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At least 469 records · Page 26
All sourcesNASA NTRSDOE OSTI
NASA NTRS1995

Characterization of the Minimum Energy Path for the Reaction of Singlet Methylene with N2: The Role of Singlet Methylene in Prompt NO

We report calculations of the minimum energy pathways connecting (1)CH2+N2 to diazomethane and diazirine, for the rearrangement of diazirine to diazomethane, for the dissociation of diazirine to HCN2+H, and of diazomethane to CH2N+N. The calculations use complete active space self-consistent field (CASSCF) derivative methods to characterize the stationary points and internally contracted configuration interaction (ICCI) to determine the energetics. The calculations suggest a potential new source of prompt NO from the reaction of (1)CH2 with N2 to give diazirine, and subsequent reaction of diazirine with hydrogen abstracters to form doublet HCN2, which leads to HCN+N(S-4) on the previously studied CH+N2 Surface. The calculations also predict accurate 0 K heats of formation of 77.7 kcal/mol and 68.0 kcal/mol for diazirine and diazomethane, respectively.

Walch, Stephen P.↗
NASA NTRS1995

Characterization of the Minimum Energy Paths for the Ring Closure Reactions of C4H3 with Acetylene

The ring closure reaction of C4H3 with acetylene to give phenyl radical is one proposed mechanism for the formation of the first aromatic ring in hydrocarbon combustion. There are two low-lying isomers of C4H3; 1-dehydro-buta-l-ene-3-yne (n-C4H3) and 2-dehydro-buta-l-ene-3-yne (iso-C4H3). It has been proposed that only n-C4H3 reacts with acetylene to give phenyl radical, and since iso-C4H3 is more stable than n-C4H3, formation of phenyl radical by this mechanism is unlikely. We report restricted Hartree-Fock (RHF) plus singles and doubles configuration interaction calculations with a Davidson's correction (RHF+1+2+Q) using the Dunning correlation consistent polarized valence double zeta basis set (cc-pVDZ) for stationary point structures along the reaction pathway for the reactions of n-C4H3 and iso-C4H3 with acetylene. n-C4H3 plus acetylene (9.4) has a small entrance channel barrier (17.7) (all energetics in parentheses are in kcal/mol with respect to iso-C4H3 plus acetylene) and the subsequent closure steps leading to phenyl radical (-91.9) are downhill with respect to the entrance channel barrier. Iso-C4H3 Plus acetylene also has an entrance channel barrier (14.9) and there is a downhill pathway to 1-dehydro-fulvene (-55.0). 1-dehydro-fulvene can rearrange to 6-dehydro-fulvene (-60.3) by a 1,3-hydrogen shift over a barrier (4.0), which is still below the entrance channel barrier, from which rearrangement to phenyl radical can occur by a downhill pathway. Thus, both n-C4H3 and iso-C4H3 can react with acetylene to give phenyl radical with small barriers.

Walch, Stephen P.↗
NASA NTRS1996

Collision Strengths for Electron Impact Excitation of Inelastic Transitions in Ar II

We have calculated collision strengths for electron impact excitation of inelastic transitions in Ar II using the R-matrix method in two independent nine- and 19-state close-coupling approximations. In the nine-state calculation the 3s(sup 2)3p(sup 5)2p(sup 0), 3S(sup 3)p(sup 6)S-2, 3p(sup 4)(P-3)4s(sup 2)P, 3p(sup 4)(P-3)3d(sup 2)P, 3p(sup 4)(D-1)4s(sup 2)D, 3p(sup 4)(P-3)3d(sup 2)D, 3p(sup 4)(S-1)4s(sup 2)S, 3p(sup 4)(D-1)3d(sup 2)S and 3p(sup 4)(D-1)4d(sup 2)S states are included, while in the 19-state calculation these states plus an additional ten states 3p(sup 4)(P-3)3d(sup 2)F, 3p(sup 4)(P-3)4p(sup 2)D(sup 0), 2p(sup 0), 2S(sup 0), 3p(sup 4)(D-1)4p(sup 2)P(sup 0), 2D(sup O), 2F(sup 0), 3p(sup 4)(D-1)3d(sup 2)D, p-2 and 3p(sup 4)(S-1)4p(sup 2)P(sup 0) are considered. These target states are represented by fairly extensive configuration-interaction wavefunctions which yield excitation energies and oscillator strengths that are generally in good agreement with the available most accurate calculations and the experimental values. Rydberg series of resonances converging to the excited state thresholds are included in the calculation. The effective collision strengths are obtained assuming a Maxwellian distribution of electron energies which are tabulated over the temperature range (0.5-20) x 10(exp 4) K.

Tayal, S. S.↗
NASA NTRS1997

Oscillator Strengths for Fine-Structure Transitions in S III

Oscillator strengths and transition probabilities for transitions among the fine-structure levels of 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 are calculated using extensive configuration-interaction wave functions. The relativistic effects in intermediate coupling are incorporated by means of the Breit-Pauli Hamiltonian. Small adjustments to the diagonal elements of the Hamiltonian matrices have been made so that the energy splittings are as close as possible to the experimental values. The present results are compared with other available calculations and experiments.

Tayal, S. S.↗
NASA NTRS1998

Cross Sections for Electron Impact Excitation of Ions Relevant to Planetary Atmospheres Observation

The goal of this research grant was to calculate accurate oscillator strengths and electron collisional excitation strengths for inelastic transitions in atomic species of relevance to Planetary Atmospheres. Large scale configuration-interaction atomic structure calculations have been performed to obtain oscillator strengths and transition probabilities for transitions among the fine-structure levels and R-matrix method has been used in the calculations of electron-ion collision cross sections of C II, S I, S II, S III, and Ar II. A number of strong features due to ions of sulfur have been detected in the spectra of Jupiter satellite Io. The electron excitation cross sections for the C II and S II transitions are studied in collaboration with the experimental atomic physics group at the Jet Propulsion Laboratory. There is excellent agreement between experiment and theory which provide an accurate and broad-base test of the ability of theoretical methods used in the calculation of atomic processes. Specifically, research problems have been investigated for: electron impact excitation cross sections of C II: electron impact excitation cross sections of S III; energy levels and oscillator strengths for transitions in S III; collision strengths for electron collisional excitation of S II; electron impact excitation of inelastic transitions in Ar II; oscillator strengths of fine-structure transitions in neutral sulfur; cross sections for inelastic scattering of electrons from atomic nitrogen; and excitation of atomic ions by electron impact.

Tayal, Swaraj S.↗
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↗