Light scattering and absorption by soot in the presence of sulfate aerosols

The radiative properties of aerosol-soot mixtures, both internal and external, are determined in the visible and near-infrared bands by use of exact indirect mode-matching solutions to electromagnetic-wave scattering from a sphere with an eccentric spherical inclusion and from a cluster of spheres. Spherical sulfate droplets are assumed to represent aerosol particles. Soot particles are represented by volume-equivalent carbon spheres, the size distribution of which is obtained from the number distribution of the primary carbon particles that aggregate into soot grains. The mean gram-specific absorption cross section and the mean albedo of aerosol-soot mixtures are obtained by integration of the corresponding characteristics of composite sulfate-carbon particles over the size range of carbon spheres. Enhanced absorption of light by soot in aerosol-soot mixtures, a result of lensing by sulfate droplets, is highlighted by maps of the electromagnetic field in a sulfate-carbon particle.     

Scattering efficiency of aggregated clusters of spheres: dependence on configuration and composition

We study the orientation average scattering cross section of various isolated aggregates of identical spherical particles as functions of their size, optical properties, and spatial configurations. Two kinds of aggregates are studied: latex particles in water and rutile titanium dioxide pigments in a polymeric resin, with size parameters varying from 0.6 to 2.3. Calculations are performed by using a recursive centered T-matrix algorithm solution of the multiple scattering equation that we previously developed [J. Quant. Spectrosc. Radiat. Transfer 79-80, 533 (2003)]. We show that for a specific size of the constituent spheres, their respective couplings apparently vanish, regardless of the aggregate configuration, and that the scattering cross section of the entire cluster behaves as if its constituents were isolated. We found that the particular radius for which this phenomenon occurs is a function of the relative refractive index of the system. We also study the correlations between the strength of the coupling among the constituent spheres, and the pseudofractal dimension of the aggregate as it varies from 1 to 30.     

Study of nanoscale photopolymerized fullerene clusters in solution droplets using an ultrasonic nebulizer unit

In a designed and developed ultrasonic nebulizer system for obtaining macroscopic-quantity photopolymerized fullerene (C60) clusters, a C60 solution was vaporized to several micro-sized droplets in vacuum, resulting in the formation of C60 aggregates by evaporating the solvent (toluene). The system was invented to produce nanoscale photopolymerized carbon clusters through the irradiation of ultraviolet (UV) light on the C60 aggregates in vacuum. The products, photopolymerized C60 clusters obtained from the system using UV-visible (UV-Vis) absorption and high-performance (or high-pressure) liquid chromatography (HPLC) spectra, were characterized. Compared with the non-irradiating C60 solution, the UV-Vis absorption spectrum of the irradiated C60 solution was drastically decreased, especially at lambda = 335 nm and in the visible region from lambda = 450-650 nm. As such, the UV-Vis absorption spectra provide information about the polymerization of C60 molecules. These photopolymerized C60 clusters can be detected as having a heavy molecular mass order through the HPLC system, and the C60 and photopolymerized C60 cluster can be extracted from the trapped solution on the molecular mass. Although there is a possibility that the products include various forms of C60 clusters, the results suggest that the products obtained from the system using a vaporizer establish a new method of obtaining macroscopic-quantity C60 clusters.     

Light scattering and absorption by fractal-like carbonaceous chain aggregates: comparison of theories and experiment

This study compares the optical coefficients of size-selected soot particles measured at a wavelength of 870 nm with those predicted by three theories, namely, Rayleigh-Debye-Gans (RDG) approximation, volume-equivalent Mie theory, and integral equation formulation for scattering (IEFS). Soot particles, produced by a premixed ethene flame, were size-selected using two differential mobility analyzers in series, and their scattering and absorption coefficients were measured with nephelometry and photoacoustic spectroscopy. Scanning electron microscopy and image processing techniques were used for the parameterization of the structural properties of the fractal-like soot aggregates. The aggregate structural parameters were used to evaluate the predictions of the optical coefficients based on the three light-scattering and absorption theories. Our results show that the RDG approximation agrees within 10% with the experimental results and the exact electromagnetic calculations of the IEFS theory. Volume-equivalent Mie theory overpredicts the experimental scattering coefficient by a factor of approximately 3.2. The optical coefficients predicted by the RDG approximation showed pronounced sensitivity to changes in monomer mean diameter, the count median diameter of the aggregates, and the geometric standard deviation of the aggregate number size distribution.     

