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At least 1,369 records · Page 76

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.↗

Grid generation on surfaces in 3 dimensions

The development of a surface grid generation algorithm was initiated. The basic adaptive movement technique of mean-value-relaxation was extended from the viewpoint of a single coordinate grid over a surface described by a single scalar function to that of a surface more generally defined by vector functions and covered by a collection of smoothly connected grids. Within the multiconnected assemblage, the application of control was examined in several instances.

Eiseman, Peter R.↗

Correlation of Oil-Water and Air-Water Contact Angles of Diverse Silanized Surfaces and Relationship to Fluid Interfacial Tensions

The use of air-water, {Theta}{sub wa}, or air-liquid contact angles is customary in surface science, while oil-water contact angles {Theta}{sub ow}, are of paramount importance in subsurface multiphase flow phenomena including petroleum reocovery, nonaqueous phase liquid fate and transport, and geological carbon sequestration. In this paper we determine both the air-water and oil-water contact angles of silica surfaces modified with a diverse selection of silanes, using hexadecane as the oil. The silanes included alkylsilanes, alkylarylsilanes, and silanes with alkyl or aryl groups that are functionalized with heteroatoms such as N, O, and S. These silanes yielded surfaces with wettabilities from water-wet to oil wet, including specific silanized surfaces functionalized with heteroatoms that yield intermediate wet surfaces. The oil-water contact angles for clean and silanized surfaces, excluding one partially fluorinated surface, correlate linearly with air-water contact angles with a slope of 1.41 (R = 0.981, n = 13). These data were used to examine a previously untested theoretical treatment relating air-water and oil-water contact angles in terms of fluid interfacial energies. Plotting the cosines of these contact angles against one another, we obtain a linear relationship in excellent agreement with the theoretical treatment; the data fit cos {Theta}{sub ow} = 0.667 cos {Theta}{sub ow} + 0.384 (R = 0.981, n = 13), intercepting cos {Theta}{sub ow} = -1 at -0.284. The theoretical slope, based on the fluid interfacial tensions {Theta}{sub wa}, {Theta}{sub ow}, and {Theta}{sub oa}, is 0.67. We also demonstrate how silanes can be used to alter the wettability of the interior of a pore network micromodel device constructed in silicon/silica with a glass cover plate. Such micromodels are used to study multiphase flow phenomena. The contact angle of the resulting interior was determined in situ. An intermediate wet micromodel gave a contact angle in excellent agreement with that obtained on an open planar silica surface using the same silane.

02 PETROLEUM↗

Enhanced Fe2O3 Reducibility via Surface Modification with Pd: Characterizing the Synergy within Pd/Fe Catalysts for Hydrodeoxygenation Reactions

The synergistic catalysis in the hydrodeoxygenation of phenolic compounds over a Pd/Fe bimetallic surface has been well established. However, the nature of this synergy is still in part a mystery. In this work, we used a combined experimental and theoretical approach to understand a potential function of the surface Pd in the reduction of Pd/Fe2O3. This function of Pd was investigated via the comparison of the reduction properties as well as other physicochemical properties of samples synthesized by the reduction of Fe2O3 nanoparticles with and without surface Pd. Temperature-programmed reduction studies demonstrated the remarkable facilitation of reduction by addition of Pd, evidenced by a 150 degrees C shift toward lower temperature of the reduction peak of Fe3+. From X-ray photoelectron spectroscopy and theoretical calculation results, the interaction between Pd and the Fe2O3 surface occurs through the exchange of electrons with both the surface Fe and O atoms. This bonding between the Pd and surface oxide elements causes the Pd to partially donate electrons to the oxide surface, making the surface electrons more delocalized. This electron delocalization stabilizes the reduced oxide surfaces, as suggested by the TPR results and theoretical prediction. Therefore, the stabilization of the reduced Fe surface as well as the facilitated water formation by introduction of Pd is expected to significantly contribute to the Pd-Fe synergy in hydrodeoxygenation catalysis.

