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Density functional theory study of transition metal porphine adsorption on gold surface and electric field induced conformation changes

Proposed for publication in the Journal of the American Chemical Society.

Rempe, Susan R.; Schultz, Peter A.; Chandross, M.

We apply density functional theory (DFT) and the DFT+U technique to study the adsorption of transition metal porphine molecules on atomistically flat Au(111) surfaces. DFT calculations using the Perdew?Burke?Ernzerhof exchange correlation functional correctly predict the palladium porphine (PdP) low-spin ground state. PdP is found to adsorb preferentially on gold in a flat geometry, not in an edgewise geometry, in qualitative agreement with experiments on substituted porphyrins. It exhibits no covalent bonding to Au(111), and the binding energy is a small fraction of an electronvolt. The DFT+U technique, parametrized to B3LYP-predicted spin state ordering of the Mn d-electrons, is found to be crucial for reproducing the correct magnetic moment and geometry of the isolated manganese porphine (MnP) molecule. Adsorption of Mn(II)P on Au(111) substantially alters the Mn ion spin state. Its interaction with the gold substrate is stronger and more site-specific than that of PdP. The binding can be partially reversed by applying an electric potential, which leads to significant changes in the electronic and magnetic properties of adsorbed MnP and 0.1 {angstrom} changes in the Mn-nitrogen distances within the porphine macrocycle. We conjecture that this DFT+U approach may be a useful general method for modeling first-row transition metal ion complexes in a condensed-matter setting.

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Emissivity-correcting near-UV pyrometry for group-III nitride OMVPE

Proposed for publication in the Journal of Crystal Growth.

Creighton, J.R.; Koleske, Daniel K.; Mitchell, Christine C.

We developed a pyrometer that operates near the high-temperature bandgap of GaN, thus solving the transparency problem once a {approx} 1 {micro}m thick GaN epilayer has been established. The system collects radiation in the near-UV (380-415 nm) and has an effective detection wavelength of {approx}405 nm. By simultaneously measuring reflectance we also correct for emissivity changes when films of differing optical properties (e.g. AlGaN) are deposited on the GaN template. We recently modified the pyrometer hardware and software to enable measurements in a multiwafer Veeco D-125 OMVPE system. A method of synchronizing and indexing the detection system with the wafer platen was developed; so signals only from the desired wafer(s) could be measured, while rejecting thermal emission signals from the platen. Despite losses in optical throughput and duty cycle we are able to maintain adequate performance from 700 to 1100 C.

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A model for ablated plasma width applied to peak X-ray power scaling for Z-pinch wire array implosions

Stygar, William A.; Cuneo, M.E.

We present the solution of a 1D radial MHD model of the plasma ablated from multi-MA wire array implosions extending a recently obtained steady state solution [J.P. Chittenden, et al. Phys. Plasmas 11, 1118 (2004)] to a driving current that is exponential in time. We obtain a solution for the flow in almost analytical form by reducing the partial differential equations to a set of ordinary differential equations with a single parameter. We compute the mass weighted density width, and find the regime in which it agrees to a few percent with that of a simpler approximation to the ablated plasma flow, for which the driving current is linear in time, and the flow velocity constant. Assuming that the density width at the end of the ablation period is proportional to width of the plasma sheath at stagnation, we obtain a scaling relationship for peak X-ray power. We compare this relationship to experimental peak X-ray powers for tungsten wire arrays on the Z pulsed power generator of Sandia National Laboratories, and to previously proposed scaling hypotheses. We also use this scaling to project peak X-ray powers on ZR, a higher peak current modification of Z, presently under design.

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The development of circuit models for ZR

Harjes, Henry C.; Struve, Kenneth W.

Summary from only given. The capabilities of the Z accelerator will be significantly enhanced by the Z Refurbishment (ZR) project [McDaniel DH, 2002]. The performance of a single ZR module is currently being characterized in the pre-production engineering evaluation test bed, Z20 [Lehr, JM, 2003]. Z20 is thoroughly diagnosed so that electrical performance of the module can be established. Circuit models of Z20 have been developed and validated in both Screamer [1985] and Bertha [1989] circuit codes. For the purposes of predicting ZR performance, a full ZR circuit model has also been developed in Bertha. The full ZR model (using operating parameters demonstrated on Z20) indicates that the required 26 MA, 100 ns implosion time, output load current pulse will be achieved on ZR. In this paper, the electrical characterization of Z20 and development of the single module circuit models will be discussed in detail. The full ZR model will also be discussed and the results of several system studies conducted to predict ZR performance will be presented.

