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At least 361 records · Page 20
All sourcesNASA NTRSDOE OSTI
NASA NTRS1978

On the electronic structure of the 2 1A1 state of methylene

The electronic structure of the 2 1A1 state of methylene is studied using multiconfiguration self-consistent-field and extended configuration interaction wavefunctions, as a prelude to a detailed investigation of the role of excited states in the chemistry of carbenes. Using selected one-electron properties as a guide, correlated wavefunctions obtained by different approaches are compared for the purpose of establishing qualitative differences between 1 1A1 and 2 1A1 states.

Bauschlicher, C. W., Jr.↗
NASA NTRS1979

SCF and CI calculations of the dipole moment function of ozone

The constant and linear terms in a Taylor series expansion of the dipole moment function of the ground state of ozone are calculated with Cartesian Gaussian basis sets ranging in quality from minimal to double zeta plus polarization. Results are presented at both the self-consistent field and configuration-interaction levels. Although the algebraic signs of the linear dipole moment derivatives are all established to be positive, the absolute magnitudes of these quantities, as well as the infrared intensities calculated from them, vary considerably with the level of theory.

Curtiss, L. A.↗
NASA NTRS1980

MCSCF wave functions for excited states of polar molecules - Application to BeO

A previously reported multi-configuration self-consistent field (MCSCF) algorithm based on the generalized Brillouin theorem is extended in order to treat the excited states of polar molecules. In particular, the algorithm takes into account the proper treatment of nonorthogonality in the space of single excitations and invokes, when necessary, a constrained optimization procedure to prevent the variational collapse of excited states. In addition, a configuration selection scheme (suitable for use in conjunction with extended configuration interaction methods) is proposed for the MCSCF procedure. The algorithm is used to study the low-lying singlet states of BeO, a system which has not previously been studied using an MCSCF procedure. MCSCF wave functions are obtained for three 1 Sigma + and two 1 Pi states. The 1 Sigma + results are juxtaposed with comparable results for MgO in order to assess the generality of the description presented here.

Bauschlicher, C. W., Jr.↗
NASA NTRS1980

Relativistic K-shell Auger rates, level widths, and fluorescence yields

Systematic relativistic (Dirac-Hartree-Slater) calculations of atomic K-shell Auger transition probabilities are reported for 25 elements with Z between 18 and 96, inclusive. K-level Auger widths are found to be enhanced by relativistic effects, while total K-level widths are reduced. Relativistic theoretical K-shell fluorescence yields are in excellent agreement with experiment. Theoretical relative intensities of K-LX Auger transitions in heavy elements, calculated in j-j coupling, agree well with measurements; for low Z, configuration interaction and intermediate coupling must apparently be included.

Chen, M. H.↗
NASA NTRS1980

New approach to hyperfine structure - Application to the Li ground state

Global identities for delta functions, given by Hiller, Sucher and Feinberg (HSF) are applied to the calculation of the hyperfine structure (HFS) of the ground state of Li. It is shown that use of the HSF identity together with configuration interaction type wavefunctions can yield values of the HFS constant f which are comparable in accuracy to that obtained by Larsson with a 100-term Hylleraas-type wavefunction. The implications of this result for HFS calculations for atoms with many electrons are discussed.

Bhatia, A. K.↗
NASA NTRS1980

An SCF and MCSCF description of the low-lying states of MgO

The paper presents the multiconfiguration-self-consistent (MCSCF) and configuration state functions (CSF) for the low-lying electronic states of MgO. It was shown that simple description of these states was possible provided the 1 Sigma(+) states are individually optimized at the MCSCF level, noting that the 1(3 Sigma)(+) and 2(1 Sigma)(+) states which nominally result from the same electron occupation are separated energetically. The molecular orbitals obtained at this level of approximation should provide a useful starting point for extended configuration interaction calculations since they have been optimized for the particular states of interest.

Bauschlicher, C. W., Jr.↗
NASA NTRS1981

The B/K/ method - Application to methylene

The B(K) method is compared with conventional Configuration Interaction (CI) and other perturbation methods for the 3B1 and 1A1 states of methylene. Use of Rayleigh-Schroedinger perturbation theory for construction of an effective Hamiltonian is seen to be more accurate for estimating the full CI energy limit.