Simulation of the optical properties of plate aggregates for application to the remote sensing of cirrus clouds

In regions of deep tropical convection, ice particles often undergo aggregation and form complex chains. To investigate the effect of the representation of aggregates on electromagnetic scattering calculations, we developed an algorithm to efficiently specify the geometries of aggregates and to compute some of their geometric parameters, such as the projected area. Based on in situ observations, ice aggregates are defined as clusters of hexagonal plates with a chainlike overall shape, which may have smooth or roughened surfaces. An aggregate representation is developed with 10 ensemble members, each consisting of between 4-12 hexagonal plates. The scattering properties of an individual aggregate ice particle are computed using either the discrete dipole approximation or an improved geometric optics method, depending upon the size parameters. Subsequently, the aggregate properties are averaged over all geometries. The scattering properties of the aggregate representation closely agree with those computed from 1000 different aggregate geometries. As a result, the aggregate representation provides an accurate and computationally efficient way to represent all aggregates occurring within ice clouds. Furthermore, the aggregate representation can be used to study the influence of these complex ice particles on the satellite-based remote sensing of ice clouds. The computed cloud reflectances for aggregates are different from those associated with randomly oriented individual hexagonal plates. When aggregates are neglected, simulated cloud reflectances are generally lower at visible and shortwave-infrared wavelengths, resulting in smaller effective particle sizes but larger optical thicknesses.     

A dynamic broadband reflector built from microscopic silica spheres in the ‘disco’ clam Ctenoides ales

The ‘disco’ or ‘electric’ clam Ctenoides ales (Limidae) is the only species of bivalve known to have a behaviourally mediated photic display. This display is so vivid that it has been repeatedly confused for bioluminescence, but it is actually the result of scattered light. The flashing occurs on the mantle lip, where electron microscopy revealed two distinct tissue sides: one highly scattering side that contains dense aggregations of spheres composed of silica, and one highly absorbing side that does not. High-speed video confirmed that the two sides act in concert to alternate between vivid broadband reflectance and strong absorption in the blue region of the spectrum. Optical modelling suggests that the diameter of the spheres is nearly optimal for scattering visible light, especially at shorter wavelengths which predominate in their environment. This simple mechanism produces a striking optical effect that may function as a signal.     

Spectral albedos of mid-latitude snowpacks

Spectral albedos of impure-nonhomogeneous snowpacks, typical for mid-latitudes, at wavelengths from 400 to 2200 nm are modeled through a numerical solution of the radiative transfer equation in the two-stream approximation. Discrete depth-dependent values of density, grain size and impurity concentration are used to characterize the snowpacks. The model is for diffuse incident radiation, and the numerical method is based on doubling and invariant imbedding. The effect of soot impurities on snowpack albedos is illustrated: when a snowpack is semi-infinite (thickness of ten centimeters or more), soot reduces the albedos at visible wavelengths; however, for smaller snowpack thicknesses soot may increase the albedos at visible wavelengths. By adjusting soot content and snow grain size, good quantitative agreement with some observations at the Cascade Mountains (Washington) and at Point Barrow (Alaska) are obtained; however, the model grain sizes are found to be fifty to four hundred percent larger than the measured values. For satellite snowcover observations, a model for effective albedo of partially snowcovered areas is developed and compared with some NOAA-2 observations of the southeastern United States.     

Fluorescence from airborne microparticles: dependence on size, concentration of fluorophores, and illumination intensity

We measured fluorescence from spherical water droplets containing tryptophan and from aggregates of bacterial cells and compared these measurements with calculations of fluorescence of dielectric spheres. The measured dependence of fluorescence on size, from both droplets and dry-particle aggregates of bacteria, is proportional to the absorption cross section calculated for homogeneous spheres containing the appropriate percentage of tryptophan. However, as the tryptophan concentration of the water droplets is increased, the measured fluorescence from droplets increases less than predicted, probably because of concentration quenching. We model the dependence of the fluorescence on input intensity by assuming that the average time between fluorescence emission events is the sum of the fluorescence lifetime and the excitation lifetime (the average time it takes for an illuminated molecule to be excited), which we calculated assuming that the intensity inside the particle is uniform. Even though the intensity inside the particles spatially varies, this assumption of uniform intensity still leads to results consistent with the measured intensity dependence.     

Plasmon Coupling in Clusters Composed of Two‐Dimensionally Ordered Gold Nanocubes

Gold nanocubes are assembled into clusters of varying numbers and ordering on indium tin oxide substrates. The plasmon coupling in the clusters is studied with both dark‐field imaging and finite‐difference time‐domain calculations. Generally, as a cluster becomes larger and more asymmetric, it exhibits more scattering peaks towards longer wavelengths. The coupling of the vertically oriented dipole in the nanocube with its image dipole in the substrate generates two scattering peaks. One is fixed in energy and the other red‐shifts with increasing cluster size. The coupling of horizontally oriented dipoles among different nanocubes produces multiple scattering peaks at lower energies. Their positions and intensities are highly dependent on the number and ordering of nanocubes in the cluster. Au nanocubes in the clusters are further welded together by thermal treatment. The scattering peaks of the thermally treated clusters generally become sharper. The lower‐energy scattering peaks arising from dipolar oscillations are red‐shifted.     