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Stress creation during Ni-Mn alloy electrodeposition

Proposed for publication in the Journal of Applied Physics.

Hearne, Sean J.; Brewer, Luke N.; Foiles, Stephen M.; Floro, Jerrold A.; Frazer, Colleen S.; Tissot, Ralph G.; Rodriguez, Marko A.; Hlava, Paul F.

The stress evolution during electrodeposition of NiMn from a sulfamate-based bath was investigated as a function of Mn concentration and current density. The NiMn stress evolution with film thickness exhibited an initial high transitional stress region followed by a region of steady-state stress with a magnitude that depended on deposition rate, similar to the previously reported stress evolution in electrodeposited Ni [S. J. Hearne and J. A. Floro, J. Appl. Phys. 97, 014901-1 (2005)]. The incorporation of increasing amounts of Mn resulted in a linear increase in the steady-state stress at constant current density. However, no significant changes in the texture or grain size were observed, which indicates that an atomistic process is driving the changes in steady-state stress. Additionally, microstrain measured by ex situ x-ray diffraction increased with increasing Mn content, which was likely the result of localized lattice distortions associated with substitutional incorporation of Mn and/or increased twin density.

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A statistical analysis of launch sinusoidal vibration data

Cap, Jerome S.; Edwards, Timothy S.; C'De Baca, John E.

The summary of this report is: (1) The Kernal Density Estimator (KDE) model using log data provides the most conservative estimates; (2) The Empirical Tolerance Limit (ETL) model provides the least conservative estimates; (3) The results for the Karhunen-Loeve (K-L) and Normal Tolerance Limit (NTL) models lie in between the extremes; (4) The NTL results ended up being as credible as any of the other methods. This may be related to the fact that the data appeared to fit a lognormal distribution for higher values of {beta}; (5) The discrepancy between these methods appears to widen for higher values of {beta} and {gamma}; (6) The reasons for the extreme difference in the KDE results depending on whether one uses the raw data or the log of the data is not clear at this time; and (7) Which model will best suit our needs is not clear at this time.

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Synthesis, optical properties, and growth mechanism of blue-emitting CdSe nanorods

Journal of the American Chemical Society

Thoma, Steven G.; Sanchez, Arturo; Provencio, P.N.; Abrams, B.L.; Wilcoxon, Jess P.

Blue-emitting, cubic phase CdSe nanorods with an approximate diameter of 2.5 nm and lengths up to 12 nm have been synthesized at low temperature (100 °C) in a single surfactant using a single-source molecular precursor. Transmission electron microscopy and dynamic light scattering measurements indicate that the nanorods are formed from self-assembly of isotropic nanoclusters. Anisotropic growth in a single surfactant appears to be favored when growth occurs below the thermal decomposition temperature of the single-source precursor. © 2005 American Chemical Society.

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XRD and NMR investigation of Ti-compound formation in solution-doping of sodium aluminum hydrides: Solubility of Ti in NaAlH4 crystals grown in THF

Journal of Alloys and Compounds

Majzoub, E.H.; Herberg, J.L.; Stumpf, Roland R.; Spangler, S.; Maxwell, R.S.

Sodium aluminum hydrides have gained attention due to their high hydrogen weight percent (5.5% ideal) compared to interstitial hydrides, and as a model for hydrides with even higher hydrogen weight fraction. The purpose of this paper is to investigate the Ti-compounds that are formed under solution-doping techniques, such as wet doping in solvents such as tetrahydrofuran (THF). Compound formation in Ti-doped sodium aluminum hydrides is investigated using X-ray diffraction (XRD) and magic angle spinning (MAS) nuclear magnetic resonance (NMR). We present lattice parameter measurements of crushed single crystals, which were exposed to Ti during growth. Rietveld refinements indicate no lattice parameter change and thus no solubility for Ti in NaAlH4 by this method of exposure. In addition, X-ray diffraction data indicate that no Ti substitutes in NaH, the final decomposition product for the alanate. Reaction products of completely reacted (33.3 at.%-doped) samples that were solvent-mixed or mechanically milled are investigated. Formation of TiAl 3 is observed in mechanically milled materials, but not solution mixed samples, where bonding to THF likely stabilizes Ti-based nano-clusters. The Ti in these clusters is activated by mechanical milling. © 2004 Elsevier B.V. All rights reserved.

