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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.

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At least 37 records · Page 2
All sourcesNASA NTRSDOE OSTI
NASA NTRS1991

Theoretical study of the bonding of Sc, Y, and La singly charged and dipositive ions to C2H2, C2H4, and C3H6

The interaction of the Sc and Y singly-charged and dipositive ions with C2H2, C2H4, and C3H6 is studied using electronic structure calculations that include high levels of electron correlation. These results are compared with comparable calculations performed previously for La(+) and La(2+). For C2H2 and C2H4, all three metal ions insert into the C-C pi bond, making a three-membered ring. The optimal structures for the MC3H6(+) ions all involve rearrangement to make a four-membered ring. The strength of the metal-ligand bond for the singly charged ions follows the order La greater than Sc equal to about Y. In contrast, the bonds involving the dipositive ions are electrostatic, so that the binding energy increases as the size of the ion decreases, leading to the trend Sc greater than Y greater than La.

Bauschlicher, Charles W., Jr.↗
NASA NTRS2001

Complex Correlation Kohn-T Method of Calculating Total and Elastic Cross Sections: Electron-Hydrogen Elastic Scattering - Part 1

We report on the first part of a study of electron-hydrogen scattering, using a method which allows for the ab initio calculation of total and elastic cross sections at higher energies. In its general form the method uses complex 'radial' correlation functions, in a (Kohn) T-matrix formalism. The titled method, abbreviated Complex Correlation Kohn T (CCKT) method, is reviewed, in the context of electron-hydrogen scattering, including the derivation of the equation for the (complex) scattering function, and the extraction of the scattering information from the latter. The calculation reported here is restricted to S-waves in the elastic region, where the correlation functions can be taken, without loss of generality, to be real. Phase shifts are calculated using Hylleraas-type correlation functions with up to 95 terms. Results are rigorous lower bounds; they are in general agreement with those of Schwartz, but they are more accurate and outside his error bounds at a couple of energies,

Bhatia, A. K.↗
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 NTRS1983

Electron affinities of the alkali dimers - Na2, K2, and Rb2

Ab initio calculations on the ground states of the alkali dimers, Na2, K2, and Rb2, and their anions are reported. The calculations employ large Gaussian basis sets and account for nearly all of the valence correlation energy. The calculated atomic electron affinities are within 0.02 eV of experiment and the calculated adiabatic electron affinities for Na2, K2, and Rb2 are, respectively, 0.470, 0.512, and 0.513 eV.

Partridge, H.↗
NASA NTRS1990

On the bonding of La(+) and La(2+) to C2H2, C2H4, and C3H6

The interaction of La(+) and La(2+) with C2H2, C2H4, and C3H6 is studied using electronic structure calculations that include correlation. The calculations show that the bonding in the dication is electrostatic in origin, and the computed binding energies are in good agreement with experiment. The La(+) forms two chemical bonds with the hydrocarbons. Since the pi bond is weaker for C2H2 than C2H4, the La(+)-C2H2 binding energy is larger than for La(+)-C2H4, LaC3H6(+) rearranges to yield a stronger bond than in LaC2H4(+) even though both hydrocarbons have a double bond.

Rosi, Marzio↗
NASA NTRS1989

The computation of C-C and N-N bond dissociation energies for singly, doubly, and triply bonded systems

The bond dissociation energies (D sub e) of C2H2, C2H4, C2H6, N2, N2H2, and N2H4 are studied at various levels of correlation treatment. The convergence of D sub e with respect to the one particle basis is studied at the single reference modified coupled-pair functional (MCPF) level. At all levels of correlation treatment, the errors in the bond dissociation energies increase with the degree of multiple bond character. The multireference configuration interaction (MRCI) D sub e values, corrected for an estimate of higher excitations, are in excellent agreement with those determined using the size extensive averaged coupled pair functional (ACPF) method. It was found that the full valence complete active space self consistent field (CASSCF)/MRCI calculations are reproduced very well by MRCI calculations based on a CASSCF calculation that includes in the active space only those electrons involved in the C-C or N-N bonds. To achieve chemical accuracy (1 kcal/mole) for the D sub e values of the doubly bonded species C2H4 and N2H2 requires one particle basis sets including up through h angular momentum functions (l = 5) and a multireference treatment of electron correlation: still higher levels of calculation are required to achieve chemical accuracy for the triply bonded species C2H2 and N2.

