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At least 451 records · Page 25
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NASA NTRS1992

Ab initio multireference study of the BN molecule

The lowest 1Sigma(+) and 3Pi states of the BN molecule are studied using multireference configuration interaction (MRCI) and averaged coupled-pair functional (ACPF) methods and large atomic natural orbital (ANO) basis sets, as well as several coupled cluster methods. Our calculations strongly support a 3Pi ground state, but the a1Sigma(+) state lies only 381 +/- 100/cm higher. The a1Sigma(+) state wave function exhibits strong multireference character and, consequently, the predictions of the perturbationally-based single-reference CCSD(T) coupled cluster method are not as reliable in this case as the multireference results. The theoretical predictions for the spectroscopic constants of BN are in good agreement with experiment for the Chi3Pi state, but strongly suggest a misassignment of the fundamental vibrational frequency for the a1Sigma(+) state.

Martin, J. M. L.↗
NASA NTRS1993

Theoretical characterization of the potential energy surface for NH + NO

The potential energy surface for NH + NO was characterized using complete active space self-consistent field (CASSCF) gradient calculation to determine the stationary point geometries and frequencies followed by CASSCF/internally contracted configuration interaction calculations to refine the energetics. The present results are in qualitative accord with the BAC-MP4 calculations, but there are differences as large as 8 kcal/mol in the detailed energetics.

Walch, Stephen P.↗
NASA NTRS1993

Computed barrier heights for H + CH2O yields CH3O yields CH2OH

The barrier heights (including zero-point effects) for H + CH2O yields CH3O and CH3O yields CH2OH have been computed using complete active space self consistent field (CASSCF)/gradient calculations to define the stationary point geometries and harmonic frequencies and internally contracted configuration-interaction (CCI) to refine the energetics. The computed barrier heights are 5.6 kcal/mol and 30.1 kcal/mol, respectively. The former barrier height compares favorably to an experimental activation energy of 5.2 kcal/mol.

Walch, Stephen P.↗
NASA NTRS1993

Theoretical characterization of the reaction CH3 + OH yields CH3OH yields products - The (1)CH2 + H2O, H2 + HCOH, and H2 + H2CO channels

The potential energy surface (PES) for the CH3OH system has been characterized for the (1)CH2 + H2O, H2 + HCOH, and H2 + H2CO product channels using complete-active-space self-consistent-field (CASSCF) gradient calculations to determine the stationary point geometries and frequencies followed by CASSCF/internally contracted configuration-interaction (CCI) calculations to refine the energetics. The (1)CH2 + H2O channel is found to have no barrier. The long range interaction is dominated by the dipole-dipole term, which orients the respective dipole moments parallel to each other but pointing in opposite directions. At shorter separations there is a dative bond structure in which a water lone pair donates into the empty 'a' orbital of CH2. Subsequent insertion of CH2 into an OH bond of water have barriers located at -5.2 kcal/mol and 1.7 kcal/mol, respectively, with respect to CH3 + OH. From comparison of the computed energetics of the reactants and products to known thermochemical data it is estimated that the computed PES is accurate to plus or minus 2 kcal/mol.

Walch, Stephen P.↗
NASA NTRS1993

Electronic and vibrational spectra of matrix isolated anthracene radical cations - Experimental and theoretical aspects

The IR vibrational and visible/UV electronic absorption spectra of the anthracene cation, An(+), were studied experimentally, in argon matrices at 12 K, as well as theoretically, using ab initio calculations for the vibrational modes and enhanced semiempirical methods with configuration interaction for the electronic spectra. It was found that both approaches predicted well the observed photoelectron spectrum. The theoretical IR intensities showed some remarkable differences between neutral and ionized species (for example, the CH in-plane bending modes and CC in-plane stretching vibrations were predicted to increase by several orders of magnitude upon ionization). Likewise, estimated experimental IR intensities showed a significant increase in the cation band intensities over the neutrals. The implication of these findings for the hypothesis that polycyclic aromatic hydrocarbon cations are responsible for the unidentified IR emission bands from interstellar space is discussed.

Szczepanski, Jan↗
NASA NTRS1993

Electron impact emission cross sections needed in modeling UV observations of the upper atmospheres of the planets

In recognition of the need for accurate collision cross-sections suitable for modeling spectroscopic observations of the planetary systems and calibrate flight instruments, NASA-JPL has determined the laboratory emission cross-sections of H, H2, N2, SO2, etc. Resonance excitation, predissociation, and non-Franck-Condon band intensity systems are determined by configuration interaction and must be taken into account in analyses of spacecraft observations. Attention is given to the application of the cross-sectional data obtained to both electron energy loss codes and models of Voyager, IUE, Galileo, and HST observations of the solar system.

Ajello, J. M.↗
NASA NTRS1991

Theoretical study of the spectroscopy of the alkali oxides LiO, NaO, and KO

A state-averaged complete-active-space self-consistent-field multireference configuration-interaction method is presented to characterize the bound-bound emission from the CPi-2 state into the two lowest ionic states of LiO, NaO, and KO. Ab initio calculations use the experimental results obtained by Woodward et al. (1989) of the emitting state as CPi-2, but indicate that the tentative experimental band assignments are incorrect.

