Brillouin Scattering Investigation of Solvation Dynamics in Succinonitrile-Lithium Salt Plastic Crystalline Electrolytes

Temperature dependent Brillouin scattering studies have been performed to ascertain the influence of solvent dynamics on ion-transport in succinonitrile-lithium salt plastic crystalline electrolytes. Though very rarely employed, we observe that Brillouin spectroscopy is an invaluable tool for investigation of solvent dynamics. Analysis of various acoustic (long wavelength) phonon modes observed in the Brillouin scattering spectra reveal the influence of trans-gauche isomerism and as well as ion-association effects on ion transport. Although pristine SN and dilute SN-LiClO(4) samples show only the bulk longitudinal-acoustic (LA) mode, concentrated SN-LiClO(4) (similar to 0.3-1 M) electrolytes display both the bulk LA mode as well as salt induced brillouin modes at ambient temperature. The appearance of more than one brillouin mode is attributed to the scattering of light from regions with different compressibilities (''compactness''). Correspondingly, these modes show a large decrease in the full width at half-maximum (abbreviated as nu(f)) as the temperature decreases. Anomalous temperature dependent behavior of nu(f) with addition of salt could be attributed to the presence of disorder or strong coupling with a neighbor. The shape of the spectrum was evaluated using a Lorentzian and Fano line shape function depending on the nature and behavior of the Brillouin modes.

Structure of the Pyridine-Chloranil Complex in Solution: A Surprise from Depolarized Hyper-Rayleigh Scattering Measurements

In this article, we report the structure of a 1:1 charge transfer complex between pyridine (PYR) and chloranil (CHL) in solution (CHCl(3)) from the measurement of hyperpolarizability (beta(HRS)) and linear and circular depolarization ratios, D and D', respectively, by the hyper-Rayleigh scattering technique and state-of-the-art quantum chemical calculations. Using linearly (electric field vector along X) and circularly polarized incident light, respectively, we have measured two macroscopic depolarization ratios D = I(X,X)(2 omega)/I(X,Z)(2 omega) and D' = I(X,C)(2 omega)/I(Z,C)(2 omega) in the laboratory fixed XYZ frame by detecting the second harmonic (SH) scattered light in a polarization resolved fashion. The stabilization energy and the optical gap calculated through the MP2/cc-pVDZ method using Gaussian09 were not significantly different to distinguish between the cofacial and T-shape structures. Only when the experimentally obtained beta(HRS) and the depolarization ratios, D and D', were matched with the theoretically computed values from single and double configuration interaction (SDCI) calculations performed using the ZINDO-SCRF technique, we concluded that the room temperature equilibrium structure of the complex is cofacial. This is in sharp contrast to an earlier theoretical prediction of the T-shape structure of the complex.

Diffuse optical tomographic imager using a single light source

Near-infrared diffuse optical tomography (DOT) technique has the capability of providing good quantitative reconstruction of tissue absorption and scattering properties with additional inputs such as input and output modulation depths and correction for the photon leakage. We have calculated the two-dimensional (2D) input modulation depth from three-dimensional (3D) diffusion to model the 2D diffusion of photons. The photon leakage when light traverses from phantom to the fiber tip is estimated using a solid angle model. The experiments are carried for single (5 and 6 mm) as well as multiple inhomogeneities (6 and 8 mm) with higher absorption coefficient in a homogeneous phantom. Diffusion equation for photon transport is solved using finite element method and Jacobian is modeled for reconstructing the optical parameters. We study the development and performance of DOT system using modulated single light source and multiple detectors. The dual source methods are reported to have better reconstruction capabilities to resolve and localize single as well as multiple inhomogeneities because of its superior noise rejection capability. However, an experimental setup with dual sources is much more difficult to implement because of adjustment of two out of phase identical light probes symmetrically on either side of the detector during scanning time. Our work shows that with a relatively simpler system with a single source, the results are better in terms of resolution and localization. The experiments are carried out with 5 and 6 mm inhomogeneities separately and 6 and 8 mm inhomogeneities both together with absorption coefficient almost three times as that of the background. The results show that our experimental single source system with additional inputs such as 2D input/output modulation depth and air fiber interface correction is capable of detecting 5 and 6 mm inhomogeneities separately and can identify the size difference of multiple inhomogeneities such as 6 and 8 mm. The localization error is zero. The recovered absorption coefficient is 93% of inhomogeneity that we have embedded in experimental phantom.

