The T-matrix technique for calculations of scattering properties of ensembles of randomly oriented particles with different size

We develop a modification of the T-matrix method that allows efficient studies of scattering properties of ensembles of independent irregular particles of different size. The advantage of the modification is quick calculations using the so-called shape-matrices (Sh-matrices), which allow more rapid calculations of scattering by particles of different size and can be used for averaging scattering properties over particle size. To illustrate the advantage we calculate the scattering-angle dependence of the intensity and degree of linear polarization of ensembles of cubes and Chebyshev particles of different size using both the new and traditional methods. Our time savings in calculating scattering properties for the particles with the new methodology is approximately a factor of ten when calculating scattering properties of one hundred of the same type of particles with different size parameter. As can be anticipated, increasing the size interval results in a smoothing of the structure of the photometric curves and a decrease in the linear polarization.     

Polarization of near-forward-scattered light from particulate substrates illuminated at near-grazing angles

Laboratory photopolarimetric measurements of light scattered by substrates consisting of semitransparent particles with sizes significantly larger than the wavelength show a polarization shoulder at small scattering angles near θ=10-30° in addition to the Brewster maximum positioned near θ=50°. With ray-tracing simulations, we find that the shoulder appears to be related to light passing through particles in the upper layers of the substrates. We study the dependence on particle absorption and packing density of particulate substrates. The studies show that the shoulder weakens with increased absorption and packing density.     

Backscattering and negative polarization of agglomerate particles

We used the discrete dipole approximation to study the backscattering of agglomerate particles consisting of oblong monomers. We varied the aspect ratio of the monomers from approximately 1 (sphere) to 4, while we kept the total particle volume equivalent to that of an x = 10 sphere for m = 1.59 + i0 and 1.50 + i0 and considered two values of agglomerate packing density: rho = 0.25 and rho = 0.1. We found that these particles do not display a prominent brightness opposition effect but do produce significant negative polarization over a range of near-backscattering angles. Increasing the monomers' aspect ratio can make the negative polarization much more prominent. We have noted also that decreasing m and p can reduce the amplitude of the negative polarization for these particles.     

Hydroxy- and alkoxy-bridged dinuclear uranyl-Schiff base complexes: hydrolysis, transamination and extraction studies

The reaction of uranyl nitrate with 1,3-bis(salicylideneamino)-2-propanol (H(3)L1) and 1,3-bis(3,5-di-tert-butylsalicylideneamino)-2-propanol (H(3)L2) in the presence of triethylamine (Et(3)N) yielded hydroxy- and alkoxy-bridged dinuclear complexes; [(UO(2))(2)(L1)(OH)(MeOH)(2)].(MeOH)(2) (.(MeOH)(2)) and [(UO(2))(2)(L2)(OH)(MeOH)(2)].(MeOH)(2) (.(MeOH)(2)). The crystal structures of .(DMF)(2) and .(DMF)(2) exhibit an unsymmetrical central U(2)O(2) core involving bridging alkoxy- and hydroxy-oxygen atoms. The geometry around the uranium center in .(DMF)(2) and .(DMF)(2) is that of a distorted pentagonal bipyramid with the solvent molecule occupying the fifth coordination site. The flexible nature of the ligand backbone is more pronounced in .(DMF)(2) compared to .(DMF)(2), yielding two molecules per unit cell in different conformations. Under similar reaction conditions, using ethylenediamine as a base, the respective Salen-based uranyl compounds, [UO(2)(Salen)(MeOH)] () and [UO(2)(Bu(t)(2)-Salen)(MeOH)] () are obtained due to transamination of the ligand backbone. Complexes .(MeOH)(2) and .(MeOH)(2) when reacted with an excess of ethylenediamine failed to yield the respective Salen-based complexes, and , respectively. The new compounds have been characterized using solution (NMR and UV-Vis) and solid-state (IR, X-ray crystallography) techniques. Hydrolysis of .(MeOH)(2) and .(MeOH)(2) in the pH range 1-14 was studied using UV-Vis spectroscopy and compared with the hydrolysis of and [UO(2)(Salophen)(MeOH)] (). A two-phase extraction study suggests quantitative removal of uranyl ions from the aqueous phase at higher pH conditions.     