Langhoff, Stephen R.↗
NASA NTRS1993

Theoretical study of the lowest 5Pi and 5Sigma(+) states of CO

Large one-particle basis sets and the internally contracted multireference configuration-interaction treatment of electron correlation were used to characterize the lowest 5Pi and 5Sigma(+) states of CO. It was found that the (1)5Sigma(+) state is weakly bound with an r(e) of 4.76 a(0), supporting results of calculations by Rosenkrantz et al. (1992). The (1)5Pi state has a weakly bound outer well and a significantly bound inner well.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1993

Theoretical characterization of the reaction NH2 + O yields products

The potential energy surface for NH2+O has been characterized using complete active space self-consistent field (CASSCF)/derivative calculations to determine stationary point geometries and frequencies followed by internally contracted configuration interaction (ICCI) calculations to determine the energetics. The calculations predict a NO bond strength of 85.8 kcal/mol for NH2O. The barrier for isomerization of NH2O to trans-HNOH is predicted to be 48.0 kcal/mol and the barriers for H+HNO forming NH2O and NHOH are predicted to be 2.1 and 8.3 kcal/mol, respectively (all corrected for zero-point energy). The computed heats of formation for NH2O and cis- and trans-HNOH are in good agreement with the present results. The barrier for H + HNO yields H2 + NO is computed to be about 0.3 kcal/mol.

Walch, Stephen P.↗
NASA NTRS1993

Theoretical characterization of the reaction NH2+NO - products

The potential energy surface (PES) for NH2+NO is characterized using complete active space self-consistent-field (CASSCF)/derivative methods to locate the stationary points, followed by internally contracted configuration interaction (ICCI) calculations to determine the energetics. Production of N2+H2O is found to involve a complex mechanism, which, however, has no barrier with respect to NH2+NO. This pathway is exothermic by 124.5 kcal/mol. Production of NH2+OH can occur with no barrier other than the exothermicity from any of three isomers of HNNOH.

Walch, Stephen P.↗
NASA NTRS1994

Symmetry breaking in O4(+): An application of the Brueckner coupled-cluster method

A recent calculation of the antisymmetric stretch frequency for the rectangular structure of quartet O4(+) using the singles and doubles quadratic configuration interaction method with a perturbational estimate of connected triple excitations (QCISD(T)) method gave a value of 3710 cm(exp -1). This anomalous frequency is shown to be a consequence of symmetry breaking effects, which occur even though the QCISD(T) solution derived from a delocalized SCF reference function lies energetically well below the two localized (symmetry-broken) solutions at the equilibrium geometry. The symmetry breaking is almost eliminated at the CCSD level of theory, but the small remaining symmetry breaking effects are magnified at the CCSD(T) level of theory so that the antisymmetric stretch frequency is still significantly in error. The use of the Brueckner coupled cluster method, however, leads to a symmetrical solution which is free of symmetry breaking effects, with an antisymmetric stretch frequency of 1322 cm(exp -1), in good agreement with our earlier calculations using the complete active space self consistent field/complete active space state interaction (CASSCF/CASSI) method.

Barnes, Leslie A.↗
NASA NTRS1994

Oscillator strengths of selected resonance transitions in neutral sulfur

Mean lives and branching ratios for the 4s (3)S(sup 0 sub 1) and 4s(double prime) (3)P(sup 0 sub 1, 2) levels of neutral sulfur were determined at the Toledo Heavy Ion Accelerator using beam-foil spectroscopic techniques. The mean lives obtained for the 4s (3)S(sup 0 sub 1) 4s(double prime) (3)P(sup 0 sub 1), and (3)P(sup 0 sub 2) levels, 1.875 +/- 0.094 ns, 2.034 +/- 0.102 ns, and 2.146 +/- 0.129 ns, respectively, represent the most accurate results available to date. Oscillator strengths for the transitions 3p(sup 4)(3)P(sub 2, 1, 0)-4s (3)S(sup 0 sub 1) and 3p(sup 4)(3)P(sub 2, 1, 0)-4s(double prime) (3)P(sup 0 sub 1, 2) were derived from these mean lives together with the measured branching ratios. For comparison with published results which present only multiplet f-values, such f-values were computed from the measured individual line oscillator strengths. The value obtained for the 3p(sup 4)(3)P-4s(sup 3)S(sup 0) multiplet at 1814 A is 0.088 +/- 0.005, in good agreement with the mean of previous experimental measurements and theoretical calculations. With the mean life for the 4s(double prime) 3P(sup 0 sub 0) level set equal to the mean of our determination for the other two 4s(double prime) (3)P(sup 0) levels (a valid assumption for LS coupling conditions, and consistent with the observed equality of the mean lives within the accuracy of our measurement), an oscillator strength for the 1299 A multiplet of 0.121 +/- 0.004 was found. Both results are in good agreement with recent large-scale theoretical calculations that incorporate the effects of configuration interaction.