Influence of anion on the quadratic nonlinearity and depolarization ratios of scattered second harmonic light from cation-pi complexes

We have investigated quadratic nonlinearity (beta(HRS)) and linear and circular depolarization ratios (D and D', respectively) of a series of 1:1 complexes of tropyliumtetrafluoroborate as a cation and methyl-substituted benzenes as pi-donors by making polarization resolved hyper-Rayleigh scattering measurements in solution. The measured D and D' values are much lower than the values expected from a typical sandwich or a T-shaped geometry of a complex. In the cation-pi complexes studied here, the D value varies from 1.36 to 1.46 and D' from 1.62 to 1.72 depending on the number of methyl substitutions on the benzene ring. In order to probe it further, beta, D and D' were computed using the Zerner intermediate neglect of differential overlap-correction vector self-consistent reaction field technique including single and double configuration interactions in the absence and presence of BF4- anion. In the absence of the anion, the calculated value of D varies from 4.20 to 4.60 and that of D' from 2.45 to 2.72 which disagree with experimental values. However, by arranging three cation-pi BF4- complexes in a trigonal symmetry, the computed values are brought to agreement with experiments. When such an arrangement was not considered, the calculated beta values were lower than the experimental values by more than a factor of two. This unprecedented influence of the otherwise ``unimportant'' anion in solution on the beta value and depolarization ratios of these cation-pi complexes is highlighted and emphasized in this paper. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4716020]

Bioconvection in an anisotropic scattering suspension of phototactic algae

Phototaxis is a directed swimming response dependent upon the light intensity sensed by microorganisms. Positive phototaxis denotes motion directed towards the source of light and negative phototaxis is motion directed away from it. In this paper, we investigate the onset of bioconvection in a suspension of anisotropic scattering phototactic algae illuminated by collimated radiation at the top. The basic state of the system is defined by the zero fluid flow and the up and down swimming, caused by the positive and negative phototaxis, is balanced by the diffusion. A comprehensive numerical study of the linear stability is presented with particular emphasis on the forward scattering effect. The onset of bioconvection occurs either via a stationary mode or an oscillatory mode. The transition from a stationary mode to an oscillatory mode or vice versa has been observed as the anisotropic coefficient is varied for certain parameter values. (C) 2012 Elsevier Masson SAS. All rights reserved.

Penetrative phototactic bioconvection in an isotropic scattering suspension

Phototaxis is a directed swimming response dependent upon the light intensity sensed by micro-organisms. Positive (negative) phototaxis denotes the motion directed towards (away from) the source of light. Using the phototaxis model of Ghorai, Panda, and Hill ''Bioconvection in a suspension of isotropically scattering phototactic algae,'' Phys. Fluids 22, 071901 (2010)], we investigate two-dimensional phototactic bioconvection in an absorbing and isotropic scattering suspension in the nonlinear regime. The suspension is confined by a rigid bottom boundary, and stress-free top and lateral boundaries. The governing equations for phototactic bioconvection consist of Navier-Stokes equations for an incompressible fluid coupled with a conservation equation for micro-organisms and the radiative transfer equation for light transport. The governing system is solved efficiently using a semi-implicit second-order accurate conservative finite-difference method. The radiative transfer equation is solved by the finite volume method using a suitable step scheme. The resulting bioconvective patterns differ qualitatively from those found by Ghorai and Hill ''Penetrative phototactic bioconvection,'' Phys. Fluids 17, 074101 (2005)] at a higher critical wavelength due to the effects of scattering. The solutions show transition from steady state to periodic oscillations as the governing parameters are varied. Also, we notice the accumulation of micro-organisms in two horizontal layers at two different depths via their mean swimming orientation profile for some governing parameters at a higher scattering albedo. (C) 2013 AIP Publishing LLC.