bimetallic catalysts↗

Hydrogen intercalation of single and multiple layer graphene synthesized on Si-terminated SiC(0001) surface

Ab initio density functional theory simulations were used to investigate the influence of hydrogen intercalation on the electronic properties of single and multiple graphene layers deposited on the SiC(0001) surface (Si-face). It is shown that single carbon layer, known as a buffer layer, covalently bound to the SiC substrate, is liberated after hydrogen intercalation, showing characteristic Dirac cones in the band structure. This is in agreement with the results of angle resolved photoelectron spectroscopy measurements of hydrogen intercalation of SiC-graphene samples. In contrast to that hydrogen intercalation has limited impact on the multiple sheet graphene, deposited on Si-terminated SiC surface. The covalently bound buffer layer is liberated attaining its graphene like structure and dispersion relation typical for multilayer graphene. Nevertheless, before and after intercalation, the four layer graphene preserved the following dispersion relations in the vicinity of K point: linear for (AAAA) stacking, direct parabolic for Bernal (ABAB) stacking and “wizard hat” parabolic for rhombohedral (ABCA) stacking.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Ab Initio Density Functional Calculations and Infra-Red Study of CO Interaction with Pd Atoms on θ-Al 2 O 3 (010) Surface

The ab initio density functional theoretical studies show that energetics favor CO oxidation on single Pd atoms supported on θ-alumina. The diffuse reflectance infra-red spectroscopy (DRIFTS) results show that carbonates are formed as intermediates when single supported Pd atoms are exposed to a gaseous mixture of CO + O 2 . The rapid agglomeration of Pd atoms under CO oxidation conditions even at 6°C leads to the presence of Pd particles along with single atoms during CO oxidation experiments. Thus, the observed CO oxidation has contributions from both single Pd atoms and Pd particles.

36 MATERIALS SCIENCE↗

Focusing effects in the synthetic aperture radar imaging of ocean waves

The paper derives the properties of the image obtained for an ocean wave whose cross section and surface profile are functions, representing the wave phenomena, whose exact properties are determined by the ocean wave surface properties, for ocean wavelength, height, and orbital frequency. The effect of defocusing of the wave image due to its temporal motion is calculated, and both the resolution of the radar system if no focus compensation is provided in the processor and the necessary distance the azimuth telescope has to be moved to provide diffraction-limited imaging are derived. These results are illustrated for data obtained by synthetic aperture radar during Hurricane Gloria on September 30, 1976, and by ERIM radar over Marineland, Florida, on December 15, 1975.

Jain, A.↗

Determination of surface tension at the phase interface

A method was developed for determining the surface tension coefficient at the interface of two immiscible liquids or of a gas and a liquid. Basic in this method is the measurement of the capillary rise of a droplet of one of the phases placed on the surface of the other phase. It is shown that the capillary rise is a function of the surface energy of the droplet and the viscous friction of the phases. A mathematical model of the dynamics of a liquid droplet is supported by experiments.

Dobychin, Y. I.↗

A morphological study of silicon carbide prepared by chemical vapor deposition

Surface morphologies of SiC deposits obtained via chemical vapor deposition (CVD) were studied as functions of substrate surface temperature and the concentration of the silicon and carbon source material, methyltrichlorosilane. Substrates of graphite and alpha-SiC crystals were used. Explanations of the observed morphologies on graphite substrates and their marked changes with temperature are given in terms of chemical kinetics and mass transport arguments. The results of thermodynamic calculations were used to help explain the observed morphologies of the deposits on alpha-SiC substrates.

Tsui, P.↗

Elliptic surface grid generation in three-dimensional space

A methodology for surface grid generation in three dimensional space is described. The method solves a Poisson equation for each coordinate on arbitrary surfaces using successive line over-relaxation. The complete surface curvature terms were discretized and retained within the nonhomogeneous term in order to preserve surface definition; there is no need for conventional surface splines. Control functions were formulated to permit control of grid orthogonality and spacing. A method for interpolation of control functions into the domain was devised which permits their specification not only at the surface boundaries but within the interior as well. An interactive surface generation code which makes use of this methodology is currently under development.

