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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 145 records · Page 8
All sourcesNASA NTRSDOE OSTI
NASA NTRS1985

Mechanism for chelated sulfate formation from SO2 and bis (triphenylphosphine) platinum

Structure and energy surface calculations using the atom superposition and electron delocalization molecular orbital theory show that the first step in the reaction between SO2 and the dioxygen complex (PPh3)2PtO2 is the coordination of SO2 with one oxygen atom of the complex, followed by metal-oxygen bond breaking and reorientation, leading to a five-membered cyclic structure. This then rearranges to form the bidentate coordinated sulfate. Alternative pathways are considered and are found to be less favorable.

Mehandru, S. P.↗
NASA NTRS1986

Adsorption of O2, SO2, and SO3, on nickel oxide - Mechanism for sulfate formation

Calculations based on the atom superposition and electron delocalization molecular orbital technique suggest that O2 will adsorb preferentially end-on at an angle 45 deg from normal on a nickel cation site on the (100) surface of NiO. SO2 adsorption is also stronger on the nickel site; SO2 bonds through the sulfur atom in a plane perpendicular to the surface. Adsorption energies for SO3 on the nickel and oxygen sites are comparable in the preferred orientation in which the SO3 plane is parallel to the surface. The calculations suggest that the strength of adsorption varies as O2 greater than SO2 greater than SO3. On activation, SO3 adsorbed to an O(2-) site forms a trigonal pyramidal SO4 species which yields, with a low barrier, a tetrahedral sulfate anion. Subsequently the anion reorients on the surface. Alternative mechanisms which require the formation of Ni(3+) or O(-) are discussed. NiSO4 thus formed may play a passivating role for the corrosion of Ni at low temperatures in the SO2 + O2 + SO3 atmospheres and an active role at high temperatures, as discussed in the experimental literature.

Mehandru, S. P.↗
NASA NTRS1987

Organic nonlinear optical materials

Recently, it became clear that organic compounds with delocalized pi electrons show a great nonlinear optical response. Especially, secondary nonlinear optical constants of more than 2 digits were often seen in the molecular level compared to the existing inorganic crystals such as LiNbO3. The crystallization was continuously tried. Organic nonlinear optical crystals have a new future as materials for use in the applied physics such as photomodulation, optical frequency transformation, opto-bistabilization, and phase conjugation optics. Organic nonlinear optical materials, e.g., urea, O2NC6H4NH2, I, II, are reviewed with 50 references.

Umegaki, S.↗
NASA NTRS1985

Transonic rotor tip design using numerical optimization

The aerodynamic design procedure for a new blade tip suitable for operation at transonic speeds is illustrated. For the first time, 3 dimensional numerical optimization was applied to rotor tip design, using the recent derivative of the ROT22 code, program R22OPT. Program R22OPT utilized an efficient quasi-Newton optimization algorithm. Multiple design objectives were specified. The delocalization of the shock wave was to be eliminated in forward flight for an advance ratio of 0.41 and a tip Mach number of 0.92 at psi = 90 deg. Simultaneously, it was sought to reduce torque requirements while maintaining effective restoring pitching moments. Only the outer 10 percent of the blade span was modified; the blade area was not to be reduced by more than 3 percent. The goal was to combine the advantages of both sweptback and sweptforward blade tips. A planform that featured inboard sweepback was combined with a sweptforward tip and a taper ratio of 0.5. Initially, the ROT22 code was used to find by trial and error a planform geometry which met the design goals. This configuration had an inboard section with a leading edge sweep of 20 deg and a tip section swept forward at 25 deg; in addition, the airfoils were modified.

Tauber, Michael E.↗
NASA NTRS1987

Nonlocal thermal transport in solar flares

A flaring solar atmosphere is modeled assuming classical thermal transport, locally limited thermal transport, and nonlocal thermal transport. The classical, local, and nonlocal expressions for the heat flux yield significantly different temperature, density, and velocity profiles throughout the rise phase of the flare. Evaporation of chromospheric material begins earlier in the nonlocal case than in the classical or local calculations, but reaches much lower upward velocities. Much higher coronal temperatures are achieved in the nonlocal calculations owing to the combined effects of delocalization and flux limiting. The peak velocity and momentum are roughly the same in all three cases. A more impulsive energy release influences the evolution of the nonlocal model more than the classical and locally limited cases.