Intensity profile of light scattered from a rough surface

We present in this paper, approximate analytical expressions for the intensity of light scattered by a rough surface, whose elevation. xi(x,y) in the z-direction is a zero mean stationary Gaussian random variable. With (x,y) and (x',y') being two points on the surface, we have h. = 0 with a correlation, = sigma(2)g(r), where r = (x - x')(2) + ( y - y')(2)](1/2) is the distance between these two points. We consider g(r) = exp-r/l)(beta)] with 1 <= beta <= 2, showing that g(0) = 1 and g(r) -> 0 for r >> l. The intensity expression is sought to be expressed as f(v(xy)) = {1 + (c/2y)v(x)(2) + v(y)(2)]}(-y), where v(x) and v(y) are the wave vectors of scattering, as defined by the Beckmann notation. In the paper, we present expressions for c and y, in terms of sigma, l, and beta. The closed form expressions are verified to be true, for the cases beta = 1 and beta = 2, for which exact expressions are known. For other cases, i.e., beta not equal 1, 2 we present approximate expressions for the scattered intensity, in the range, v(xy) = (v(x)(2) + v(y)(2))(1/2) <= 6.0 and show that the relation for f(v(xy)), given above, expresses the scattered intensity quite accurately, thus providing a simple computational methods in situations of practical importance.

Monte Carlo simulation of light transport in turbid medium with embedded object-spherical, cylindrical, ellipsoidal, or cuboidal objects embedded within multilayered tissues

Monte Carlo modeling of light transport in multilayered tissue (MCML) is modified to incorporate objects of various shapes (sphere, ellipsoid, cylinder, or cuboid) with a refractive-index mismatched boundary. These geometries would be useful for modeling lymph nodes, tumors, blood vessels, capillaries, bones, the head, and other body parts. Mesh-based Monte Carlo (MMC) has also been used to compare the results from the MCML with embedded objects (MCML-EO). Our simulation assumes a realistic tissue model and can also handle the transmission/reflection at the object-tissue boundary due to the mismatch of the refractive index. Simulation of MCML-EO takes a few seconds, whereas MMC takes nearly an hour for the same geometry and optical properties. Contour plots of fluence distribution from MCML-EO and MMC correlate well. This study assists one to decide on the tool to use for modeling light propagation in biological tissue with objects of regular shapes embedded in it. For irregular inhomogeneity in the model (tissue), MMC has to be used. If the embedded objects (inhomogeneity) are of regular geometry (shapes), then MCML-EO is a better option, as simulations like Raman scattering, fluorescent imaging, and optical coherence tomography are currently possible only with MCML. (C) 2014 Society of Photo-Optical Instrumentation Engineers (SPIE)

Ray tracing based path-length calculations for polarized light tomographic imaging

A ray tracing based path length calculation is investigated for polarized light transport in a pixel space. Tomographic imaging using polarized light transport is promising for applications in optical projection tomography of small animal imaging and turbid media with low scattering. Polarized light transport through a medium can have complex effects due to interactions such as optical rotation of linearly polarized light, birefringence, diattenuation and interior refraction. Here we investigate the effects of refraction of polarized light in a non-scattering medium. This step is used to obtain the initial absorption estimate. This estimate can be used as prior in Monte Carlo (MC) program that simulates the transport of polarized light through a scattering medium to assist in faster convergence of the final estimate. The reflectance for p-polarized (parallel) and s-polarized (perpendicular) are different and hence there is a difference in the intensities that reach the detector end. The algorithm computes the length of the ray in each pixel along the refracted path and this is used to build the weight matrix. This weight matrix with corrected ray path length and the resultant intensity reaching the detector for each ray is used in the algebraic reconstruction (ART) method. The proposed method is tested with numerical phantoms for various noise levels. The refraction errors due to regions of different refractive index are discussed, the difference in intensities with polarization is considered. The improvements in reconstruction using the correction so applied is presented. This is achieved by tracking the path of the ray as well as the intensity of the ray as it traverses through the medium.