Observations and calculations of light scattering from clusters of spheres

Two-dimensional angular optical scattering (TAOS) patterns from clusters of polystyrene latex spheres are measured in the near-forward and near-backward directions. In both cases, the scattering pattern contains a rich and complicated structure that is the result of the interaction and interference of light among the primary particles. Calculations are made for aggregates that are similar to those generated experimentally and also demonstrate the rich structure in the scattering pattern. A comparison of the experimental and theoretical TAOS patterns gives good qualitative agreement.     

Two‐Photon In Vivo Imaging with Porous Silicon Nanoparticles

A major obstacle in luminescence imaging is the limited penetration of visible light into tissues and interference associated with light scattering and autofluorescence. Near‐infrared (NIR) emitters that can also be excited with NIR radiation via two‐photon processes can mitigate these factors somewhat because they operate at wavelengths of 650–1000 nm where tissues are more transparent, light scattering is less efficient, and endogenous fluorophores are less likely to absorb. This study presents photolytically stable, NIR photoluminescent, porous silicon nanoparticles with a relatively high two‐photon‐absorption cross‐section and a large emission quantum yield. Their ability to be targeted to tumor tissues in vivo using the iRGD targeting peptide is demonstrated, and the distribution of the nanoparticles with high spatial resolution is visualized.     

Mean-field approximation of Mie scattering by fractal aggregates of identical spheres

We apply the recent exact theory of multiple electromagnetic scattering by sphere aggregates to statistically isotropic finite fractal clusters of identical spheres. In the mean-field approximation the usual Mie expansion of the scattered wave is shown to be still valid, with renormalized Mie coefficients as the multipolar terms. We give an efficient method of computing these coefficients, and we compare this mean-field approach with exact results for silica aggregates of fractal dimension 2.     

Development of a near-infrared/mid-infrared dual-region spectrometer for online process analysis

A near-infrared (NIR) and mid-infrared (mid-IR) dual-region spectrometer having two immersion probes, a transmission probe for NIR, and an attenuated total reflection (ATR) probe for mid-IR has been developed for highly reliable process monitoring and deep process understanding. This spectrometer facilitates sequential acquisition of both NIR (10,000-4000 cm(-1)) and mid-IR (5000-1200 cm(-1)) spectra by switching the light path leading to the probes without the need for probe replacement. The use of a single light source and a single beam splitter enables achievement of a permanent alignment of the optical system and sequential data acquisition. The transmission NIR and ATR mid-IR probes designed and developed in the present study facilitate the acquisition of NIR/mid-IR spectra with optimized absorption intensities in both regions by simply placing the probes into a sample solution. The performance of the developed spectrometer was demonstrated in monitoring the ethanol fermentation process. NIR/mid-IR spectra of the fermentation solution with multiplicative scatter correction (MSC) represent the relative changes in the concentrations of glucose and ethanol in both regions. Principal component analysis (PCA) was performed on the MSC-treated spectra in the regions 6300-5650 cm(-1), 4850-4300 cm(-1), and 3500-2880 cm(-1) to detect the end-point of the fermentation as an example of process monitoring. For all the regions, the score plot of the first principal component (PC) indicates that the fermentation progresses with the fermentation time and stops after 210 minutes and thus the end-point of the fermentation exists at around 210 minutes. The loading plot indicates that all of the first PCs are the relative changes in the concentrations of glucose and ethanol. This result reveals that the same chemical changes are observed in both transmission NIR and ATR mid-IR spectra. Multiple and simultaneous analysis was also performed, and intensity change in light scattering relating the growth of yeasts was monitored by the NIR spectra.     

Relationship between surface plasmon and transmittance enhancement in indium-tin-oxide/Ag/indium-tin-oxide multilayer electrodes

The transmittance of indium-tin-oxide (ITO)/Ag/ITO multilayer electrodes under various annealing conditions was investigated. The surface morphology of the Ag layer was modified according to the annealing conditions. Depending on the surface formation of the Ag layer, the enhancement of the transmittance was differentiated into two types. Because of a change of the surface plasmon (SP) mode, connected Ag clusters with coverage of 60% resulted in transmittance enhancement over all visible wavelengths due to decreased absorption while those with coverage of 50% resulted in transmittance enhancement with a peak shift due to increased scattering by localized SP.     