Kania, Lee↗

Scanning Tunneling Microscopy Studies of Diamond Films and Optoelectronic Materials

We present a summary of the research, citations of publications resulting from the research and abstracts of such publications. We have made no inventions in the performance of the work in this project. The main goals of the project were to set up a Chemical Vapor Deposition (CVD) diamond growth system attached to an UltraHigh Vacuum (UHV) atomic resolution Scanning Tunneling Microscopy (STM) system and carry out experiments aimed at studying the properties and growth of diamond films using atomic resolution UHV STM. We successfully achieved these goals. We observed, for the first time, the atomic structure of the surface of CVD grown epitaxial diamond (100) films using UHV STM. We studied the effects of atomic hydrogen on the CVD diamond growth process. We studied the electronic properties of the diamond (100) (2x1) surface, and the effect of alkali metal adsorbates such as Cs on the work function of this surface using UHV STM spectroscopy techniques. We also studied, using STM, new electronic materials such as carbon nanotubes and gold nanostructures. This work resulted in four publications in refereed scientific journals and five publications in refereed conference proceedings.

Perez, Jose M.↗

Sensitivity of Surface Temperature to Oceanic Forcing via q -Flux Green’s Function Experiments. Part I: Linear Response Function

This paper explores the use of the linear response function (LRF) to relate the mean sea surface temperature (SST) response to prescribed ocean heat convergence ( q flux) forcings. Two methods for constructing the LRF based on the fluctuation–dissipation theorem (FDT) and Green’s function (GRF) are examined. A 900-yr preindustrial simulation by the Community Earth System Model coupled with a slab ocean model (CESM–SOM) is used to estimate the LRF using FDT. For GRF, 106 pairs of CESM–SOM simulations with warm and cold q-flux patches are performed. FDT is found to have some skill in estimating the SST response to a q-flux forcing when the local SST response is strong, but it fails in inverse estimation of the q-flux forcing for a given SST pattern. In contrast, GRF is shown to be reasonably accurate in estimating both SST response and q-flux forcing. Possible degradation in FDT may be attributed to insufficient data sampling, significant departure of the SST distribution from Gaussianity, and the nonnormality of the constructed operator. The GRF-based LRF is then used to (i) generate a global surface temperature sensitivity map that shows the q-flux forcing in higher latitudes to be 3–4 times more effective than low latitudes in producing global surface warming, and (ii) identify the most excitable SST mode (neutral vector) that shows marked resemblance to the interdecadal Pacific oscillation (IPO). The latter discovery suggests that the IPO-like fluctuation exists in the absence of the coupling to the ocean dynamics. Coupling to the ocean dynamics in CESM, on the other hand, only enhances the spectral power of the IPO at interannual time scales.

54 ENVIRONMENTAL SCIENCES↗

Atomic hydrogen adsorption on lithium-doped graphite surfaces

The effects of lithium doping of pristine and defective graphite surfaces on hydrogen adsorption are studied by the first-principles Plane-Wave Density Functional Theory. The surface defects are simulated by a single atomic vacancy. The DFT calculation is corrected for long-range effects through semi-empirical London terms for each constituent of the system. The lithium doping of the graphite surfaces notably reinforces hydrogen atom binding. Qualitative comparison with experimental results is given using the lithium 1s energy level shifts induced by the atomic vacancy and/or hydrogen trapping.

