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Walch, Stephen P.

Publications and source records attributed to Walch, Stephen P..

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NASA NTRS1987

Calculated potential surfaces for the reactions - O + N2 - NO + N and N + O2 - NO + O

Complete active space SCF/contracted CI calculations using large Gaussian basis sets are presented for selected portions of the potential surfaces for reactions in the Zeldovich mechanism for the conversion of N2 to NO. The N + O2 reaction is exoergic by 32 kcal/mol and is computed to have an early barrier of 10.2 kcal/mol for the 2A-prime surface and 18.0 kcal/mol for the 4A-prime surface. The O + N2 reaction is endoergic by 75 kcal/mol. The 3A-double prime surface is calculated to have a late barrier of 0.5 kcal/mol, while the 3A-prime surface has a late barrier of 14.4 kcal/mol relative to NO + N. These results are significant for determining the physical and chemical conditions which aeroassisted orbital transfer vehicles will encounter while transferring between high and low altitude earth orbits.

Walch, Stephen P.↗
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

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

Extended active space CASSCF/MRSD CI calculations of the barrier height for the reaction O + H2 yields OH + H

The convergence of the barrier height for the O + H2 yields OH + H reaction is studied as a function of the size of the active space in the CASSCF calculation and the size of the basis set. The basis set employed in this study is described. The sources of the differences between the POL-CI and MRSD-CI calculations for barrier height are examined. It is observed that the barrier height is rapidly convergent with respect to the expansion of the active space. The effects of adding active orbitals on the barrier height are investigated. The barrier height estimated from corrected MRSD-CI data is 12.4 kcal/mol.

Walch, Stephen P.↗
NASA NTRS1987

Computed potential surfaces for six low-lying states of Ni3

Selected portions of the potential surfaces for six low lying states of Ni3 are the subject of the present SCF/CCI calculations using the effective core potentials developed by Hay and Wadt (1985); the four states are studied for near-equilateral triangle geometries are within 0.04 eV of each other. Two states are studied for linear geometries, of which the first is 0.16 eV higher than the corresponding near-equilateral triangle state and the second is estimated to be nearly degenerate with the near-equilateral triangle structures.

Walch, Stephen P.↗
NASA NTRS1987

On nd bonding in the transition metal trimers: Comparison of Sc3 and Y3

CASSCF/CCI calculations are presented for the low-lying states of Y3. Comparison of the wave functions for Y3 and Sc3 indicates substantial 4d-5p hybridization in Y3, but little 3d-4p hybridization in Sc3. The increased 4d-5p hybridization leads to stabilization of 4dpi bonding with respect to 4dsigma bonding for equilateral triangle Y3, and also leads to 4d-5p bonding for linear geometries. These effects lead to a different ordering of states for equilateral triangle geometries and a smaller excitation energy to the linear configuration for Y3 as compared to Sc3.

Walch, Stephen P.↗
NASA NTRS1987

A theoretical study of the excited states of Ag3

Recently there was considerable interest in the properties and reactivities of small metal clusters. However, for the transition metal trimers, gas phase spectroscopy exists only for Cu3. Calculations are reported for the excited states of the Ag3 molecule. The excitation energies, geometries, derived harmonic frequencies, and transition moments are presented. The electronic structure of these states is very similar to the analogous states of Cu3. From the VCI wave functions transition moments were calculated between each of the Rydberg excited states and the ground state for an equilateral triangle geometry with R sub Ag-Ag = 5.3 a sub 0. One state was computed for the configuration 4d29 5sa sup prime 2 sub 1 5se sup prime 1 sub x 5se sup prime 1 sub y. This configuration was considered since the corresponding configuration for Cu3 is low-lying. Calculations were carried out for a quartet wavefunction in which the 4d hole was localized on the central Ag atom. The spectrum for Ag3 is expected to be simpler than for Cu3 since the 5s2 4d9 states are shifted to higher energy.

Walch, Stephen P.↗
NASA NTRS1986

Extended active space CASSCF/MRSD CI calculations of the barrier height for the reaction: O + H2 yields OH + H

The convergence of the barrier height for the O + H2 yields OH + H reaction was studied as a function of the size of the active space and basis set completeness. The barrier height is rapidly convergent with respect to expansion of the active space. Addition of 2p yields 2p' correlation terms to the active space lowers the barrier to the O + H2 reaction by about 2.0 kcal/mole, but addition of 3d and other terms has little additional effect. Multireference singles and doubles contracted CI plus Davidson's correction calculations using a (5s5p3d2f1g/4s3p2d1f) basis set with a 5 sigma 2 pi active space lead to a barrier height of 12.7 kcal/mole. Including an estimate of the CI contraction error and basis set superposition error leads to 12.4 kcal/mole as the best estimate of the barrier height.

Walch, Stephen P.↗
NASA NTRS1986

Calculated potential surfaces for the reactions: O + N2 yields NO + N and N + O2 yields NO + O

Complete Active Space SCF/Contracted CI (CASSCF/CCI) calculations, using large Gaussian basis sets, are presented for selected portions of the potential surfaces for the reactions in the Zeldovich mechanism for the conversion of N2 to NO. The N + O2 reaction is exoergic by 32 kcal/mole and is computed to have an early barrier of 10.2 kcal/mole for the (sup 2)A(sup prime) surface and 18.0 kcal/mole for the (sup 4)A(sup prime) surface. The O + N2 reaction is endoergic by 75 kcal/mole. The (sup 3)A(sup double prime) surface is calculated to have a late barrier of 0.5 kcal/mole, while the (sup 3)A(sup prime) surface is calculated to have a late barrier of 14.4 kcal/mole.