Group 13 decamethylmetallocenium cations

Salts containing the decamethylmetallocenium cations, [(C(5)Me(5))(2)M](+) (or Cp*(2)M(+)) of the group 13 "metals" B, Al and Ga have been prepared using a variety of synthetic routes. Precursor molecules of the type Cp*(2)MX (X=Cl, Br, Me) exhibit structural features that vary significantly depending on the size and electronegativity of the central atom. While salt metathesis, halide abstraction and methanide abstraction methods represent viable routes for the preparation of salts of Cp*(2)B(+) and Cp*(2)Al(+), acidolysis of a Cp* group from Cp*(3)Ga is the most reliable method for the synthesis of the analogous gallium cation. Gallocenium cations are less stable than either of the lighter congeneric cations since they prove to be susceptible to decomposition reactions involving the "back-transfer" of ligands from the counter anion. Density functional theory (DFT) calculations revealed that, whereas Cp*(2)Ga(+) is predicted to adopt a molecular structure more similar to that of Cp*(2)B(+), the electronic structure of the gallium cation bears a greater resemblance to that of Cp*(2)Al(+).     

Sequestered plutonium: [Pu(IV){5LIO(Me-3,2-HOPO)}2]--the first structurally characterized plutonium hydroxypyridonate complex

The first single-crystal X-ray diffraction analysis of a hydroxypyridonate plutonium(IV) complex is presented, that of the tetradentate ligand 5LIO(Me-3,2-HOPO) with Pu(IV). The [Pu(IV){5LIO(Me-3,2-HOPO)}(2)] complex crystallizes in the space group Pna2(1) with the asymmetric unit cell containing two unique eight-coordinate plutonium complexes and one perchlorate anion. According to shape measure analysis, the geometry of both Pu centers is closest to a bicapped trigonal prism (C(2v) symmetry, for Pu 1: S(C(2v))=13.48 degrees , S(D(4d))=15.43 degrees , S(D(4d))=16.10 degrees ). The average bond length for the Pu--O(phenolic) is 2.31(4) A, whereas the Pu--O(amide) distances are slightly longer, averaging 2.40(2) A. The preparative chemistry of this compound and the implications of the structure are discussed.     

Light scattering by Gaussian particles with internal inclusions and roughened surfaces using ray optics

We study light scattering by Gaussian-random-sphere particles that are large compared to the wavelength of the incident light using ray optics that, in addition to Fresnellian reflection and refraction, accounts for diffuse scattering. We consider two types of diffusely scattering media. One type of media constitutes a uniform medium inside the particle, i.e. a diffuse internal medium. The second type of media constitutes a layer on the surface of the particle that is thin compared to the particle dimensions and acts as a diffuse external medium mimicking the particle surface roughness. We illustrate the effects of the diffuse media on the scattering characteristics for both cases and show that incorporating diffuse scatterers allows us to explain the scattering matrices measured experimentally for Saharan sand particles large compared to the wavelength.     

Seismic scattering from a spherical inclusion eccentrically located within a homogeneous, spherical host: theoretical derivation

The scattered fields from a spherical body eccentrically located within an otherwise homogeneous host sphere are derived by satisfying the boundary conditions at both interfaces simultaneously. The source, which may be composed of any linear combination of S and P waves, is also located arbitrarily within the host sphere. The scattering system may have applications in seismic scattering, by cavities or dense bodies located near the Earth surface or to the Slichter mode.     

Particle size effect on the opposition spike and negative polarization

We report results of experiments designed to increase our understanding of the influence of particle size on the photometric opposition spike and negative polarization observed in the reflectance and polarization phase curves of particulate surfaces. We concentrate our studies on particle-size separates of alumina (bright powders) and boron carbide (absorbing powders). We use two photopolarimeters that span small (0.2-17°) and large (2-160°) phase-angle ranges. The results suggest that the negative polarization has two dominant mechanisms: (1) the coherent-backscatter enhancement and (2) single-particle scatter, and that the contributions of the mechanisms are a function of particle size. The measured photometric and polarimetric phase functions can be applied to evaluate models used to calculate scattering properties of particulate surfaces.