Davidson, E. R.↗
NASA NTRS1981

Theoretical calculation of low-lying states of NaAr and NaXe

Potential curves as well as dipole moments and linking transition moments are calculated for the ground X 2 Sigma + and low lying excited A 2 Pi, B 2 Sigma +, C 2 Sigma +, (4) 2 Sigma +, (2) 2 Pi and (1) 2 Delta states of NaAr and NaXe. Calculations are performed using a self-consistent field plus configuration-interaction procedure with the core electrons replaced by an ab initio effective core potential. The potential curves obtained are found to be considerably less repulsive than the semiempirical curves of Pascale and Vandeplanque (1974) and to agree well with existing experimental data, although the binding energies of those states having potential minima due to van der Waals interactions are underestimated. Emission bands are also calculated for the X 2 Sigma + - C 2 Sigma + excimer transitions of NaAr and NaXe using the calculated transition moments and potential curves, and shown to agree well with experiment on the short-wavelength side of the maximum.

Laskowski, B. C.↗
NASA NTRS1981

Theoretical electronic transition moments for the Ballik-Ramsay, Fox-Herzberg, and Swan systems of C2

Electronic transition moments and their variation with internuclear separation are calculated for the Ballik-Ramsay (b 3 Sigma g - a 3 Pi u), Fox-Herzberg (e 3 Pi g-a 3 Pi u) and Swan (d 3 Pi g-a 3 Pi u) band systems of C2, which appear in a variety of terrestrial and astrophysical sources. Electronic wave functions of the a 3 Pi u, b 2 Sigma g -, d 3 Pi g and e 3 Pi g states of C2 are obtained by means of a self-consistent field plus configuration interaction calculation using an atomic basis of 46 Slater-type orbitals, and theoretical potential energy curves and spectroscopic constants for the four electronic states were computed. The results obtained for both the potential energy curves and electronic transition moments are found to be in good agreement with experimental data.

Cooper, D. M.↗
NASA NTRS1982

Oscillator strengths and collision strengths for some ions of oxygen and sulphur

Collision strengths for electron impact excitation of the O II, O III, S II and S III for some transitions in the ultraviolet of the type ns(sup 2) np(sup q) yields ns np(sup q +1), ns(sup 2) np(sup q) yields ns(sup 2) np(sup q-1) (n+1)s and 3s2 3p(sup q) yields 352 3p(sup q -1) 3d are calculated in a close coupling approximation for an energy rate up to one million K. Configuration interaction target wave functions which give oscillator strengths accurate to 10% for O II and O III, and 20-30% for S II and S III, are used in the expansion. Accurate knowledge of the electron impact excitation cross sections is particularly significant for a proper interpretation of the combined ultraviolet observations of the Voyager UVS and IUE results on properties of the Io plasma torus.

Ho, Y. K.↗
NASA NTRS1982

Theoretical study of IR band intensities and electronic transition moments for the beta and delta systems of NO

The variation of the electronic transition moment with internuclear separation has been calculated for the beta and delta systems of NO. Theoretical band intensities for the fundamental and first two overtones have also been calculated for the ground state. The results are based on the self-consistent-field plus configuration-interaction technique, and they are compared with the existing experimental data. Theoretical potential-energy curves and the spectroscopic constants for the X-squared Pi, B-squared Pi, and C-squared Pi electronic states of NO are also reported.

Cooper, D. M.↗
NASA NTRS1982

Molecular processes in comets

Potential energy curves for the two lowest 2 sigma- states of OH are computed at the configuration-interaction level using four different basis sets. Electronic transition dipole moments connecting the excited 1 2 sigma- and 2(D) 2 sigma- states with each other and with he ground X2pi state are presented as functions of internuclear distance. The theoretical absorption oscillator strengths for the D 2 sigma-(v prime=0) reverser to X 2pi (v prime prime=0) transition are in good agreement with the empirical value derived from astronomical measurements. The photodissociation cross sections for absorption rom the v prime prime=0,1, and levels of the ground state into the continuum of the 1 2 sigma- state are calculated, and the interstellar and cometary photodissociation rates are derived.

