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At least 163 records · Page 9

Why Are Buckyonions Round?

Multi-layered round carbon particles (onions) containing tens to hundreds of thousands of atoms form during electron irradiation of graphite carbon. However, theoretical models of large icosahedral fullerenes predict highly faceted shapes for molecules with more than a few hundred atoms. This discrepancy in shape may be explained by the presence of defects during the formation of carbon onions. Here, we use the semi-empirical tight-binding method for carbon to simulate the incorporation of pentagon-heptagon defects on to the surface of large icosahedral fullerenes. We show a simple mechanism that results in energetically competitive derivative structures and a global change in molecular shape from faceted to round. Our results provide a plausible explanation of the apparent discrepancy between experimental observations of round buckyonions and theoretical predictions of faceted icosahedral fullerenes.

Bates, Kevin R.↗

Why are Buckyonions Round?

Multi-layered round carbon particles (onions) containing tens to hundreds of thousands of atoms form during electron irradiation of graphite. However. theoretical models or large icosahedral fullerenes predict highly faceted shapes for molecules with more than a few hundred atoms. This discrepancy in shape may be explained by the presence of defects during the formation of carbon onions. Here, we use the semi-empirical tight-binding method for carbon to simulate the incorporation of pentagon-heptagon defects on to the surface of large icosahedral fullerenes. We show a simple mechanism that results in energetically competitive derivative structures and a global change in molecular shape from faceted to round. Our results provide a plausible explanation of the apparent discrepancy between experimental observations or round buckyonions and theoretical predictions of faceted icosahedral fullerenes.

Bates, Kevin R.↗

Semi-empirical crack tip analysis

Experimentally observed crack opening displacements are employed as the solution of the multiple crack interaction problem. Then the near and far fields are reconstructed analytically by means of the double layer potential technqiue. Evaluation of the effective stress intensity factor resulting from the interaction of the main crack and its surrounding crazes in addition to the remotely applied load is presented as an illustrative example. It is shown that crazing (as well as microcracking) may constitute an alternative mechanism to Dugdale-Berenblatt models responsible for the cancellation of the singularity at the crack tip.

Chudnovsky, A.↗

Macromolecular recognition: Structural aspects of the origin of the genetic system

Theoretical simulation of prebiotic chemical processes is an invaluable tool for probing the phenomenon of evolution of life. Using computational and modeling techniques and guided by analogies from present day systems we, seek to understand the emergence of genetic apparatus, enzymatic catalysis and protein synthesis under prebiotic conditions. In one possible scenario, the RNA enzymatic reaction plays a key role in the emergence of the self-replicating and offers a clue to the onset of enzymatic catalysis prior to the existence of the protein biosynthetic machinery. Our ultimate goal is to propose a simple RNA segment which contains the specificity and catalytic activity of the contemporary RNA enzyme and which could emerge in a primordial chemical environment. To understand the mechanism of ribozyme catalyzed reactions, ab initio and semi-empirical (ZINDO) programs were used to investigate the reaction path of transphosphorylation. A special emphasis was placed on the possible catalytic and structural roles played by the coordinated magnesium cation. Both the inline and adjacent mechanisms of transphosphorylation have been studied. Another important aspect of this reaction is the identity of the functional groups which are essential for the acid base catalysis. The structural characteristics of the target helices, particularly a possible role of G center dot T pair, is under examination by molecular dynamics (MD) simulation technique. Modeling of the ancestral aminoacyl-tRNA synthetases (aRS) may provide important clues to the emergence of the genetic code and the protein synthetic machinery. Assuming that the catalytic function evolved before the elements of specific recognition of a particular amino acid, we are exploring the minimal structural requirements for the catalysis of tRNA aminoacylation. The molecular modeling system SYBYL was used for this study based on the high resolution crystallographic structures of the present day tyrosyl-adenylate:tyrRS and tRNA(Gln): ATP:glnRS complexes. The trinucleotide CCA of the 3'-end tRNA is placed into the active site pocket of tyrRS, based on the scheme of interaction between tRNA(Gln) and glnRS, and upon the stereochemistry of the tyrRS:tRNA:Tyr-AMP transition state. This provides a model of the non-specific recognition of a tRNA's 3'-end by an aRS, which might be similar to that of the ancestral aRS's. In the next step, modeling of the rest of the acceptor stem of tRNA (Tyr) with tyrRS is carried out.

