Nonlinear Optical Properties of Stacked Conjugated Systems

We study linear and nonlinear optical properties of two push-pull polyenes stacked in head to head (HtH) and head to tail (HtT) configurations, at different stacking angles within the Pariser-Parr-Pople model using exact diagonalization method. By varying the stacking angle between the polyenes, we find that the optical gap varies marginally, but transition dipoles show large variations. We find that the dominant first-order hyperpolarizability component beta(XXX) for HtH arrangement and beta(YYY) for HtT arrangement strongly depend on the distance of separation between molecules, while the other smaller component beta(XYY) for HtH arrangement and beta(XXY) for HtT arrangement) does not show this variation with distance. We find that the beta(XXX) for HtH configuration shows a maximum at an angle away from 0, in contrast with the oriented gas model. This angle varies with distance between the polyenes, and at large distance it falls to 0. The ratio of all components of beta of a dimer to monomer is less than two for HtH configuration for all angles. But for HtT configurations the ratio of the dominant beta component is greater than two at large angles. Our ZINDO study on two monomers (4-hydroxy-4'-nitroazobenzene) connected in a nonconjugative fashion shows a linear increase in vertical bar(beta) over right arrow (av)vertical bar without much red shift in optical gap. There is a linear increase in vertical bar(beta) over right arrow (av)vertical bar with increase in number of monomers connected nonconjugatively without resulting in a red shift in optical gap.

Non-interferometric methods of phase estimation for application in optical tomography

We describe here two non-interferometric methods for the estimation of the phase of transmitted wavefronts through refracting objects. The phase of the wavefronts obtained is used to reconstruct either the refractive index distribution of the objects or their contours. Refraction corrected reconstructions are obtained by the application of an iterative loop incorporating digital ray tracing for forward propagation and a modified filtered back projection (FBP) for reconstruction. The FBP is modified to take into account non-straight path propagation of light through the object. When the iteration stagnates, the difference between the projection data and an estimate of it obtained by ray tracing through the final reconstruction is reconstructed using a diffraction tomography algorithm. The reconstruction so obtained, viewed as a correction term, is added to the estimate of the object from the loop to obtain an improved final refractive index reconstruction.

Nonlinear optical activity of anhydrous and hydrated sodium p-nitrophenolate

Differently hydrated sodium p-nitrophenolate (NPNa) crystals were obtained while growing them from different solvents such as methanol and water. Thermal analysis and powder X-ray diffraction studies were carried out on these crystals. Kurtz powder SHG technique was used for qualitative assessment of their nonlinear optical (NLO) activity. From the detailed single-crystal X-ray diffraction studies it is established that NPNa has three different forms, of which only one is found to possess NLO activity. Additionally, a new NLO active crystal was also found to grow from aqueous solution. (C) 1999 Elsevier Science B.V. All rights reserved.

Relaxation behavior of twin nonlinear optical chromophores: Effect of the spacer length

A new series of twin nonlinear optical (NLO) molecules, having two 4-nitrophenol chromophores that are linked via a flexible polymethylene spacer of varying length [(CH2)(n), n = 1-12], were synthesized. Powder second harmonic generation measurements of these twin samples indicated a pronounced odd-even oscillation, with the odd twins exhibiting a high SHG value while the even ones gave no measurable SH signal. This behavior reflects the crystal packing preferences in such twin NLO systems that have odd and even numbers of atoms linking them - the even ones appear to prefer a centrosymmetric packing arrangement. The orientational/disordering dynamics of these twin NLO molecules, doped in a polymer (poly(methyl methacrylate)) matrix, has also been studied using SHG in electric field poled samples. Interestingly, the maximum attainable SH signal, chi((2)), in, the poled samples also showed an odd-even oscillation; the odd ones again having a higher value of chi((2)) This unprecedented odd-even oscillation in such molecularly doped systems is rationalized as being due to the intrinsically greater ease of a parallel alignment of the two chromophores in the twins with an odd spacer than in those with an even one. Further, the temporal stability of the SHG intensity at 70 degrees C, after the removal of the applied corona, was also studied. The relaxation of all the twin chromophores followed a biexponential decay; the characteristic relaxation time (tau(2)) for the slow decay component suggests that while the twin with a single methylene unit relaxes relatively slowly, the relaxation is significantly faster in cases where n = 2 and 3. In the twins with even longer spacer segments, the relaxation again becomes slower and reaches a saturation value. The observed minimum appears to reflect the interplay of two competing factors that affect the chromophore alignment in such twin systems, namely, the electrostatic repulsion between neighboring oriented dipoles and the intrinsic flexibility of the spacer.