Dalgarno, A.↗
NASA NTRS1983

The low-lying 2-sigma-minus states of OH

The configuration-interaction method is used to determine the electronic wave functions of the two lowest 2-sigma-minus states of OH using four different atomic orbital basis sets. Potential energy curves, transition moments, oscillator strengths, and photodissociation cross sections are obtained. Electronic transition dipole moments connecting the excited 1 2-sigma-minus and 2(D)2-sigma-minus states with each other and with the ground chi-2-pi state are presented as functions of internuclear distance. The theoretical absorption oscillator strengths for the D-2-sigma-minus(v prime = 0) from chi-2-pi(v double prime = 0) transition are in good agreement with the empirical value derived from astronomical measurement. The photodissociation cross sections for absorption from the v prime = 0, 1, and 2 levels of the ground state into the continuum of the 1 2-sigma-minus state are calculated, and the interstellar and cometary photodissociation rates are derived.

Van Dishoeck, E. F.↗
NASA NTRS1983

A theoretical study on the mechanism of electronic to vibrational energy transfer in Hg/3P/ + CO

The mechanism of electronic-to-vibrational (E-V) energy transfer in Hg(3P) + CO collisions has been studied theoretically. The configuration interaction (CI) method was employed to calculate potential energy surfaces of the collision system. A simplified theoretical model, based on the reaction coordinate concept and the calculated potential energy characteristics, was used to discuss the mechanism of the singlet-triplet transition and the energy disposal in the collision. The results obtained were that: (a) the quenching process processed via a collision complex mechanism; and that (b) the triplet-singlet transition occurs near the collinear geometry. A model classical trajectory calculation gives a product CO vibrational distribution in good agreement with the experimental result.

Kato, S.↗
NASA NTRS1983

Oscillator strengths and collision strengths for S II

Calculations are presented of the collision strengths for electron impact excitation of S II from the ground 3s(2)3p(3)(4)S0 state to excited states 3s3p(4)(4)p, 3s(2(3p(2)4s(4)P, and 3s(2)3p(2)3d(4)P. The collision strengths are calculated in a close-coupling approximate ion for the energy range up to 10 to the 6th K. In addition, oscillator strengths are given for these transitions, as well as for some UV lines which have lower states 3s(2)3p(3)(2)D(O) and 3s(2)3p(3)(2)P(0). The calculation of the collision strengths involves the use of configuration interaction target wave functions which give oscillator strengths accurate to 30 percent in most cases.

Ho, Y. K.↗
NASA NTRS1984

Atomic inner-shell transitions

Atomic inner-shell processes have quite different characteristics, in several important aspects, from processes in the optical regime. Energies are large, e.g., the 1s binding energy reaches 100 keV at Z = 87; relativistic and quantum-electrodynamic effects therefore are strong. Radiationless transitions vastly dominate over photon emission in most cases. Isolated inner-shell vacancies have pronounced single-particle character, with correlations generally contributing only approximately 1 eV to the 1s and 2p binding energies; the structure of such systems is thus well tractable by independent-particle self-consistent-field atomic models. For systems containing multiple deep inner-shell vacancies, or for highly stripped ions, the importance of relativistic intermediate coupling and configuration interaction becomes pronounced. Cancellation of the Coulomb interaction can lead to strong manifestations of the Breit interaction in such phenomena as multiplet splitting and hypersatellite X-ray shifts. Unique opportunities arise for the test of theory.

Crasemann, B.↗
NASA NTRS1984

Hydrogen atom abstraction from aldehydes - OH + H2CO and O + H2CO

The essential features of the potential energy surfaces governing hydrogen abstraction from formaldehyde by oxygen atom and hydroxyl radical have been characterized with ab inito multiconfiguration Hartree-Fock (MCHF) and configuration interaction (CI) wave functions. The results are consistent with a very small activation energy for the OH + H2CO reaction, and an activation energy of a few kcal/mol for the O + H2CO reaction. In the transition state structure of both systems, the attacking oxygen atom is nearly collinear with the attacked CH bond.

Dupuis, M.↗
NASA NTRS1984

Theoretical electric quadrupole transition probabilities for Ca, Sr and Ba

The 1D-1S quadrupole transition probabilities for Ca, Sr and Ba have been computed using extended GTO and STO valence basis sets and configuration-interaction wavefunctions that include the important core-valence correlation effects. For Ba and Sr, the relativistic contraction of the core orbitals was accounted for in the GTO calculations by a relativistic effective-core potential. The computed Einstein coefficient for Ca of 39.6/s is in excellent agreement with the recent experimental value of 40 + or - 8/s. The best Einstein coefficients for Sr (44.7/s) and Ba (2.98/s) imply increasing quadrupole line strengths down the column. Relativistic effects substantially increase the quadrupole Einstein coefficient for Ba.

Bauschlicher, C. W., Jr.↗