Engineering Papers⌕ Search

SEARCH · Engineering Papers

Results for “Configuration interaction”

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 217 records · Page 12
All sourcesNASA NTRSDOE OSTI
NASA NTRS1998

Oscillator Strengths of Allowed and Intercombination Transitions in Neutral Sulfur

We have calculated oscillator strengths and transition probabilities of electric-dipole allowed and intercombination transitions from fine-structure levels of the ground 3s(sup 2)3p(sup 4) configuration to the levels belonging to configurations 3s(sup 2)3p(sup 3)4s, 3s(sup 2) 3p(sup 3)5s, 3(sup 2)3p(sup 3)3d, 3s(sup 2)3p(sup 3)4d of neutral sulfur. Extensive configuration-interaction wave functions are used to represent these levels. The relativistic corrections have been included through the Breit-Pauli Hamiltonian. The results are compared with previous theoretical calculations and with measurements.

Tayal, S. S.↗
NASA NTRS1995

Energy Levels and Oscillator Strengths for Allowed Transitions in S III

We have calculated energy levels and oscillator strengths for dipole-allowed transitions between the terms belonging to the 3s(sup 2)3p(sup 2), 3s3p(sup 3), 3S(sup 2)3p3d, 3S(sup 2)3p4s, 3S(sup 2)3p4p and 3s(sup 2)3p4d configurations of S iii in the LS-coupling scheme. We used flexible radial functions and included a large number of configurations in the configuration-interaction expansions to ensure convergence. The calculated energy levels are in close agreement with the recent laboratory measurement. The present oscillator strengths are compared with other calculations and experiments and most of the existing discrepancies between the available calculations are resolved.

Tayal, S. S.↗
NASA NTRS1997

Collision Strengths for Electron Collisional Excitation of S II

Electron collisional excitation strengths for inelastic transitions in S II are calculated using the R-matrix method in a 19-state (3s(sup 2)3p(sup 3)(sup 4)S(sup o), (sup 2)D(sup o), (sup 2)p(sup o), 3s3p(sup 4)(sup 4)P, (sup 2)D, (sup 2)S, 3S(sup 2)3p(sup 2)3d(sup 2)P, (sup 4)F, (sup 4)D, (sup 2)F, (sup 4)P, 3s(sup 2)3p(sup 2)4s(sup 4)P, (sup 2)P, 3s(sup 2)3p(sup 2)4p(sup 2)S(s o), (sup 4)D(sup o), (sup 4)P(sup o), (sup 2)D(sup o), (sup 4)S(sup o), (sup 2)P(sup o)) close-coupling approximation. These target states are represented by extensive configuration-interaction wave functions that give excitation energies and oscillator strengths that are usually in good agreement with the experimental values and the available accurate calculations. The present results for collision strengths are in very good agreement with the recent merged beams energy loss measurement of Liao et al. and agree reasonably well with the 18-state R-matrix calculation of Ramsbottom, Bell, & Stafford, but show significant differences from the 12-state R-matrix calculation of Cai & Pradhan.

Tayal, S. S.↗
NASA NTRS1997

Effective Collision Strengths for Electron Impact Excitation of Inelastic Transitions in S III

We have calculated electron collisional excitation strengths for all electric dipole forbidden, semi-forbidden, and allowed transitions among the lowest 17 LS states 3s(exp 2)3p(exp 2) P-3, D-1, S-1, 3s3p(exp 3)S-5(exp 0), D-3(exp 0), P-3(exp 0), P-1(exp 0), S-3(exp 0), D-1(exp 0), 3S(exp 2)3p3d D-1(exp 0), F-3(exp 0), P-3(exp 0), D-3(exp 0), F-3(exp 0), P-1(exp 0), and 3S(exp 2)3p4S P-3(exp 0), P-l(exp 0) of S III using the R-matrix method. These S m states are represented by fairly extensive configuration-interaction wave functions that yield excited state energies in close agreement with recent laboratory measurements. Rydberg series of resonances converging to the excited state thresholds are explicitly included in the scattering calculation. The effective collision strengths are determined assuming Maxwellian distribution of electron energies. These are listed over a wide temperature range ([0.5-10] x 10(exp 4) K) and compared, where possible, with other available calculations. Subject headings: atomic data - atomic processes

Tayal, S. S.↗
NASA NTRS1986

Theoretical Study of the Electric Dipole Moment Function of the CIO Molecule

The potential energy function and electric dipole moment function (EDMF) are computed for CIO Chi(sup 2)Pi using several different techniques to include electron correlation. The EDMF is used to compute Einstein coefficients, vibrational lifetimes, and dipole moments in higher vibrational levels. Remaining questions concerning the position of the maximum of the EDMF may be resolved through experimental measurement of dipole moments of higher vibrational levels. The band strength of the 1-0 fundamental transition is computed to be 12 +/- 2 /sq cm atm in good agreement with three experimental values, but larger than a recent value of 5 /sq cm atm determined from infrared heterodyne spectroscopy. The theoretical methods used include SCF, CASSCF, multireference singles plus doubles configuration interaction (MRCI) and contracted CI, coupled pair functional (CPF), and a modified version of the CPF method. The results obtained using the different methods are critically compared.