Ultraviolet DIAL measurements of O3 profiles in regions of spatially inhomogeneous aerosols

The differential absorption lidar (DIAL) technique generally assumes that atmospheric optical scattering is the same at the two laser wavelengths used in the DIAL measurement of a gas concentration profile. Errors can arise in this approach when the wavelengths are significantly separated, and there is a range dependence in the aerosol scattering distribution. This paper discusses the errors introduced by large DIAL wavelength separations and spatial inhomogeneity of aerosols in the atmosphere. A Bernoulli solution for determining the relative distribution of aerosol backscattering in the UV region is presented, and scattering ratio boundary values for these solutions are discussed. The results of this approach are used to derive a backscatter correction to the standard DIAL analysis method. It is shown that for the worst cases of severe range dependence in aerosol backscattering, the residual errors in the corrected DIAL O3 measurements were <10 ppbv for DIAL wavelengths at 286 and 300 nm.     

Blood platelet aggregometer: predicted effects of aggregation, photometer geometry, and multiple scattering

The in vitro aggregation of blood platelets is usually monitored with a visible light transmittance photometer (aggregometer). These cells in plasma are large (alpha = 2pi a/lambda approximately = 16) soft (m = 1.04) particles. The factors which significantly influence transmittance include the inherent scattering properties, multiple scattering, and photometer design. Now scattering theory and numerical methods for radiative transfer are used to survey how aggregation should influence transmittance as measured with various photometers. The results should help expand the analytical power of the transmittance photometer as a tool for monitoring aggregation. Evidence is also presented that scattering by aggregates of aerosol particles, which are of a higher relative refractive index, should also be adequately predicted by these approximate methods.     

Use of circular cylinders as surrogates for hexagonal pristine ice crystals in scattering calculations at infrared wavelengths

We investigate the errors associated with the use of circular cylinders as surrogates for hexagonal columns in computing the optical properties of pristine ice crystals at infrared (8-12-microm) wavelengths. The equivalent circular cylinders are specified in terms of volume (V), projected area (A), and volume-to-area ratio that are equal to those of the hexagonal columns. We use the T-matrix method to compute the optical properties of the equivalent circular cylinders. We apply the finite-difference time-domain method to compute the optical properties of hexagonal ice columns smaller than 40 microm. For hexagonal columns larger than 40 microm we employ an improved geometric optics method and a stretched scattering potential technique developed in previous studies to calculate the phase function and the extinction (or absorption) efficiency, respectively. The differences between the results for circular cylinders and hexagonal columns are of the order of a few percent. Thus it is quite reasonable to use a circular cylinder geometry as a surrogate for pristine hexagonal ice columns for scattering calculations at infrared (8-12-microm) wavelengths. Although the pristine ice crystals can be approximated as circular cylinders in scattering calculations at infrared wavelengths, it is shown that optical properties of individual aggregates cannot be well approximated by those of individual finite columns or cylinders.     

Albedo and flux extinction coefficients of impure snow for diffuse short-wave radiation

Impurities enter a snowpack as a result of fallout or scavenging by falling snow crystals. Albedos and flux extinction coefficients of soot-contaminated snowcovers are studied using a two-stream approximation of the radiative transfer equation. The effect of soot is calculated by two methods: independent scattering by ice grains and impurities, and the average refractive index for ice grains. Both methods predict a qualitatively similar effect of soot; the albedo is decreased and the extinction coefficient is increased relative to that for pure snow in the visible region, while the infrared properties are largely unaffected. Quantitatively, however, the effect of soot is more pronounced in the average refractive index method. We find that soot contamination provides qualitative explanation for several snow observations.     

Method for integrating the absorption cross sections of spheres over wavelength or diameter

The absorption cross sections of spherical particles and droplets must be integrated over frequency or droplet size or both for various applications. Morphology-dependent resonances (MDRs) of the spheres can make evaluation of such integrals difficult because the MDRs can contribute significantly to the integrals even when their linewidths are extremely narrow, especially when the absorption is weak. A method of evaluating these integrals by use of Lorentzian approximations near MDRs is described. Calculated frequency-integrated absorption cross sections illustrate how the method obtains accurate cross sections with far fewer integration points than a method that uses equally spaced points. The method reported here suggests a way to integrate over frequency in more-complicated scattering and emission problems and should also be useful for integrating scattering and absorption by other shapes, e.g., spheroids and cylinders, for which the MDR positions and linewidths can be calculated.     

Absorption and scattering properties of dense ensembles of nonspherical particles

The purpose of this work is to show that an appropriate multiple T-matrix formalism can be useful in performing qualitative studies of the optical properties of colloidal systems composed of nonspherical objects (despite limitations concerning nonspherical particle packing densities). In this work we have calculated the configuration averages of scattering and absorption cross sections of different clusters of dielectric particles. These clusters are characterized by their refraction index, particle shape, and filling fraction. Computations were performed with the recursive centered T-matrix algorithm (RCTMA), a previously established method for solving the multiple scattering equation of light from finite clusters of isotropic dielectric objects. Comparison of the average optical cross sections between the different systems highlights variations in the scattering and absorption properties due to the electromagnetic interactions, and we demonstrate that the magnitudes of these quantities are clearly modulated by the shape of the primary particles.