Measurement of Partition Coefficients of Substituted Benzoic Acids between Two Immiscible Solvents by Hyper-Rayleigh Scattering

We demonstrate that the hyper-Rayleigh scattering technique can be employed to measure the partition coefficient (k(p)) of a solute in a mixture of two immiscible solvents. Specifically, partition coefficients of six substituted benzoic acids in water/toluene (1:1 v/v) and water/chloroform (1:1 v/v) systems have been measured. Our values compare well with the k(p) values measured earlier by other techniques, The advantages offered by this technique are also discussed.

Geometry and quadratic nonlinearity of charge transfer complexes in solution using depolarized hyper-Rayleigh scattering

We report large quadratic nonlinearity in a series of 1:1 molecular complexes between methyl substituted benzene donors and quinone acceptors in solution. The first hyperpolarizability, beta(HRS), which is very small for the individual components, becomes large by intermolecular charge transfer (CT) interaction between the donor and the acceptor in the complex. In addition, we have investigated the geometry of these CT complexes in solution using polarization resolved hyper-Rayleigh scattering (HRS). Using linearly (electric field vector along X direction) and circularly polarized incident light, respectively, we have measured two macroscopic depolarization ratios D = I-2 omega,I-X,I-X/I-2 omega,I-Z,I-X and D' = I-2 omega,I-X,I-C/I-2 omega,I-Z,I-C in the laboratory fixed XYZ frame by detecting the second harmonic scattered light in a polarization resolved fashion. The experimentally obtained first hyperpolarizability, beta(HRS), and the value of macroscopic depolarization ratios, D and D', are then matched with the theoretically deduced values from single and double configuration interaction calculations performed using the Zerner's intermediate neglect of differential overlap self-consistent reaction field technique. In solution, since several geometries are possible, we have carried out calculations by rotating the acceptor moiety around three different axes keeping the donor molecule fixed at an optimized geometry. These rotations give us the theoretical beta(HRS), D and D' values as a function of the geometry of the complex. The calculated beta(HRS), D, and D' values that closely match with the experimental values, give the dominant equilibrium geometry in solution. All the CT complexes between methyl benzenes and chloranil or 1,2-dichloro-4,5-dicyano-p-benzoquinone investigated here are found to have a slipped parallel stacking of the donors and the acceptors. Furthermore, the geometries are staggered and in some pairs, a twist angle as high as 30 degrees is observed. Thus, we have demonstrated in this paper that the polarization resolved HRS technique along with theoretical calculations can unravel the geometry of CT complexes in solution. (C) 2011 American Institute of Physics. doi:10.1063/1.3514922]

Determination of critical micelle concentration by hyper-Rayleigh scattering

The critical micelle concentration (CMC) of several surfactants that contain an NLO chromophore, either at the hydrocarbon tail, or at the hydrophilic headgroup, or even as a counterion, was determined by hyper-Rayleigh scattering (HRS). In all cases, the HRS signal exhibited a similar variation with surfactant concentration, wherein the CMC is inferred from a rather unprecedented drop in the signal intensity. This drop is attributed to the formation of small pre-micellar aggregates, whose concentrations become negligible above CMC. In addition, a probe molecule, which upon protonation yielded a species with significantly enhanced HRS intensity, was developed and its utility for the determination of the CIVIC of simple fatty acids was demonstrated.

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.

Incoherent subharmonic light scattering in isotropic media

Incoherent subharmonic light scattering in isotropic media is a new kind of nonlinear light scattering, which involves single input photon and multiple output photons of equal frequency. We investigate theoretically the dependence of the subharmonic scattering intensity on the hyperpolarizability of molecules and the incident intensity using nonlinear optics theory similar to that used for Hyper-Rayleigh scattering and degenerate optical parametric oscillators. It is derived that the subharmonic scattering intensities grow exponentially or superexponentially with the hyperpolarizability of molecules and the incident intensity. (C) 2004 Elsevier B.V. All rights reserved.

Distributed Temperature Sensing System Based on Rayleigh Scattering BOTDA

A distributed temperature sensor based on Rayleigh scattering Brillouin optical time domain analysis (Rayleigh-BOTDA) is proposed in this paper. The sensor uses Rayleigh backscattering effect of microwave modulated pulse base sidebands as probe wave and a high sensitive photon counting detector for Brillouin signal intensity detection. Compared with a conventional BOTDA system, the Rayleigh-BOTDA effectively suppresses polarization-induced signal fluctuation resulting in improved signal intensity. The experimental scheme presented is simplified by using a single laser with one-end access. The temperature accuracy of the new sensing system was demonstrated as 1 degrees C on spatial resolution of 3 m.