Rein, Robert↗

A new calibration of the semi-empirical photometric theory for Halley and other comets

The semiempirical photometric theory of gas and dust production in comets (Newburn, 1979, 1981, and 1982) is recalibrated on the basis of the 17-comet compilation of spectrophotometric data of Newburn and Spinrad (1984). The results are presented in graphs and tables, and it is shown that no corrections are required for the constant R and the function delta, but that the mixing ratios (obtained as functions of heliocentric distance) can be improved, with implications for the visual-photometric comet model. Recently calculated light curves for comet Halley are compared, and the use of the nearly identical curves of Bortle and Morris (1984) and Marcus (1983) is recommended.

Newburn, R. L., Jr.↗

Material characterization of structural adhesives in the lap shear mode

A general method for characterizing structural adhesives in the bonded lap shear mode is proposed. Two approaches in the form of semi-empirical and theoretical approaches are used. The semi-empirical approach includes Ludwik's and Zhurkov's equations to describe respectively, the failure stresses in the constant strain rate and constant stress loading modes with the inclusion of the temperature effects. The theoretical approach is used to describe adhesive shear stress-strain behavior with the use of viscoelastic or nonlinear elastic constitutive equations. Three different model adhesives are used in the simple lap shear mode with titanium adherends. These adhesives (one of which was developed at NASA Langley Research Center) are currently considered by NASA for possible aerospace applications. Use of different model adhesives helps in assessment of the generality of the method.

Schenck, S. C.↗

The whistler heat flux instability: Threshold conditions in the solar wind

Solar wind electrons are observed often to consist of two components: a core and a halo. The anisotropics and relative average speeds of these components correspond to a heat flux that has the potential to excite several different electromagetic instabilities; wave-particle scattering by the resulting enhanced fluctuations can limit this heat flux. This manuscript describes theoretical studies using the linear Vlasco dispersion equation for drifting bi-Maxwellian component distributions in a homogeneous plasma to examine the threshold of the whistler heat flux instability. Expressions for this threshold are obtained from two different parametric baselines: a local model that yields scalings as functions of local dimensionless plasma paramaters, and a global model based on average electron properties observed during the in-eliptic phase of the Ulysses mission. The latter model yields an expression for the heat flux at threshold of the whistler instability as a function of helisopheric radius that scales in the same way as the average heat flux observed form Ulysses and that provides an approximate upper bound for that same quantity. This theoretical scaling is combined with the observational results to yield a semi-empirical closure relation for the average electron heat flux in the solar wind between 1 and 5 AU.

Gary, S. Peter↗

Modeling of Branched (L, T and Y) Carbon Nanotubes

Models for connecting two or three carbon nanotubes (CNT) using topological defects (i.e., pentagons and heptagons) are presented for the characterization of experimentally observed L, T and Y CNT junctions. The effects of the separation and orientation of the topological defects on the structures and energetics of these junctions are investigated using the nonlocal density function theory (DFT) and semi-empirical molecular orbital (AM1) calculations, and the Brenner empirical potential molecular mechanics simulations. The potential applications of L, Y and T CNT junctions in nanoelectronic devices are also discussed.

