Optical behavior of composite carbonaceous aerosols: DDA and EMT approaches

Atmospheric particles may contain a small amount of black carbon (BC) that may affect their optical properties. These optical properties also depend strongly on the particle morphology and internal topology. The efficiency factors for scattering Q_sca, absorption Q_abs, extinction Q_ext, backscattering Q_bk, as well as the asymmetry parameter cos, linear polarization P, and scattering phase functions S₁₁ are analyzed in detail as functions of morphology and internal topology. Backscattering quantities (like Q_bk and P and S₁₁ at large scattering angles) are affected most significantly. The behavior of these quantities depends strongly on the internal mixing of the constituent materials making up the particle. Effective medium theories (EMTs), which assume that the particle is homogeneous and are applied frequently in radiative transfer studies, can underestimate Q_sca and S₁₁ especially when high carbon contents are considered. Contrarily, EMTs also tend to overestimate the values of the asymmetry parameter and Q_abs.     

DDA simulations of light scattering by small irregular particles with various structure

We present DDA investigations of light scattering by irregular particles whose size is comparable with wavelength. We consider four types of randomly irregular particles: strongly damaged spheres, rough-surface spheres, pocked spheres, and agglomerated debris particles. Each type of particle is generated with a well defined algorithm producing an ensemble of stochastically different particles that have a common origin. The different types of irregular particles produce different angular dependencies of intensity and linear polarization degree. Transformation of phase curves of intensity and polarization with changing size parameter for irregular particles tends to be more monotonic, unlike spheres. We find that the magnitude of the negative polarization branch (NPB) tends to shrink as particle absorption increases; whereas, the maximal value and position of the positive polarization branch tends to increase. The most frequently observed shape of the negative polarization at small phase angles is asymmetric with a shift of the minimum position towards the angle of polarization sign inversion. All types of considered irregular particles reveal such asymmetry at x<10. Symmetric negative polarization branches occur seldom. The necessary conditions for their appearance are a relatively large size parameter x?10 to 12 and low absorption.     

Charge‐induced electromagnetic resonances in nanoparticles

Electromagnetic theories have reproduced the scattering properties of differently shaped particles and successfully been used to characterize numerous systems. However, certain anomalous features remain unexplained that include enhanced extinction when particles are much smaller than the wavelength. Here we explain these features exploiting recent research in electromagnetic scattering theories that suggests incorporating the effect of particle charge results in new physical outcomes that deviate appreciably from what is predicted by electromagnetic interaction from uncharged systems. For electrically charged particles, the resonant excitation of surface modes is governed by excess charges deposited on the particle surface. Charge effects become large when particles are small compared to the incident wavelength, and we show that the electrostatic approximation is not valid for modelling the electromagnetic interaction from such particles. Charge‐induced resonances appear in such systems that can reproduce previously unexplained phenomena, for instance, amplified microwave attenuation observed in sandstorms.

     

Digital holographic imaging of aerosol particles in flight

This work describes the design and application of an apparatus to image aerosol particles using digital holography in a flow-through, contact-free manner. Particles in an aerosol stream are illuminated by a triggered, pulsed laser and the pattern produced by the interference of this light with that scattered by the particles is recorded by a digital camera. The recorded pattern constitutes a digital hologram from which an image of the particles is computationally reconstructed using a fast Fourier transform. This imaging is validated using a cluster of ragweed pollen particles. Examples involving mineral-dust aerosols demonstrate the technique's in situ imaging capability for complex-shaped particles over a size range of roughly 15-500 μm micrometers. The focusing-like character of the reconstruction process is demonstrated using a NaCl aerosol particle and is compared to a similar particle imaged with a conventional microscope.     

Kinetic mass spectrometric determination of the absolute rate coefficient for the reaction NH3 (ν = 0) + NH3 → NH4 + NH2 at thermal kinetic energies

The absolute thermal rate coefficient for the reaction NH₃⁺ + NH₃ → NH₄⁺ + NH₂ has been determined experimentally for the first time for NH₃⁺ (ν = 0) reactant ions. An increase in E_vib results in a decrease in the rate coefficient for proton transfer.     

Novel supramolecular architectures in group 13 perfluoroaryl complexes. Synthesis and structures of [AlMe(C6F5)(mu-Me)]2 and GaMe(C6F5)2

Novel supramolecular architectures are observed in the solid state structures of [AlMe(C6F5)(mu-Me)]2 (1) and Ga(C6F5)2Me (2) via pi-pi stacking between C6F5 rings and intermolecular aryl-F-->Ga interactions, respectively.     

Novel dinuclear uranyl complexes with asymmetric schiff base ligands: synthesis, structural characterization, reactivity, and extraction studies

The reaction of uranyl nitrate with asymmetric [3O, N] Schiff base ligands in the presence of base yields dinuclear uranyl complexes, [UO2(HL1)]2.DMF (1), [UO2(HL2)]2.2DMF.H2O (2), and [UO2(HL3)]2.2DMF (3) with 3-(2-hydroxybenzylideneamino)propane-1,2-diol (H3L1), 4-((2,3-dihydroxypropylimino)methyl)benzene-1,3-diol (H3L2), and 3-(3,5-di-tert-butyl-2-hydroxybenzylideneamino)propane-1,2-diol (H3L3), respectively. All complexes exhibit a symmetric U2O2 core featuring a distorted pentagonal bipyramidal geometry around each uranyl center. The hydroxyl groups on the ligands are attached to the uranyl ion in chelating, bridging, and coordinate covalent bonds. Distortion in the backbone is more pronounced in 1, where the phenyl groups are on the same side of the planar U2O2 core. The phenyl groups are present on the opposite side of U2O2 core in 2 and 3 due to electronic and steric effects. A similar hydrogen-bonding pattern is observed in the solid-state structures of 1 and 3 with terminal hydroxyl groups and DMF molecules, resulting in discrete molecules. Free aryl hydroxyl groups and water molecules in 2 give rise to a two-dimensional network with water molecules in the channels of an extended corrugated sheet structure. Compound 1 in the presence of excess Ag(NO3) yields {[(UO2)(NO3)(C6H4OCOO)](NH(CH2CH3)3)}2 (4), where the geometry around the uranyl center is hexagonal bipyrimidal. Two-phase extraction studies of uranium from aqueous media employing H3L3 indicate 99% reduction of uranyl ion at higher pH.