Beideck, D. J.↗
NASA NTRS1994

Motion of the heliospheric termination shock 3: Incident interplanetary shocks

In this paper the response of the heliospheric termination shock to an incident interplanetary shock is examined. This paper is an extension of a recent study by Barnes (1993), which treated the analogous problem for an incident contact discontinuity. The termination shock is treated as a strong gas-dynamic shock. The post-interaction configuration consists of a moving termination shock, a postshock contact discontinuity, and either a shock or rarefaction wave propagating the disturbance signal into the downstream medium. For a decrease in dynamic pressure a rarefaction wave propagates downstream, and the new termination shock propagates inward, while, for an enhancement of dynamic pressure, the termination shock moves outwards and a weak outer shock propagates into the downstream medium; speeds of motion of the termination shock are typically of the order of approximately 100 km/s. The results are similar to those presented by Barnes (1993) indicating that the results of that paper are robust within the gas-dynamic model, in the sense of being independent of the details of the initial disturbance.

Naidu, Kamcilla↗
NASA NTRS1995

Characterization of the Minimum Energy Paths and Energetics for the Reaction of Vinylidene with Acetylene

The reaction of vinylidene (CH2C) with acetylene may be an initiating reaction in soot formation. We report minimum energy paths and accurate energetics for a pathway leading to vinyl-acetylene and for a number of isomers of C4H4. The calculations use complete active space self-consistent field (CASSCF) derivative methods to characterize the stationary points and internally contacted configuration interaction (ICCI) and/or coupled cluster singles and doubles with a perturbational estimate of triple excitations (CCSD(T)) to determine the energetics. We find an entrance channel barrier of about 5 kcal/mol for the addition of vinylidene to acetylene, but no barriers above reactants for the reaction pathway leading to vinyl-acetylene.

Walch, Stephen P.↗
NASA NTRS1995

Characterization of the Minimum Energy Paths and Energetics for the reaction of Vinylidene with Acetylene

The reaction of vinylidene (CH2C) with acetylene may be an initiating reaction in soot formation. We report minimum energy paths and accurate energetics for a pathway leading to vinylacetylene and for a number of isomers Of C4H4. The calculations use complete active space self-consistent field (CASSCF) derivative methods to characterize the stationary points and internally contacted configuration interaction (ICCI) and/or coupled cluster singles and doubles with a perturbational estimate of triple excitations (CCSD(T)) to determine the energetics. We find an entrance channel barrier of about 5 kcal/mol for the addition of vinylidene to acetylene, but no barriers above reactants for the reaction pathway leading to vinylacetylene.

Walch, Stephen P.↗
NASA NTRS1994

The Fraternal Twins of Quartet O4(+)

Eleven stationary geometries of quartet O4(+) have been studied by ab initio methods. The geometries were optimized at the Complete Active Space Self-Consistent Field (CASSCF) level of theory and the energies were calculated by the multiconfigurational second order pertubation method (CASPT2), using Double-Zeta Plus polarization (DZP), Triple-Zeta Plus Double Polarization (TZ2P), average Atomic Natural Orbital (ANO) (5s4p2d) and average ANO (6s5p3d2f) basis sets. The rectangular and trans-planar structures are found to be the most stable, with an energy barrier to conversion between the two at the threshold of dissociation. Both have a delocalized hole and are stable relative to separated 02 and 02(+)by 11.0 and 11.5 kcal/mol for the rectangular and the 2 trans-planar structure, respectively, compared with the experimentally deduced energy in the range of 9.2 to 10.8 kcal/mol. The adiabatic ionization potentials of 04 and 02 are computed to be 11.67 and 12.21 eV, while experimental values are 11.66 and 12.07 eV, respectively. The vibrational frequencies have been computed for all degrees of freedom at the CASSCF level of theory. Symmetry breaking is found to be a particular problem in the computation of the antisymmetric stretch frequency for the delocalized structures at the CASSCF level of theory. Attempts to rectify these problems using the restricted active space self-consistent field (RASSCF) method leads to additional difficulties, but further analysis yields insight into the symmetry breaking and problems with earlier calculations. Finally, a nonorthogonal configuration interaction (CI) calculation based on the interaction of localized CASSCF wave functions using the Complete Active Space State Interation (CASSI) method leads to a balanced treatment of the antisymmetric stretch which is free from symmetry breaking. The study explains the four most prominent absorption frequencies observed in the partially unassigned IR spectrum of O4(+) isolated in solid neon as the antisymmetric OO stretch, and the combination band of the symmetric and antisymmetric 00 stretch of both the rectangular and trans-planar structures.

Lindh, Roland↗
NASA NTRS1995

A New Potential Energy Surface for N+O2: Is There an NOO Minimum?

We report a new calculation of the N+02 potential energy surface using complete active space self-consistent field internally contracted configuration interaction with the Dunning correlation consistent basis sets. The peroxy isomer of N02 is found to be a very shallow minimum separated from NO+O by a barrier of only 0.3 kcal/mol (excluding zero-point effects). The entrance channel barrier height is estimated to be 8.6 kcal/mol for ICCI+Q calculations correlating all but the Ols and N1s electrons with a cc-p VQZ basis set.

Walch, Stephen P.↗
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 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 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.↗