Resent radar observations of asteroid 1566 Icarus

We report Doppler-only radar observations of Icarus at Goldstone at a transmitter frequency of 8510 MHz (3.5 cm wavelength) during 8-10 June 1996, the first radar detection of the object since 1968. Optimally filtered and folded spectra achieve a maximum opposite-circular (OC) polarization signal-to-noise ratio of about 10 and help to constrain Icarus' physical properties. We obtain an OC radar cross section of 0.05 km(2) (with a 35% uncertainty), which is less than values estimated by Goldstein (1969) and by Pettengill et al. (1969), and a circular polarization (SC/OC) ratio of 0.5+/-0.2. We analyze the echo power spectrum with a model incorporating the echo bandwidth B and a spectral shape parameter it, yielding a coupled constraint between B and n. We adopt 25 Hz as the lower bound on B, which gives a lower bound on the maximum pole-on breadth of about 0.6 km and upper bounds on the radar and optical albedos that are consistent with Icarus' tentative QS classification. The observed circular polarization ratio indicates a very rough near-surface at spatial scales of the order of the radar wavelength. (C) 1999 Elsevier Science Ltd. All rights reserved.

Structural, dielectric and optical properties of lithium borate-bismuth tungstate glass-ceramicsc

Glasses in the system (1 - x)Li2B4O7-xBi(2)WO(6) (0.1 less than or equal to x less than or equal to 0.35) were prepared by splat quenching technique. Powder X-ray diffraction (XRD) and differential thermal analysis (DTA) were employed to characterize the as-quenched glasses. High-resolution transmission electron microscopy (HR TEM) revealed the presence of fine, nearly spherical crystallites of Bi2WO6 varying from 1.5 to 20 nm in size, depending on x in the as-quenched glasses. The glasses (corresponding to x = 0.3) heat-treated at 723 K for 6 h gave rise to a clear crystalline phase of Bi2WO6 embedded in the Li2B4O7 glass matrix, as observed by X-ray studies. The dielectric constants of the as-quenched glasses as well as the glass-ceramics decreased with increase in frequency (40Hz-100 kHz) at 300 K, and the value obtained for the glass-ceramic (x = 0.2) is in agreement with the values predicted using Maxwell's model and the logarithmic mixture rule. The dielectric constants for both the as-quenched glass and the glass-ceramic increased with increase in temperature (300 - 873 K) and exhibited anomalies close to the onset of the crystallization temperature of the host glass matrix. The optical transmission properties:of these glass-ceramics were found to be compositional dependant. (C) 2000 Elsevier Science Ltd.

Structural dielectric and optical properties of SrB4O7-BaO-TiO2 glasses

Glass samples with compositions (100-2x)SrB4O7-xBaO-xTiO(2) (10 less than or equal to x less than or equal to 40) were prepared by conventional melt quenching and the influence of the addition of BaO-TiO2 on the structural, dielectric and optical properties of SBO glasses was studied The molar volume, glass transition temperature and the optical polarisability of the glass samples were found to decrease with increase in BaO-TiO2 content while the refractive index and optical band gap increase with increase in BaO-TiO2 content.

Wavelet based compression and denoising of optical tomography data

Two methods based on wavelet/wavelet packet expansion to denoise and compress optical tomography data containing scattered noise are presented, In the first, the wavelet expansion coefficients of noisy data are shrunk using a soft threshold. In the second, the data are expanded into a wavelet packet tree upon which a best basis search is done. The resulting coefficients are truncated on the basis of energy content. It can be seen that the first method results in efficient denoising of experimental data when scattering particle density in the medium surrounding the object was up to 12.0 x 10(6) per cm(3). This method achieves a compression ratio of approximate to 8:1. The wavelet packet based method resulted in a compression of up to 11:1 and also exhibited reasonable noise reduction capability. Tomographic reconstructions obtained from denoised data are presented. (C) 1999 Published by Elsevier Science B.V. All rights reserved,

Aryl monosulphides and symmetrical disulphides based second order nonlinear optical chromophores with transparency in the visible

A series of aryl monosulphides and disulphides have been synthesized and characterized. Their molecular hyperpolarizability (beta) has been measured in solution with the hyper-Rayleigh Scattering technique and also calculated by semiempirical AMI method. The trend in the observed and calculated values of first hyperpolarizability of these compounds has been found to be in good agreement. These compounds show moderate P values and excellent transparency in the visible region.

Cross-polarization from the dipolar reservoir under the mismatched Hartmann-Hahn condition

Cross-polarization from the dipolar reservoir for a range of mismatched Hartmann-Hahn conditions has been considered. Experiment, in general, agrees with the dispersive Lorentzian behavior expected on the basis of quasi-equilibrium theory. It is observed that inclusion of additional mechanisms of polarization transfer lead to an improvment of the fit of the experimental results. The utility of extending the technique to the case of ordered long chain molecules, such as liquid crystals, for the measurement of the local dipolar field is also presented. (C) 2002 Elsevier Science (USA).

Kinetics of hydrogen evolution on submicron size Co, Ni, Pd and CoNi alloy powder electrodes by d.c. polarization and a.c. impedance studies

Submicron size Co, Ni and Co-Ni alloy powders have been synthesized by the polyol method using the corresponding metal malonates and Pd powder by reduction of PdOx in methanol. The kinetics of the hydrogen evolution reaction ( HER) in 6 M KOH electrolyte have been studied on electrodes made from the pressed powders. The d.c. polarization measurements have resulted in a value close to 120 mV decade(-1) for the Tafel slope, suggesting that the HER follows the Volmer-Heyrovsky mechanism. The values of exchange current density (i(o)) are in the range 1-10 mA cm(-2) for electrodes fabricated in the study. The a.c. impedance spectra measured at several potentials in the HER region showed a single semicircle in the Nyquist plots. Exchange current density (i(o)) and energy transfer coefficient (alpha) have been calculated by employing a nonlinear least square-fitting program.