Han, Jie↗

Macromolecular recognition: Structural aspects of the origin of the genetic system

Theoretical simulation of prebiotic chemical processes is an invaluable tool for probing the phenomenon of the evolution of life. Using computational and modeling techniques and guided by analogies from present day systems, we seek to understand the emergence of the genetic apparatus, enzymatic catalysis and protein synthesis under prebiotic conditions. Modeling of the ancestral aminoacyl-tRNA-synthetases (aRS) may provide important clues to the emergence of the genetic code and the protein synthetic machinery. The minimal structural requirements for the catalysis of tRNA aminoacylation are being explored. A formation of an aminoacyl adenylate was studied in the framework of ab initio molecular orbital theory. The role of individual residues in the vicinity of the TyrRS active site was examined, and the effect of all possible amino acids substitutions near the active site was examined. A formation of aminoacyl tRNA was studied by the molecular modeling system SYBYL with the high resolution crystallographic structures of the present day tRNA, aRS's complexes. The ultimate goal is to propose a simple RNA segment that is small enough to be build in the primordial chemical environment but maintains the specificity and catalytic activity of the contemporary RNA enzyme. To understand the mechanism of ribozyme catalyzed reactions, ab initio and semi-empirical (ZINDO) programs were used to investigate the reaction path of transphosphorylation. A special emphasis was placed on the possible catalytic and structural roles played by the coordinated magnesium cation. Both the inline and adjacent mechanisms of transphosphorylation were studied. The structural characteristics of the target helices, particularly a possible role for the G-T pair, is also studied by a molecular dynamics (MD) simulation technique.

Rein, Robert↗

Jet Aeroacoustics: Noise Generation Mechanism and Prediction

This report covers the third year research effort of the project. The research work focussed on the fine scale mixing noise of both subsonic and supersonic jets and the effects of nozzle geometry and tabs on subsonic jet noise. In publication 1, a new semi-empirical theory of jet mixing noise from fine scale turbulence is developed. By an analogy to gas kinetic theory, it is shown that the source of noise is related to the time fluctuations of the turbulence kinetic theory. On starting with the Reynolds Averaged Navier-Stokes equations, a formula for the radiated noise is derived. An empirical model of the space-time correlation function of the turbulence kinetic energy is adopted. The form of the model is in good agreement with the space-time two-point velocity correlation function measured by Davies and coworkers. The parameters of the correlation are related to the parameters of the k-epsilon turbulence model. Thus the theory is self-contained. Extensive comparisons between the computed noise spectrum of the theory and experimental measured have been carried out. The parameters include jet Mach number from 0.3 to 2.0 and temperature ratio from 1.0 to 4.8. Excellent agreements are found in the spectrum shape, noise intensity and directivity. It is envisaged that the theory would supercede all semi-empirical and totally empirical jet noise prediction methods in current use.

Tam, Christopher↗

A harmonic analysis of lunar gravity

An improved model of lunar global gravity has been obtained by fitting a sixteenth-degree harmonic series to a combination of Doppler tracking data from Apollo missions 8, 12, 15, and 16, and Lunar Orbiters 1, 2, 3, 4, and 5, and laser ranging data to the lunar surface. To compensate for the irregular selenographic distribution of these data, the solution algorithm has also incorporated a semi-empirical a priori covariance function. Maps of the free-air gravity disturbance and its formal error are presented, as are free-air anomaly and Bouguer anomaly maps. The lunar gravitational variance spectrum has the form V(G; n) = O(n to the -4th power), as do the corresponding terrestrial and martian spectra. The variance spectra of the Bouguer corrections (topography converted to equivalent gravity) for these bodies have the same basic form as the observed gravity; and, in fact, the spectral ratios are nearly constant throughout the observed spectral range for each body. Despite this spectral compatibility, the correlation between gravity and topography is generally quite poor on a global scale.

Bills, B. G.↗

Extensional flow of dilute polymer solution

Simultaneous effects of temperature and concentration on tensile viscosity are investigated using a semi-empirical scaling law established to relate the concentration, temperature and deformation rate by a reduced deformation rate variable. Results show the onset of high viscosity occurring in the vicinity of the onset of non-Newtonian viscosity observed in a simple shear flow experiment. High viscosity is also compared with steady and dynamic shear data. Finally, the asymptotic solution of Hassager's kinetic theory of a bead-rod model for macromolecular solutions is compared with the data, indicating that tensile viscosity depends strongly on the molecular weight, the higher the molecular weight, the more sensitive the tensile viscosity in terms of the deformation rate.