Walch, Stephen P.↗
NASA NTRS1986

Ab initio study of the ground state surface of Cu3

The ground state surface of the metallic trimer Cu3 is investigated theoretically. Relativistic and correlation effects are taken into account in ab initio computations, which are calibrated against analogous computations for the 1Sigma(g)+ state of Cu2; the results are presented in tables and analyzed. The Cu3 ground state is found to have a 2B2 C(2v) structure with angle greater than 60 deg, lying 59/cm below a 2A1 C(2v) geometry and 280/cm below the D(3h) equilateral geometry. These findings are shown to be in good agreement with the experimental measurements of Rohlfing and Valentini (1986) and their analysis (in terms of a Jahn-Teller distortion of 2E-prime equilateral-triangle geometry) by Truhlar et al. (1986).

Langhoff, Stephen R.↗
NASA NTRS1986

Theoretical studies of diatomic and triatomic systems containing the group IB atoms Cu, Ag, and Au

Selected portions of the ground state potential energy surfaces of the Cu3, Ag3, AgCu2, and AuCu2 trimers are studied at the single-reference singles plus doubles configuration interaction and couple pair functional levels correlating 33 electrons. The calculations use the effective core potentials of Hay and Wadt (1985) to replace the deep core levels. The Cu3 and Ag3 molecules are found to have 2B2 obtuse-angled ground states, with low-lying 2A1 acute-angled excited states. The AgCu2 and AuCu2 molecules have 2A1 acute-angled ground states. The Cu3 molecule has a smaller 3d population than Ag3, and Cu3 has a smaller s electron density in the open-shell orbital than does Ag3, in agreement with recent ESR experiments.

Walch, Stephen P.↗
NASA NTRS1986

The nature of the bonding in the transition metal trimers

The electronic structure of the transition metal (TM) trimers was studied by comparing the bonding in the Ca3, Sc3, and Cu3 molecules. The complete active space SCF/externally contracted configuration interaction (CI) ratio for the low-lying states of Sc3 and Sc3(+) and the SCF/CI ratio for Ca3 and Cu3 trimers, all for near equilateral triangle geometries, were calculated. In addition, vertical excitation energies for Cu3 were computed, leading to a new assignment of the upper state in the resonant two-photon ionization spectrum. Based on these studies, bonding in other TM trimers was discussed.

Walch, Stephen P.↗
NASA NTRS1986

The importance of atomic and molecular correlation on the bonding in transition metal compounds

The determination of accurate spectroscopic parameters for molecular systems containing transition metal atoms is shown to require extensive data sets and a high level correlation treatment, and techniques and their limitations are considered. Extensive results reported on the transition metal atoms, hydrides, oxides, and dimers makes possible the design of a calculation to correctly describe the mixing of different atomic asymptotes, and to give a correct balance between molecular bonding and exchange interactions. Examples considered include the dipole moment of the 2Delta state of NiH, which can help determine the mixture of 3d(8)4s(2) and 3d(9)4s(1) in the NiH wavefunction, and the bonding in CrO, where an equivalent description of the relative energies associated with the Cr 3d-3d atomic exchange and the Cr-O bond is important.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1986

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

The spectroscopic parameters and separations between the three low-lying X 3 Pi u, A 3 Sigma g -, and a 1 Sigma g + states of Al2 are studied as a function of both the one-particle and n-particle basis set. Approximate correlation treatments are calibrated against full Cl calculations correlating the six valence electrons in a double-zeta plus two d-function basis set. Since the CASSCF/MRCI 3 Pi u to 3 Sigma g - separation is in excellent agreement wtih the FCI value, the MRCI calculations were carried out in an extended (20s13p6d4f)/(6s5p3d2f) gaussian basis. Including a small correction for relativistic effects, the best estimate is that 3 Sigma g - state lies 174/cm above the 3 Pi u ground state. The 1 Sigma g + state lies at least 2000/cm higher in energy. At the CPF level, inclusion of 2s and 2p correlation has little effect on D sub e, reduces T sub e by only 26/cm, and shortens the bond lengths by about 0.02 a sub o. Further strong support for a 3 Pi u ground state comes from the experimental absorption spectra, since both observed transitions can be convincingly assigned as 3 Pi u yields 3 Pi g. The (2) 3 Pi g state is observed to be sensitive to the level of correlation treatment, and to have its minimum shifted to shorter rho values, such that the strongest experimental absorption peak probably corresponds to the 0 yields 2 transition.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1985

Theoretical studies of transition metal dimers

The CASSCF approach was used to perform the MCSCF calculations for a number of transition metal dimers, including the Sc2, Ti2, Cr2, Cu2, TiV, Y2, Nb2, and Mo2 molecules; in addition, CASSCF/CI calculations were carried out for Sc2, Ti2, Cu2, and Y2. The CASSCF procedure is shown to provide a consistent set of calculations for these molecules, from which trends and a simple qualitative picture of the electronic structure may be derived. In particular, the calculations confirmed the ground states of the Sc2 and the TiV, and led to predictions for other molecules in this series. In addition to specific predictions, the study provides a simple qualitative picture of the bonding in these dimers.

Walch, Stephen P.↗