Lithium borate-strontium bismuth tantalate glass nanocomposite: a novel material for nonlinear optic and ferroelectric applications

Glass nanocomposites in the system (100 - x)Li2B4O7-xSrBi(2)Ta(2)O(9) (0 less than or equal to x less than or equal to 22.5, in molar ratio) were fabricated via a melt quenching technique followed by controlled heat-treatment. The as-quenched samples were confirmed to be glassy and amorphous by differential thermal analysis (DTA) and X-ray powder diffraction (XRD) techniques, respectively. The phase formation and crystallite size of the heat-treated samples (glass nanocomposites) were monitored by XRD and transmission electron microscopy (TEM). The relative permittivities (epsilon(tau)') of the glass nanocomposites for different compositions were found to lie in between that of the parent host glass (Li2B4O7) and strontium bismuth tantalate (SBT) ceramic in the frequency range 100 Hz-40 MHz at 300 K, whereas the dielectric loss (D) of the glass nanocomposite was less than that of both the parent phases. Among the various dielectric models employed to predict the effective relative permittivity of the glass nanocomposite, the one obtained using the Maxwell's model was in good agreement with the experimentally observed value. Impedance analysis was employed to rationalize the electrical behavior of the glasses and glass nanocomposites. The pyroelectric response of the glasses and glass nanocomposites was monitored as a function of temperature and the pyroelectric coefficient for glass and glass nanocomposite (x = 20) at 300 K were 27 muC m(-2) K-1 and 53 muC m(-2) K-1, respectively. The ferroelectric behavior of these glass nanocomposites was established by P vs. E hysteresis loop studies. The remnant polarization (P-r) of the glass nanocomposite increases with increase in SBT content. The coercive field (E-c) and P-r for the glass nanocomposite (x = 20) were 727 V cm(-1) and 0.527 muC cm(-2), respectively. The optical transmission properties of these glass nanocomposites were found to be composition dependent. The refractive index (n = 1.722), optical polarizability (am = 1.266 6 10 23 cm 3) and third-order nonlinear optical susceptibility (x(3) = 3.046 6 10(-21) cm(3)) of the glass nanocomposite (x = 15) were larger than those of the as-quenched glass. Second harmonic generation (SHG) was observed in transparent glass nanocomposites and the d(eff) for the glass nanocomposite (x = 20) was found to be 0.373 pm V-1.

New transparent crystallized glasses with optical nonlinear LiBGeO4 crystals

Crystallization behaviors of the glass with a composition of 25Li(2)O.25B(2)O(3).50GeO(2) corresponding to lithium borogermanate LiBGeO4 have been examined. It has been confirmed that the LiBGeO4 crystalline phase is formed at the surface of heat-treated glasses. The second harmonic (SH) generation is found from transparent surface crystallized glasses, demonstrating for the first time that the LiBGeO4 phase shows optical nonlinearity. The SH intensity of LiBGeO4 crystallites (powdered state) prepared through crystallization is about ten times as large as that of pulverized alpha-quartz. The SH intensity of transparent crystallized glasses (bulk state) with crystalline layers of 3-4.5 mum thickness increases with increasing heat treatment temperature (540-560degreesC) and time (1-6 h), and the maximum SH intensity among the samples studied is in the order of 1/10 in comparison with that of alpha-quartz single crystal. The transparent crystallized glass obtained by heat treatment at 550alphaC for 3 h exhibits a clear and fine Maker fringe pattern, indicating a highly orientation of LiBGeO4 crystals at the surface.

Polarization switching studies in ferroelectric glycine phosphite single crystals

Glycine Phosphite [NH3CH2COOH3PO3], abbreviated as GPI, undergoes a para-ferroelectric phase transition from the monoclinic symmetry P2(1)/a to P2(1) at 224.7 K. We report here a systematic study of the polarization switching process in this crystal. Growth of these crystals from aqueous solution has been undertaken employing both solvent evaporation and slow cooling methods. Hysteresis loop measurements along the polar b-axis yielded a spontaneous polarization value of 0.5 muC/cm(2) and a coercive field of 2.5 kV/cm. Conventional Merz technique was employed for polarization switching studies, wherein bipolar square pulses were applied to the sample to induce domain reversal. The transient switching pulse that flows through the sample on application of the field was recorded. The maximum switching time required for domain switching was measured both as a function of electric field and temperature. The experimentally observed switching curves were fitted with the model based on the Pulvari-Kuebler theory of nucleation and growth of domains. From the experimental data, the values of mobility and activation field were obtained. It was observed that switching process in this crystal is predominantly governed by the forward growth of domain walls in the high field region. However, switching process in GPI crystal was found to be slower than that found in other glycine based ferroelectric crystals.