Peng, S. T. J.↗

Performance of an INTEGRAL spectrometer model

Model calculations for the INTEGRAL spectrometer (SPI) onboard the future INTErnational Gamma Ray Astrophysics Laboratory (INTEGAL) are presented, where the sensitivity for narrow lines is based on estimates of the background level and the detection efficiency. The instrumental background rates are explained as the sum of various components that depend on the cosmic ray intensity and the spectrometer characteristics, such as the mass distribution around the Ge detectors, the passive material, the characteristics of the detector system and the background reduction techniques. Extended background calculations were performed with Monte Carlo simulations and using semi-empirical and calculated neutron and proton cross sections. In order to improve the INTEGRAL spectrometer sensitivity, several designs and background reduction techniques were compared for an instrument with a fixed detector volume.

Jean, P.↗

Bidirectional Reflectance of a Macroscopically Flat, High-Albedo Particulate Surface: An Efficient Radiative Transfer Solution and Applications to Regoliths

Many remote sensing applications rely on accurate knowledge of the bidirectional reflection function (BRF) of surfaces composed of discrete, randomly positioned scattering particles. Theoretical computations of BRFs for plane-parallel particulate layers are usually reduced to solving the radiative transfer equation (RTE) using one of existing exact or approximate techniques. Since semi-empirical approximate approaches are notorious for their low accuracy, violation of the energy conservation law, and ability to produce unphysical results, the use of numerically exact solutions of RTE has gained justified popularity. For example, the computation of BRFs for macroscopically flat particulate surfaces in many geophysical publications is based on the adding-doubling (AD) and discrete ordinate (DO) methods. A further saving of computer resources can be achieved by using a more efficient technique to solve the plane-parallel RTE than the AD and DO methods. Since many natural particulate surfaces can be well represented by the model of an optically semi-infinite, homogeneous scattering layer, one can find the BRF directly by solving the Ambartsumian's nonlinear integral equation using a simple iterative technique. In this way, the computation of the internal radiation field is avoided and the computer code becomes highly efficient and very accurate and compact. Furthermore, the BRF thus obtained fully obeys the fundamental physical laws of energy conservation and reciprocity. In this paper, we discuss numerical aspects and the computer implementation of this technique, examine the applicability of the Henyey-Greenstein phase function and the sigma-Eddington approximation in BRF and flux calculations, and describe sample applications demonstrating the potential effect of particle shape on the bidirectional reflectance of flat regolith surfaces. Although the effects of packing density and coherent backscattering are currently neglected, they can also be incorporated. The FORTRAN implementation of the technique is available on the World Wide Web, and can be applied to a wide range of remote sensing problems. BRF computations for undulated (macroscopically rough) surfaces are more complicated and often rely on time consuming Monte Carlo procedures. This approach is especially inefficient for optically thick, weakly absorbing media (e.g., snow and desert surfaces at visible wavelengths since a photon may undergo many internal scattering events before it exists the medium or is absorbed. However, undulated surfaces can often be represented as collections of locally flat tilted facets characterized by the BRF found from the traditional plane parallel RTE. In this way the MOnte Carlo procedure could be used only to evaluate the effects of surface shadowing and multiple surface reflections, thereby bypassing the time-consuming ray tracing inside the medium and providing a great savings of CPU time.

Mishchenko, Michael I.↗

Supercritical wing sections 2, volume 108

A mathematical theory for the design and analysis of supercritical wing sections was previously presented. Examples and computer programs showing how this method works were included. The work on transonics is presented in a more definitive form. For design, a better model of the trailing edge is introduced which should eliminate a loss of fifteen or twenty percent in lift experienced with previous heavily aft loaded models, which is attributed to boundary layer separation. How drag creep can be reduced at off-design conditions is indicated. A rotated finite difference scheme is presented that enables the application of Murman's method of analysis in more or less arbitrary curvilinear coordinate systems. This allows the use of supersonic as well as subsonic free stream Mach numbers and to capture shock waves as far back on an airfoil as desired. Moreover, it leads to an effective three dimensional program for the computation of transonic flow past an oblique wing. In the case of two dimensional flow, the method is extended to take into account the displacement thickness computed by a semi-empirical turbulent boundary layer correction.