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DSMC simulations in support of the STS-107 accident investigation

AIP Conference Proceedings

Gallis, Michael A.; Boyles, Katie A.; Lebeau, Gerald J.

Three-dimensional Direct Simulation Monte Carlo simulations of Columbia Shuttle Orbiter flight STS-107 are presented. The aim of this work is to determine the aerodynamic and heating behavior of the Orbiter during aerobraking maneuvers and to provide piecewise integration of key scenario events to assess the plausibility of the candidate failure scenarios. The flight of the Orbiter is examined at two altitudes: 350 kft and 300 kft. The flow field around the Orbiter and the heat transfer to it are calculated for the undamaged configuration. The flow inside the wing for an assumed damage to the leading edge in the form of a 10-inch hole is studied. © 2005 American Institute of Physics.

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A wall-function approach to incorporating Knudsen-layer effects in gas micro flow simulations

AIP Conference Proceedings

Lockerby, D.A.; Reese, J.M.; Gallis, Michail A.

For gas flows in microfluidic configurations, the Knudsen layer close to the wall can comprise a substantial part of the entire flowfield and has a major effect on quantities such as the mass flow rate through micro devices. The Knudsen layer itself is characterized by a highly nonlinear relationship between the viscous stress and the strain rate of the gas, so even if the Navier-Stokes equations can be used to describe the core gas flow they are certainly inappropriate for the Knudsen layer itself. In this paper we propose a "wall-function" model for the stress/strain rate relations in the Knudsen layer. The constitutive structure of the Knudsen layer has been derived from results from kinetic theory for isothermal shear flow over a planar surface. We investigate the ability of this simplified model to predict Knudsen-layer effects in a variety of configurations. We further propose a semi-empirical Knudsen-number correction to this wall function, based on high-accuracy DSMC results, to extend the predictive capabilities of the model to greater degrees of rarefaction. © 2005 American Institute of Physics.

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Nitrogen incorporation effects on gain properties of GaInNAs lasers: Experiment and theory

Applied Physics Letters

Thränhardt, A.; Kuznetsova, I.; Schlichenmaier, C.; Koch, S.W.; Shterengas, L.; Belenky, G.; Yeh, J.Y.; Mawst, L.J.; Tansu, N.; Hader, J.; Moloney, J.V.; Chow, Weng W.

Gain properties of GaInNAs lasers with different nitrogen concentrations in the quantum wells are investigated experimentally and theoretically. Whereas nitrogen incorporation induces appreciable modifications in the spectral extension and the carrier density dependence of the gain, it is found that the linewidth enhancement factor is reduced by inclusion of nitrogen, but basically unaffected by different nitrogen content due to the balancing between gain and index changes. © 2005 American Institute of Physics.

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Long-range transition state theory

Journal of Chemical Physics

Georgievskii, Yuri; Klippenstein, Stephen J.

The implementation of variational transition state theory (VTST) for long-range asymptotic potential forms is considered, with particular emphasis on the energy and total angular momentum resolved (μJ -VTST) implementation. A long-range transition state approximation yields a remarkably simple and universal description of the kinetics of reactions governed by long-range interactions. The resulting (μJ -VTST) implementation is shown to yield capture-rate coefficients that compare favorably with those from trajectory simulations (deviating by less than 10%) for a wide variety of neutral and ionic long-range potential forms. Simple analytic results are derived for many of these cases. A brief comparison with a variety of low-temperature experimental studies illustrates the power of this approach as an analysis tool. The present VTST approach allows for a simple analysis of the applicability conditions for some related theoretical approaches. It also provides an estimate of the temperature or energy at which the "long-range transition state" moves to such short separations that short-range effects, such as chemical bonding, steric repulsion, and electronic state selectivity, must be considered. © 2005 American Institute of Physics.

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Results 84626–84650 of 96,771
Results 84626–84650 of 96,771