08 HYDROGEN↗

Adsorption on transition metal surfaces: Transferability and accuracy of DFT using the ADS41 dataset

We present a benchmarking study of adsorption energies on transition metal surfaces computed with select functionals across different density functional theory codes. In addition to gradient corrected functionals, we evaluate the accuracies of representative metaGGAs, including MS2, SCAN, and SCAN+rVV10 , as well as a short-range screened hybrid functional, HSE06. The study shows that the challenge of finding a functional that can simultaneously capture both covalent and noncovalent molecule-surface interactions persists, with no single functional in the benchmarking study with average errors < 0.2 eV. We find that HSE06 on average does not improve the accuracy compared to PBE for the surface chemistry of transition metals. The BEEF-vdW dispersion-corrected generalized gradient approximation (GGA) and the MS2 metaGGA yield the lowest errors in both chemisorption and dispersion energies, demonstrating that moving up the Jacob's ladder of functionals to screened hybrids does not necessarily improve the description of transition metal surface chemistry.

36 MATERIALS SCIENCE↗

On the choice of orbits for an altimetric satellite to study ocean circulation and tides

The choice of an orbit for satellite altimetric studies of the ocean's circulation and tides requires an understanding of the orbital characteristics that influence the accuracy of the satellite's measurements of sea level and the temporal and spatial distribution of the measurements. The orbital characteristics that influence accurate calculations of the satellite's position as a function of time are examined, and the pattern of ground tracks laid down on the ocean's surface as a function of the satellite's altitude and inclination is studied. The results are used to examine the aliases in the measurements of surface geostrophic currents and tides. Finally, these considerations are used to specify possible orbits that may be useful for the upcoming Topex/Poseidon mission.

Parke, Michael E.↗

A density functional theory model of mechanically activated silyl ester hydrolysis

To elucidate the mechanism of the mechanically activated dissociation of chemical bonds between carboxymethylated amylose (CMA) and silane functionalized silicon dioxide, we have investigated the dissociation kinetics of the bonds connecting CMA to silicon oxide surfaces with density functional calculations including the effects of force, solvent polarizability, and pH. We have determined the activation energies, the pre-exponential factors, and the reaction rate constants of candidate reactions. The weakest bond was found to be the silyl ester bond between the silicon and the alkoxy oxygen atom. Under acidic conditions, spontaneous proton addition occurs close to the silyl ester such that neutral reactions become insignificant. Upon proton addition at the most favored position, the activation energy for bond hydrolysis becomes 31 kJ mol{sup −1}, which agrees very well with experimental observation. Heterolytic bond scission in the protonated molecule has a much higher activation energy. The experimentally observed bi-exponential rupture kinetics can be explained by different side groups attached to the silicon atom of the silyl ester. The fact that different side groups lead to different dissociation kinetics provides an opportunity to deliberately modify and tune the kinetic parameters of mechanically activated bond dissociation of silyl esters.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Formic Acid Dissociative Adsorption on NiO(111): Energetics and Structure of Adsorbed Formate

Here, the dissociative adsorption of carboxylic acids on oxide surfaces is important for understanding adsorbed carboxylates, which are important as intermediates in catalytic reactions, for the organo-functionalization of oxide surfaces, and in many other aspects of oxide surface chemistry. We present here the first direct experimental measurement of the heat of dissociative adsorption of any carboxylic acid on any single-crystal oxide surface. The enthalpy of the dissociative adsorption of formic acid, the simplest carboxylic acid, to produce adsorbed formate and hydrogen (as a surface hydroxyl) on a (2 × 2)-NiO(111) surface is measured by single crystal adsorption calorimetry. The differential heat of adsorption decreases with formic acid coverage from 202 to 99 kJ/mol at saturation (0.25 ML). The structure of the adsorbed products is clarified by density functional theory (DFT) calculations, which provide energies in reasonable agreement with the calorimetry. These calculations show that formic acid readily dissociates on both the oxygen and Ni terminations of the octapolar NiO(111) surfaces, donating its acid H to a surface lattice oxygen, while HCOO adsorbs preferentially with bridging-type geometry near the M-O 3 /O-M 3 sites. The calculated energetics at low coverages agrees well with experimental data, while larger differences are observed at high coverage (0.25 ML). The large decrease in experimental heat of adsorption with coverage can be brought into agreement with the DFT energies if we assume that both types of octapolar surface terminations (O- and Ni-) are present on the starting surface.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