Threshold Optimization for Energy Detection-Based Spectrum Sensing Over Hyper-Rayleigh Fading Channels

Spectrum sensing is a key function of cognitive radio systems. Sensing performance is determined by three main factors including the wireless channel between the primary system and the cognitive radio nodes, the detection threshold, and the sensing time. In this letter a closed-form expression for the average probability of detection for energy detection based spectrum sensing over two-wave with diffuse power fading channels is derived. This expression is then used to optimize the detection threshold for cognitive radio nodes, which operate in confined structures that exhibit worse than Rayleigh fading conditions. Such fading conditions can represent a behavioral model of cognitive machine-to-machine systems deployed in enclosed structures such as in-vehicular environments.

Rayleigh scattering by hexagonal ice crystals and the interpretation of dual-polarisation radar measurements

Dual-polarisation radar measurements provide valuable information about the shapes and orientations of atmospheric ice particles. For quantitative interpretation of these data in the Rayleigh regime, common practice is to approximate the true ice crystal shape with that of a spheroid. Calculations using the discrete dipole approximation for a wide range of crystal aspect ratios demonstrate that approximating hexagonal plates as spheroids leads to significant errors in the predicted differential reflectivity, by as much as 1.5 dB. An empirical modification of the shape factors in Gans's spheroid theory was made using the numerical data. The resulting simple expressions, like Gans's theory, can be applied to crystals in any desired orientation, illuminated by an arbitrarily polarised wave, but are much more accurate for hexagonal particles. Calculations of the scattering from more complex branched and dendritic crystals indicate that these may be accurately modelled using the new expression, but with a reduced permittivity dependent on the volume of ice relative to an enclosing hexagonal prism.

Ultra-long raman laser with a feedback based on the Rayleigh scattering

This paper reports the Rayleigh scattering effects in ultra-long Raman fibre laser. It has been found that in a long fibre cavity (-100 km) the distributed feedback due to Rayleigh back scattering at propagation of light between fibre Bragg grating reflectors may be comparable with the lumped feedback provided by the FBG itself. As a result, Raman lasing in the fibre span limited by lumped (FBG) reflector at one side only appears possible due to significant reflection from the RS-based "random" distributed mirror at the other side. Thus, it concludes that a distributed Rayleigh scattering "random" mirror can form a cavity together with a single FBG spliced to the opposite cavity end.

Dual-wavelength, ultralong Raman laser with Rayleigh-scattering feedback

We present experimental demonstration of a 200-km-long, dual-wavelength Raman laser utilizing two slightly different-wavelength fiber Bragg gratings, one on each side of the fiber span. The obtained results clearly prove the generation of two independent Raman lasers with a distributed “random” Rayleigh scattering mirror forming a cavity together with each of the individual fiber Bragg grating reflectors.

Ultra-long raman laser with a feedback based on the Rayleigh scattering

This paper reports the Rayleigh scattering effects in ultra-long Raman fibre laser. It has been found that in a long fibre cavity (-100 km) the distributed feedback due to Rayleigh back scattering at propagation of light between fibre Bragg grating reflectors may be comparable with the lumped feedback provided by the FBG itself. As a result, Raman lasing in the fibre span limited by lumped (FBG) reflector at one side only appears possible due to significant reflection from the RS-based "random" distributed mirror at the other side. Thus, it concludes that a distributed Rayleigh scattering "random" mirror can form a cavity together with a single FBG spliced to the opposite cavity end.

Effect of Rayleigh-scattering distributed feedback on multiwavelength Raman fiber laser generation

We experimentally demonstrate a Raman fiber laser based on multiple point-action fiber Bragg grating reflectors and distributed feedback via Rayleigh scattering in an ∼22-km-long optical fiber. Twenty-two lasing lines with spacing of ∼100 GHz (close to International Telecommunication Union grid) in the C band are generated at the watt level. In contrast to the normal cavity with competition between laser lines, the random distributed feedback cavity exhibits highly stable multiwavelength generation with a power-equalized uniform distribution, which is almost independent on power. © 2011 Optical Society of America.

Effect of Rayleigh-scattering distributed feedback on multiwavelength Raman fiber laser generation

We experimentally demonstrate a Raman fiber laser based on multiple point-action fiber Bragg grating (FBG) reflectors and distributed feedback via Rayleigh scattering in a ∼22 km long optical fiber. Twenty two lasing lines with spacing of ∼100 GHz (close to ITU grid) in C-band are generated at Watts power level. In contrast to the normal cavity with competition between laser lines, the random distributed feedback cavity exhibits highly stable multiwavelength generation with a power-equalized uniform distribution which is almost independent on power. The current set up showing the capability of generating Raman gain of about 100-nm wide giving the possibility of multiwavelength generation at different bands. © 2011 SPIE.