Karpen, Judith T.↗
NASA NTRS1987

Prediction of high-speed rotor noise with a Kirchhoff formula

A new methodology has been developed to predict the impulsive noise generated by a transonic rotor blade. The formulation uses a full-potential finite-difference method to obtain the pressure field close to the blade. A Kirchhoff integral formulation is then used to extend these finite-difference results into the far-field. This Kirchhoff formula is written in a blade-fixed coordinate system. It requires initial data across a plane at the sonic radius. This data is provided by the finite-difference solution. Acoustic pressure predictions show excellent agreement with hover experimental data for two hover cases of 0.88 and 0.90 tip Mach number, the latter of which has delocalized transonic flow. These results represent the first successful prediction technique for peak pressure amplitudes using a computational code.

Purcell, Timothy W.↗
NASA NTRS1987

Geometrical acoustics and transonic helicopter sound

A new method is presented for predicting the impulsive noise generated by a transonic rotor blade. The method is a combined approach involving computational fluid dynamics and geometrical acoustics. A full-potential finite-difference method is used to obtain the pressure field close to the blade. A Kirchhoff integral formulation is then used to extend these finite-difference results into the far field. This Kirchhoff formula is based on geometrical acoustics approximations. It requires initial data across a plane at the sonic radius in a blade-fixed coordinate system. This data is provided by the finite-difference solution. Acoustic pressure predictions show good agreement with hover experimental data for cases with hover tip Mach numbers of 0.88 through 0.96. The cases above 0.92 tip Mach number are dominated by non-linear transonic effects seen as strong shocks on and off the blade tip. This paper gives the first successful predictions of far-field acoustic pressures for high-speed impulsive noise over a range of Mach numbers after delocalization.

Isom, Morris↗
NASA NTRS1989

Oxygen evolution on a SrFeO3 anode - Mechanistic considerations from molecular orbital theory

Various pathways proposed in the literature for the evolution of O2 in electrochemical oxidations are explored using the atom superposition and electron delocalization molecular orbital (ASED-MO) theory and the cluster models of the SrFeO3 surface as a prototype material. Calculations indicate that oxygen atoms can be easily formed on the (100) surface as well as on the edge cation sites of a SrFeO3 anode by the discharge of OH(-), followed by its deprotonation and electron transfer to the electrode. The O atoms can form O2 on the edge and corner sites, where the Fe(4+) is coordinated to four and three bulk oxygen anions, respectively. The calculations strongly disfavor mechanisms involving coupling of oxygen atoms adsorbed on different cations as well as a mechanism featuring an ozone intermediate.

Mehandru, S. P.↗
NASA NTRS1989

A prediction of high-speed rotor noise

A combined computational (CFD) and integral approach solves the acoustic pressure fields of two high-speed helicopter rotors. A CFD code supplies boundary data to a non-linear type of Kirchhoff integral formulation to find the far-field pressures. Direct calculations of pressures are given by the CFD code up to the sonic cylinder where the Kirchhoff method takes over. This paper shows predictions and measurements of High-Speed Impulsive (HSI) noise in hover for two different rotor geometries. One rotor has a conventional rectangular planform, while the other rotor is highly swept and tapered. The swept rotor analysis forms the majority of this paper. Test data from both rotors are shown and compared with predictions for a range of tip Mach numbers from .85 to .95 (including delocalization). The correlation with the near-field pressures from the straight bladed experiment is excellent and good to excellent correlation is seen for the far-field pressures from both experiments.