Langhoff, Stephen R.↗
NASA NTRS1978

Theory of the classical electron gas

In a previous paper Cohen and Murphy (1969) used the Meeron resummation (1958) of the Mayer diagrams (1950) to calculate the pair correlation for the classical electron gas in thermal equilibrium. They found that successive terms in the expression for the pair correlation were more and more singular for small interparticle spacing, actually dominating the Debye-Hueckel result for sufficiently small distances. This led to apparent divergence in the higher order contributions to the internal energy. The present paper shows that the apparent anomalies in the Cohen-Murphy results can be removed without further resummation by a more careful treatment of the region of small interparticle spacing. It is shown that there is really no anomalous behavior at short range in any order and all integrals in the expression for the internal energy converge.

Guernsey, R. L.↗
NASA NTRS1991

Theoretical study of the bonding of Nb(2+) to CH2, C2H2, and C2H4

The bonding of Nb(2+) with CH2, C2H2, and C2H4 is studied by using electronic structure calculations that include high levels of electron correlation. The binding energy for NbCH2(2+) is in good agreement with the lower bound determined from the reaction with CH4 but is significantly smaller than the value determined from the binding energy and ionization potential of NbCH2(+). The calculations and a new interpretation of the experiment indicate that the larger value is in error primarily because the ionization potential of NbCH2(+) determined from bracketing charge-exchange reactions is too small. The computed binding energy of NbC2H2(2+) is in good agreement with experiment. The calculations show that the bonding is predominantly covalent in character for both NbCH2(2+) and NbC2H2(2+), whereas for NbC2H4(2+) the electronic states that are predominantly ionic and covalent are nearly degenerate. The trend in binding energies, CH2 greater than C2H2 greater than C2H4, is consistent with the energy required to prepare the ligands for bonding.

Bauschlicher, Charles W., Jr.↗
NASA NTRS1974

Electromagnetic processes in the atmosphere of pulsars

The work consists of two parts. The first deals with the fine structure of radio pulses. Based on kinetic theory, processes occurring in the plasma shell of a pulsar when external electromagnetic radiation is present are investigated. It is shown that electromagnetic waves cause electrons to drift relative to ions, and initiate longitudinal oscillations. A dispersion equation describing the longitudinal oscillations in magnetized plasma is derived. Conditions for excitation of oscillations are found. Correlation functions of electron density are calculated, along with the coefficients of electromagnetic wave scattering. It is shown that variations in the amplitude of pulsar pulses are associated with scintillations caused by fluctuations in the plasma electron density. The second part of the study presents a mechanism for the radio emission of pulsars. The model of a rotating and a pulsating star, a neutron star with dipolar or more complex magnetic field, is examined.

Yukhimuk, A. K.↗
NASA NTRS1981

Properties of the X 1 Sigma state of BF

A perturbation theoretical approach for treating electron correlation has been used to calculate the potential energy curve and dipole moment function of BF near its equilibrium bond length. A dipole moment of 0.89 D (B- F+) is predicted at R sub e. When the bond is stretched by approximately 0.2 A the dipole reverses sign.

Kurtz, H. A.↗
NASA NTRS1985

Theoretical research program to study transition metal trimers and embedded clusters

Small transition metal clusters at a high level of approximation i.e. including all the valence electrons in the calculation and also including extensive electron correlation were studied. Perhaps the most useful end result of these studies is the qualitative information about the electronic structure of these small metal clusters, including the nature of the bonding. The electronic structure studies of the small clusters are directly applicable to problems in catalysis. From comparison of dimers, trimers and possibly higher clusters, it is possible to extrapolate the information obtained to provide insights into the electronic structure of bulk transition metals and their interaction with other atoms and molecules at both surface and interior locations.