Pettersson, Lars G. M.↗
NASA NTRS1999

On Photospheric Fluorescence and the Nature of the 17.62 Angstrom Feature in Solar X-ray Spectra

The identification of the emission line feature at 17.62 Angstroms in solar x-ray spectra is re-examined. Using a Monte Carlo technique, we compute a realistic theoretical upper limit to the observed Fe L-alpha photospheric fluorescent line strength caused by irradiation from an overlying corona. These calculations demonstrate that the photospheric Fe L-alpha characteristic line is much too weak to account for the observed 17.62 Angstrom line flux. Instead, we identify this line with the configuration interaction 2s2p3p2P-2s2p6 2S transition in Fe XVIII seen in Electron Beam Ion Trap spectra and predicted in earlier theoretical work on the Fe XVIII x-ray spectrum.

Drake, Jeremy J.↗
NASA NTRS1994

The Low-Lying States of AlCu and AlAg

The singlet and triplet states of AlCu and AlAg below about 32 000/cm are studied using the internally contracted multireference configuration-interaction method. A more elaborate study of the X(sup 1)Sum(sup +) ground state of AlCu is undertaken using extended Gaussian basis sets, including the effect of inner-shell correlation and including a perturbational estimate of relativistic effects. Our best estimate of the spectroscopic constants (r(sub 0), DeltaG(sub 1/2), and D(sub 0)) for the X(sup 1)Sum(sup+) state with the experimental values in parentheses are: 4.416(4.420) a(sub 0), 295 (294) /cm, and 2.318 (2.315) eV. The calculations definitively assign the upper state in the observed transition at 14 892/cm to the lowest (sup 1)Prod state. The calculated spectroscopic constants and radiative lifetime for the (sup 1)Prod state are in good agreement with experiment. The calculations support the tentative assignments of Behm et al. for three band systems observed in the visible region between 25 000 and 28 000 / cm. However, the computed spectroscopic constants are in very poor agreement with those deduced from an analysis of the spectra. Analogous theoretical results for AlAg suggest that the (2)(sup 3)Prod, (3)(sup 3)Prod, and (3)(sup 1)Sum(sup +) states account for the bands observed, but not assigned, by Duncan and co-workers.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1994

Theoretical Study of the Low-Lying States of TiHe(+),TiNe(+),TiAr(+),VAr(+),CrHe(+),CrAr(+),FeHe(+),FeAr(+),CoHe(+),and CoAr(+)

The potential energy curves for the manifold of molecular states dissociating to the lowest transition metal ion states derived from the 3d(sup n+1) and 3d(sup n)4s(sup 1) occupations have been determined for selected transition-metal ion- rare gas systems. These curves have been computed using large basis sets, and the state-averaged complete- active-space self-consistent-field/multireference configuration interaction level of electron correlation treatment. In general, the families of curves derived from the 3d(sup n+1) and 3d(sup n)4s(sup 1) metal occupations are disjoint; however, for Ti(+) there is a strong mixing of the 3d(sup 2)4s(sup 1) and 3d(sup 3) asymptotes, because of the small separation between the asymptotes. This mixing leads to a failure of single-reference-based techniques; this is discussed in the context of our previous single-reference-based treatments.

Partridge, Harry↗
NASA NTRS1990

An Ab Initio Study of the Low-Lying Doublet States of AgO and AgS

Spectroscopic constants (D(sub o), r(sub e), mu(sub e), T(sub e)) are determined for the doublet states of AgO and AgS below approx. = 30000/cm. Large valence basis sets are employed in conjunction with relativistic effective core potentials (RECPs). Electron correlation is included using the modified coupled-pair functional (MCPF) and multireference configuration interaction (MRCI) methods. The A(sup 2)Sigma(sup +) - X(sup 2)Pi band system is found to occur in the near infrared (approx. = 9000/cm) and to be relatively weak with a radiative lifetime of 900 microns for A(sup 2)Sigma(sup +) (upsilon = 0). The weakly bound C(sup 2)Pi state (our notation), the upper state of the blue system, is found to require high levels of theoretical treatment to determine a quantitatively accurate potential. The red system is assigned as a transition from the C(sup 2)Pi state to the previously unobserved A(sup 2)Sigma(sup +) state. Several additional transitions are identified that should be detectable experimentally. A more limited study is performed for the vertical excitation spectrum of AgS. In addition, a detailed all-electron study of the X(sup 2)Pi and A(sup 2)Sigma(sup +) states of AgO is carried out using large atomic natural orbital (ANO) basis sets. Our best calculated D(sub o) value for AgO is significantly less than the experimental value, which suggests that there may be some systematic error in the experimental determination.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1981