Purcell, Timothy W.↗
NASA NTRS1989

Influence of gap states on the nonresonant second hyperpolarizabilities of conjugated organic polymers

The presence of conjugation and substitution defects introduces gap states in finite polyenes that are shown to influence the size and sign of the second molecular hyperpolarizability (SMH). Using a one-electron tight-binding model, the dependence of SMH on the defect-state occupancy and energy in finite polyenes is calculated. Defects can cause a significant decrease or enhancement of SMH by impeding charge delocalization or by creating partly filled bands (mimicking the one-band limit), respectively. Concomitant sign changes in SMH are predicted. Calculation results suggest strategies for designing molecules that can be either photochemically or electrochemically switched between states with considerably different SMHs.

Beratan, David N.↗
NASA NTRS1988

CFD and transonic helicopter sound

A computational method which predicts far-field impulsive noise from a transonic motor blade is demonstrated. This method couples near-field results from a full-potential finite-difference method with a new Kirchhoff integral formulation to extend the finite-difference results into the acoustic far-field. This Kirchhoff formula is written in a blade-fixed coordinate system. It requires initial data from the potential code on a plane at the sonic radius. A recent hovering rotor experiment is described where accurate pressure measurements were recorded on the sonic cylinder and at 2 and 3 radii. The potential code prediction of sonic cylinder pressures is excellent. Acoustic far-field pressure predictions show good agreement with hover experimental data over the range of speeds from 0.85 to 0.92 tip Mach number, the latter of which have delocalized transonic flow. These results are some of the first successful predictions for peak pressure amplitudes using a computational code.

Purcell, Timothy W.↗
NASA NTRS1990

Magnetism and electron pairing in high-Tc superconductors

Correlated wave functions are used for YBa2Cu3O(7-y) where epsilon(d)-epsilon(p) is about 0 for Cu3d- and 02p-electrons. The electrons are delocalized (metallic) for y less than 0.5 with weak and temperature-independent paramagnetism. In contrast, the systems are conventional antiferromagnetic insulators for y greater than 0.6 with a narrow y between 0.5 and 0.6 transition region. These results are in agreement with magnetic and neutron diffraction data.

Tsang, T.↗
NASA NTRS1993

Ab initio calculation of a global potential, vibrational energies, and wave functions for HCN/HNC, and a simulation of the (A-tilde)-(X-tilde) emission spectrum

A potential energy surface for the HCN/HNC system which is a fit to extensive, high-quality ab initio, coupled-cluster calculations is presented. All HCN and HNC states with energies below the energy of the first delocalized state are reported and characterized. Vibrational transition energies are compared with all available experimental data on HCN and HNC, including high CH-overtone states up to 23,063/cm. A simulation of the (A-tilde)-(X-tilde) stimulated emission pumping (SEP) spectrum is also reported, and the results are compared to experiment. Franck-Condon factors are reported for odd bending states of HCN, with one quantum of vibrational angular momentum, in order to compare with the recent assignment by Jonas et al. (1992), on the basis of axis-switching arguments of a number of previously unassigned states in the SEP spectrum.

Bowman, Joel M.↗
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 NTRS1992

Evaluation of a doubly-swept blade tip for rotorcraft noise reduction

A computational study was performed for a doubly-swept rotor blade tip to determine its benefit for high-speed impulsive (HSI) and blade-vortex interaction (BVI) noise. This design consists of aft and forward sweep. For the HSI-noise computations, unsteady Euler calculations were performed for several variations to a rotor blade geometry. A doubly-swept planform was predicted to increase the delocalizing Mach number to 0.94 (representative of a 200+ kt helicopter). For the BVI-noise problem, it had been hypothesized that the doubly-swept blade tip, by producing a leading-edge vortex, would reduce the tip-vortex effect on BVI noise. A procedure was used in which the tip vortex velocity profile computed by a Navier-Stokes solver was used to compute the inflow associated with BVI. This inflow was used by a Euler solver to compute the unsteady pressures for an acoustic analysis. The results of this study were inconclusive due to the difficulty in accurately predicting the viscous tip vortex downstream of the blade. Also, for the condition studied, no leading-edge vortex formed at the tip.