Walch, S. P.↗
NASA NTRS1993

Anode power deposition in magnetoplasmadynamic thrusters

Results of anode heat-flux and anode fail measurements from a multimegawatt self-field quasi-steady magnetoplasmadynamic (MPD) thruster are presented. Measurements were obtained with argon and helium propellants for a variety of currents and mass flow rates. Anode heat flux was directly measured with thermocouples attached to the inner surface of a hollowed section. Anode falls were determined both from floating probes and through heat flux measurements. Comparison of data acquired through either method shows excellent agreement. Anode falls varied between 4-50 V with anode power fractions reaching 70 percent with helium at 150 kW, and 50 percent with argon at 1.9 MW. The anode fall was found to correlate well with electron Hall parameters calculated from triple Langmuir and magnetic probe data collected near the anode. Two possible explanations for this result are proposed: (1) the establishment of large electric fields at the anode to maintain current conduction across the strong magnetic fields; and (2) anomalous resistivity resulting from the onset of microturbulence in the plasma. To investigate the latter hypothesis, electric field, magnetic field, and current density profiles measured in the vicinity of the anode were incorporated into Ohm's law to estimate the electrical conductivity. Results of this analysis show a substantial deviation of the measured conductivity from that calculated with classical formulas. These results imply that anomalous effects are present in the plasma near the anode.

Gallimore, A. D.↗
NASA NTRS1977

Precision calculation of the lowest 1S resonance in e-H scattering

The position and width of the lowest resonance in electron-hydrogen scattering have been calculated using a Hylleraas correlation function with up to 95 terms in the optical potential formalism. The results should be useful as calibration points for experimental electron scattering purposes. A formula relating the conventional (Breit-Wigner) width with the Feschbach formalism is derived.

Ho, Y. K.↗
NASA NTRS1973

The scattering of low energy positrons by helium

Kohn's variational method is used to calculate the positron-helium scattering length and low energy S-wave phase shifts for a quite realistic Hylleraas type of helium function containing an electron-electron correlation term. The zero energy wavefunction is used to calculate the value of the annihilation rate parameter Z sub eff. All the results are significantly different from those for Drachman's helium model B, but are in better agreement with the available experimental data.

Humberston, J. W.↗
NASA NTRS1989

Theoretical studies of the transition metal-carbonyl systems MCO and M(CO)2, M = Ti, Sc, and V

Large Gaussian basis sets and an electron correlation treatment are used in ab initio calculations on the transition metal-carbonyl systems MCO and N(CO)2 for M = Ti, Sc, and V. The results show that high-spin ground states are favored for the monocarbonyl molecules, and that for the dicarbonyl molecules there is a competition between high, intermediate, and low spin states which are very close in energy. Dissociation energies of 0.62 eV for Ti-CO and 1.02 for Ti(CO)2 are found, relative to the ground state Ti atomic asymptote and CO 1Sigma(+). The binding energy per carbonyl for the three metal atoms is shown to be significantly lower for the dicarbonyl than for the the monocarbonyl molecules.

Barnes, Leslie A.↗
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 NTRS1987

Positive ions of the first- and second-row transition metal hydrides

Theoretical dissociation energies for the first- and second-row transition metal hydride positive ions are critically compared against recent experimental values obtained from ion beam reactive scattering methods. Theoretical spectroscopic parameters and dipole moments are presented for the ground and several low-lying excited states. The calculations employ large Gaussian basis sets and account for electron correlation using the single-reference single- and double-excitation configuration interaction and coupled-pair-functional methods. The Darwin and mass-velocity contributions to the relativistic energy are included in the all-electron calculations on the first-row systems using first-order perturbation theory, and in the second-row systems using the Hay and Wadt relativistic effective core potentials. The theoretical D(0) values for the second-row transition metal hydride positive ions should provide a critical measure of the experimental values, which are not as refined as many of those in the first transition row.

Pettersson, Lars G. M.↗
NASA NTRS1987

Inclusion of electron correlation for the target wave function in low- to intermediate-energy e-N2 scattering

In a recent calculation, an exact exchange method was developed for use in the partial-differential-equation approach to electron-molecule scattering and was applied to e-N2 scattering in the fixed-nuclei approximation with an adiabatic polarization potential at low energies (0-10 eV). Integrated elastic cross sections were calculated and found to be lower than experiment at energies both below and above the Pi(g) resonance. It was speculated at that time that improved experimental agreement could be obtained if a correlated target representation were used in place of the uncorrelated one. The present paper implements this suggestion and demonstrates the improved agreement. These calculations are also extended to higher energies (0-30 eV) so asd to include the Sigma(u) resonance. Some discrepancies among the experiments and between experiment and the various calculations at very low energy are noted.

Weatherford, C. A.↗