Theoretical Treatment of the X(sup 1)Sigma(sup +), A(sup 1)Sigma(sup +), and B(sup 1)Pi states of LiH

Ab initio self-consistent-field plus configuration-interaction calculations are reported for the X(sup 1)Sigma(sup +), A(sup 1)Sigma(sup +), and B(sup 1)Pi states of LiH using a 22(sugma)12(pi)7(delta) function Slater basis set. The resulting dissociation energies, with the experimental values in parentheses, are D(sub e)(X(sup 1)Sigma(sup +)) = 19 972 (20288)/ cm, and D(sub e)(A(sup 1)Sigma(sup +)) = 9042 (8682)/ cm, and D(sup e)(B(sup 1)Pi) = 284 (288) /cm. This is the first ab initio treatment to quantitatively account for the binding in the B(sup 1)Pi state. Calculated dipole moments and electronic transition moments for the X(sup 1)Sigma(sup+)-A(sup 1)Sigma(sup +), X(sup 1)Sigma(sup +)-B((sup 1)Pi, and A(sup 1)Sigma(sup +)- B(sup 1)PI band systems are in excellent agreement with existing theoretical and experimental data. Radiative transition probabilities and lifetimes, including both the bound-bound and bound-free contributions, are computed for all vibrational levels of the A(sup 1)Sigma(sup+) and B(sup 1)Pi states. Comparison with previous results using experimentally based potentials provides insight into the sensitivity of the radiative lifetimes to the detailed nature of the uppermost region of the potentials. Our calculated lifetimes for the lower vibrational levels of the A(sup 1)Sigma(sup +) state are within the experimental uncertainty. Our calculated lifetimes for the three vibrational levels of the B(sup 1)Pi state are in excellent agreement with those of Zemke and Stwalley (values in parentheses), increasing with (upsilon)' from 11.3 (11.3) nsec at (upsilon)' = 0, to 17.0 (17.0) nsec at (upsilon)' = 1, and then to 23.5 (24.0) nsec at (upsilon)' = 2.

Partridge, Harry↗
NASA NTRS2001

The A6Sigma+ - X6Sigma+ Transition of CrH, Einstein Coefficients and an Improved Description of the A State

The spectrum of CrH has been reinvestigated in the 9000-15000/cm region using the Fourier transform spectrometer of the National Solar Observatory. The 1-0 and 1-1 bands of the A6Sigma+ - X6Sigma+ transition have been measured and improved spectroscopic constants have been determined. A value for the 2-0 band origin has been obtained from the band head using estimated spectroscopic constants. These data provide a set of much improved equilibrium vibrational and rotational constants for the A6Sigma+ state. An accurate description of the A-X transition has been obtained using a multi-reference configuration interaction approach. The inclusion of both scalar relativity and Cr 3s3p correlation are required to obtain a good description of both states. The ab initio computed Einstein coefficients and radiative lifetimes are reported.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1994

The Low-Lying Electronic States of Mg2(+)

The low-lying doublet and quartet states of Mg+ have been studied using a multireference configuration interaction approach. The effect of inner-shell correlation has been included using the core-polarization potential method. The computed spectroscopic constants, lifetimes, and oscillator strengths should help resolve the difference between the recent experiments and previous theoretical calculations.

Ricca, Alessandra↗
NASA NTRS1994

Electronic spectroscopy of diatomic molecules

This article provides an overview of the principal computational approaches and their accuracy for the study of electronic spectroscopy of diatomic molecules. We include a number of examples from our work that illustrate the range of application. We show how full configuration interaction benchmark calculations were instrumental in improving the understanding of the computational requirements for obtaining accurate results for diatomic spectroscopy. With this understanding it is now possible to compute radiative lifetimes accurate to within 10% for systems involving first- and second-row atoms. We consider the determination of the infrared vibrational transition probabilities for the ground states of SiO and NO, based on a globally accurate dipole moment function. We show how we were able to assign the a(sup "5)II state of CO as the upper state in the recently observed emission bands of CO in an Ar matrix. We next discuss the assignment of the photoelectron detachment spectra of NO and the alkali oxide negative ions. We then present several examples illustrating the state-of-the-art in determining radiative lifetimes for valence-valence and valence-Rydberg transitions. We next compare the molecular spectroscopy of the valence isoelectronic B2, Al2, and AlB molecules. The final examples consider systems involving transition metal atoms, which illustrate the difficulty in describing states with different numbers of d electrons.

