied in the saddle point and entrance channel regions. Using a large (5s 5p 3d 2f 1g/4s 3p 2d) atomic natural orbital basis set, a classical barrier height of 1.86 kcal/mole was obtained at the CASSCF/multireference CI level (MRCI) after correcting for basis set superposition error and including a Davidson correction (+Q) for higher excitations. Based upon an analysis of the computed results, the true classical barrier is estimated to be about 1.4 kcal/mole. The location of the bottleneck on the lowest vibrationally adiabatic potential curve was also computed and the translational energy threshold determined from a one-dimensional tunneling calculation. Using the difference between the calculated and experimental threshold to adjust the classical barrier height on the computed surface yields a classical barrier in the range of 1.0 to 1.5 kcal/mole. Combining the results of the direct estimates of the classical barrier height with the empirical values obtained from the approximation calculations of the dynamical threshold, it is predicted that the true classical barrier height is 1.4 + or - 0.4 kcal/mole. Arguments are presented in favor of including the relatively large +Q correction obtained when nine electrons are correlated at the CASSCF/MRCI level.

Bauschlicher, Charles W., Jr.↗

NASA NTRS1987

The 2D Rydberg series in Al I

High quality ab initio electonic structure calculations were performed on the 2D Rydberg series in Al I. The configuration 3s3p2(2D) is shown to contribute substantially to the lowest four 2D Rydberg states. The same configuration also contributes substantially to a 2D state embedded in the ionization continuum. Computed oscillator strengths for the first six members of the 2D Rydberg transitions are given: these should be of substantially high accuracy than currently available values.

Taylor, Peter R.↗

NASA NTRS1987

Theoretical approaches to metal chemistry

Theoretical calculations on metals ranging from very accurate ab initio studies of diatomic and triatomic systems to model studies of larger clusters are presented. Recent improvements in the representation of one-particle and n-particle spaces have made possible the prediction that Al2 has a 3Pi(u) ground state, even though the 3Sigma(-)g state lies within 200/cm. Results suggest that cluster geometry varies dramatically with cluster size, and that rather large clusters are required before the bulk structure becomes optimal. Al cluster studies show that three-body terms are needed for quantitative agreement with ab initio calculations.

Bauschlicher, Charles W.↗