Wake, Brian E.↗
NASA NTRS1995

Proton affinity determinations and proton-bound dimer structure indications in C2 to C15, (alpha),(omega)-alkyldiamines

The 'kinetic method' was used to determine the proton affinity (PA) of a,coalkyldiamines from collision induced dissociation (CID) studies of protonated heterodimers. These PA values were consistently lower than those reported in the proton affinity scale. The apparent discrepancy was rationalized in terms of differences in the conformation of the protonated diamine monomers. The minimum energy species, formed by equilibrium proton transfer processes, have a cyclic conformation and the ion charge is shared by both amino-groups which are bridged by the proton. On the other hand, the species formed through dissociation of protonated dimers have a linear structure and the charge is localized on one of the amino-groups. Thus, the difference in the PA values obtained by both methods is a measure of the additional stability acquired by the protonated diamines through cyclization and charge delocalization. The major collision dissociation pathway of the protonated diamine monomers involved elimination of an ammonia moiety. Other reactions observed included loss of the second amino-group and several other bond cleavages. CID of the protonated dimers involved primarily formation of a protonated monomer through cleavage of the weaker hydrogen bond and subsequently loss of ammonia at higher collision energies. As observed from the CID studies, doubly charged ions were also formed from the diamines under conditions of the electrospray ionization.

Karpas, Z.↗
NASA NTRS1995

Boson localization and universality in YBa2Cu(3-x)M(x)O(7-delta)

We consider a two component mixture of charged fermions on neutralizing background with all sign combinations and arbitrarily small mass ratios. In the two impurity limit for the heavier component we show that the pair forms a bound state for all charge combinations. In the lowest order approximation we derive a closed form expression Veff(r) for the binding potential which has short-range repulsion followed by attraction. In the classical limit, when the mass of embedded particles is large m2 much greater than m, we can calculate from Veff(r) also the cohesive energy E and the bond length R of a metallic crystal such as lithium. The lowest order result is R = 3.1 A, E = -0.9 eV, not entirely different from the experimental result for lithium metal. The same interaction for two holes on a parabolic band with m2 greater than m gives the quantum mechanical bound state which one may interpret as a boson or local pair in the case of high-Te and heavy fermion superconductors. We also show that for compounds of the type YBa2Cu(3 - x)M(x)O(7 - delta) one can understand most of the experimental results for the superconducting and normal states with a single temperature dependent boson breaking function f(T) for each impurity content x governing the decay of bosons into pairing fermions. In the normal state f(T) turns out to be a linear, universal function, independent of the impurity content I and the oxygen content delta. We predict with universality a depression in Tc(x) with slight down bending in agreement with experiment. As a natural consequence of the model the bosons become localized slightly above Tc due to the Wigner crystallization, enhanced with lattice local field minima. The holes remain delocalized with a linearly increasing concentration in the normal state, thus explaining the rising Hall density. The boson localization temperature T(sub BL) shows up as a minimum in the Hall density R(sub ab)(exp -1). We also give explanation for very recently observed scaling of temperature dependent Hall effect in La(2 - x)Sr(x)CuO4.

Kallio, A.↗
NASA NTRS1996

The Calculation of Accurate Harmonic Frequencies of Large Molecules: The Polycyclic Aromatic Hydrocarbons, a Case Study

The vibrational frequencies and infrared intensities of naphthalene neutral and cation are studied at the self-consistent-field (SCF), second-order Moller-Plesset (MP2), and density functional theory (DFT) levels using a variety of one-particle basis sets. Very accurate frequencies can be obtained at the DFT level in conjunction with large basis sets if they are scaled with two factors, one for the C-H stretches and a second for all other modes. We also find remarkably good agreement at the B3LYP/4-31G level using only one scale factor. Unlike the neutral PAHs where all methods do reasonably well for the intensities, only the DFT results are accurate for the PAH cations. The failure of the SCF and MP2 methods is caused by symmetry breaking and an inability to describe charge delocalization. We present several interesting cases of symmetry breaking in this study. An assessment is made as to whether an ensemble of PAH neutrals or cations could account for the unidentified infrared bands observed in many astronomical sources.

Bauschlicher, Charles W., Jr.↗