Bauer, F.↗

Developing a gas rocket performance prediction technique

A simple, semi-empirical performance correlation/prediction technique applicable to gaseous and liquid propellant rocket engines is presented. Excellent correlations were attained for over 100 test firings by adjusting the computation of the gaseous mixing of an unreactive, coaxial jet using a correlation factor, F, which resulted in prediction of the experimental combustion efficiency for each firing. Static pressure, mean velocity and turbulence intensity in the developing region of non-reactive coaxial jets, typical of those of coaxial injector elements were determined. Detailed profiles were obtained at twelve axial locations (extending from the nozzle exit for a distance of five diameters) downstream from a single element of the Bell Aerospace H2/O2 19-element coaxial injector. These data are compared with analytical predictions made using both eddy viscosity and turbulence kinetic energy mixing models and available computer codes. Comparisons were disappointing, demonstrating the necessity of developing improved turbulence models and computational techniques before detailed predictions of practical coaxial free jet flows are attempted.

Morgenthaler, J. H.↗

Modeling and Real-Time Process Monitoring of Organometallic Chemical Vapor Deposition of III-V Phosphides and Nitrides at Low and High Pressure

The purpose of this paper is to review modeling and real-time monitoring by robust methods of reflectance spectroscopy of organometallic chemical vapor deposition (OMCVD) processes in extreme regimes of pressure. The merits of p-polarized reflectance spectroscopy under the conditions of chemical beam epitaxy (CBE) and of internal transmission spectroscopy and principal angle spectroscopy at high pressure are assessed. In order to extend OMCVD to materials that exhibit large thermal decomposition pressure at their optimum growth temperature we have designed and built a differentially-pressure-controlled (DCP) OMCVD reactor for use at pressures greater than or equal to 6 atm. We also describe a compact hard-shell (CHS) reactor for extending the pressure range to 100 atm. At such very high pressure the decomposition of source vapors occurs in the vapor phase, and is coupled to flow dynamics and transport. Rate constants for homogeneous gas phase reactions can be predicted based on a combination of first principles and semi-empirical calculations. The pressure dependence of unimolecular rate constants is described by RRKM theory, but requires variational and anharmonicity corrections not included in presently available calculations with the exception of ammonia decomposition. Commercial codes that include chemical reactions and transport exist, but do not adequately cover at present the kinetics of heteroepitaxial crystal growth.

Bachmann, K. J.↗

Prediction of static aerodynamic characteristics for slender bodies alone and with lifting surfaces to very high angles of attack

An engineering-type method is presented for computing normal-force and pitching-moment coefficients for slender bodies of circular and noncircular cross section alone and with lifting surfaces. In this method, a semi-empirical term representing viscous-separation crossflow is added to a term representing potential-theory crossflow. For many bodies of revolution, computed aerodynamic characteristics are shown to agree with measured results for investigated free-stream Mach numbers from 0.6 to 2.9. The angles of attack extend from 0 deg to 180 deg for M = 2.9 from 0 deg to 60 deg for M = 0.6 to 2.0. For several bodies of elliptic cross section, measured results are also predicted reasonably well over the investigated Mach number range from 0.6 to 2.0 and at angles of attack from 0 deg to 60 deg. As for the bodies of revolution, the predictions are best for supersonic Mach numbers. For body-wing and body-wing-tail configurations with wings of aspect ratios 3 and 4, measured normal-force coefficients and centers are predicted reasonably well at the upper test Mach number of 2.0. Vapor-screen and oil-flow pictures are shown for many body, body-wing and body-wing-tail configurations. When spearation and vortex patterns are asymmetric, undesirable side forces are measured for the models even at zero sideslip angle. Generally, the side-force coefficients decrease or vanish with the following: increase in Mach number, decrease in nose fineness ratio, change from sharp to blunt nose, and flattening of body cross section (particularly the body nose).

Jorgensen, L. H.↗