Partridge, Harry↗
NASA NTRS1994

Large Atomic Natural Orbital Basis Sets for the First Transition Row Atoms

Large atomic natural orbital (ANO) basis sets are tabulated for the Sc to Cu. The primitive sets are taken from the large sets optimized by Partridge, namely (21s 13p 8d) for Sc and Ti and (20s 12p 9d) for V to Cu. These primitive sets are supplemented with three p, one d, six f, and four g functions. The ANO sets are derived from configuration interaction density matrices constructed as the average of the lowest states derived from the 3d(sup n)4s(sup 2) and 3d(sup n+1)4s(sup 1) occupations. For Ni, the 1S(3d(sup 10)) state is included in the averaging. The choice of basis sets for molecular calculations is discussed.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1994

Accurate Energetics for the Unimolecular Decomposition of HN2

We report internally contracted configuration interaction (ICCI) calculations along the constrained energy minimum (CEM) path for the addition of H to N2 with both CC-pVQZ and augmented CC-pVQZ basis sets. The results agree to within 0.5 kcal/mol with the larger basis set results of Walch, which were used to calibrate the HN2 potential energy surface used by Koizumi, Schatz, and Walch in coupled channel calculations to determine the lifetimes for unimolecular decay of the lowest vibrational levels of HN2. These small changes in the potential energy surface should have no significant effect on the computed lifetimes.

Walch, Stephen P.↗
NASA NTRS1994

Computed Minimum Energy Pathway for Isomerization in Ketene

A minimum energy pathway for interchange of the CH groups in ketene via a C2v structure has been obtained using complete active space self consistent field (CASSCF) derivative methods with a polarized valence double zeta basis set to define the reaction pathway followed by multi-reference internally contracted configuration interaction (ICCI) calculations with a [3s3p2d/3s2p] basis set to determine the energetics. Qualitatively, the C2v structure is found to be a shallow minimum on the potential energy surface separated from ketene by a small barrier (0.2 kcal/mol), a second minimum, and a larger barrier (3.0 kcal/mol). The minimum energy pathway leading from the C2v minimum to ketene starts by simultaneous rotation of the farther CH group out of the plane and away from the oxygen followed by increase of the CCO angle and subsequent 1,2-migration of the H of the nearer CH group toward the carbon of the farther CH group.

Walch, Stephen P.↗
NASA NTRS1994

Theoretical Study of the Low-Lying States of MgN+2

The structure and binding energies of the low-lying states of MgN2+ have been computed at the multireference configuration interaction level of theory. The effect of Mg inner-shell correlation have been included using the core-polarization potential method. The charge-quadrupole interaction results in a linear 2Sigma+ ground state as expected. The excited states can arise from either the interaction of the 2-P state of Mg+ with N2 or from charge transfer states with Mg(sup 2+)N2- bonding character. The lowest lying excited state, 2-B2, is mixture of these two mechanisms, which results in a C2v, geometry with Mg atoms sitting at the N2 bond midpoint. The small barrier in the bending potential exists between this state and the 2-II State which is the lowest lying linear excited state.

Maitre, Philippe↗
NASA NTRS1994

A New Global Potential Energy Surface for the Hydroperoxyl Radical, HO2: Reaction Coefficients for H + O2 and Vibrational Splittings for H Atom Transfer

A new analytic global potential energy surface describing the hydroperoxyl radical system H((sup 2)S) + O2(X (sup 3)Sigma((sup -)(sub g))) (reversible reaction) HO2 ((X-tilde) (sup 2)A'') (reversible reaction) O((sup 3)P) + O H (X (sup 2)Pi) has been fitted using the ab initio complete active space SCF (self-consistent-field)/externally contracted configuration interaction (CASSCF/CCI) energy calculations of Walch and Duchovic. Results of quasiclassical trajectory studies to determine the rate coefficients of the forward and reverse reactions at combustion temperatures will be presented. In addition, vibrational energy levels were calculated using the quantum DVR-DGB (discrete variable representation-distributed Gaussian basis) method and the splitting due to H atom migration is investigated. The material of the proposed presentation was reviewed and the technical content will not reveal any information not already in the public domain and will not give any foreign industry or government a competitive advantage.

Dateo, Christopher E.↗