Nonlinear conduction in charge-ordered Pr0.63Ca0.37MnO3: Effect of magnetic fields

Nonlinear conduction in a single crystal of charge-ordered Pr0.63Ca0.37MnO3 has bren investigated in an applied magnetic field. In zero field, the nonlinear conduction, which starts at T< T-CO, can give rise to a region of negative differential resistance (NDR) which shows up below the Neel temperature. Application of a magnetic field Inhibits the appearance of NDR and makes the nonlinear conduction strongly hysteritic on cycling of the bias current. This is most severe in the temperature range where the charge-ordered state melts in an applied magnetic field. Our experiment strongly suggests that application of a magnetic field in the charge-ordering regime causes a coexistence of two phases.

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.

Effect of screening of intermicellar interactions on the linear and nonlinear rheology of a viscoelastic gel

We report our studies of the linear and nonlinear rheology of aqueous solutions of the surfactant cetyl trimethylammonium tosylate (CTAT) with varying amounts of sodium chloride (NaCl). The CTAT concentration is fixed at 42 mM, and the salt concentration is varied between 0 and 120 mM. On increasing the salt (NaCl) concentration, we see three distinct regimes in the zero-shear viscosity and the high-frequency plateau modulus data. In regime 1, the zero-shear viscosity shows a weak increase with salt concentration due to enhanced micellar growth. The decrease in the zero-shear viscosities with salt concentration in regimes II and III can be explained in terms of intermicellar branching. The most intriguing feature of our data, however, is the anomalous behavior of the high-frequency plateau modulus in regime II (0.12 less than or equal to [NaCl]/[CTAT] less than or equal to 1.42). In this regime, the plateau modulus increases with an increase in NaCl concentration. This is highly interesting, since the correlation length of concentration fluctuations and hence the plateau modulus G(0) are not expected to change appreciably in the semidilute regime. We propose to explain the changes in regime II in terms of a possible unbinding of the organic counterions (tosylate) from the CTA(+) surfaces on the addition of NaCl. In the nonlinear flow curves of the samples with high salt content, significant deviations from the predictions of the Giesekus model for entangled micelles are observed.

Effect of nonlinear wave-current interaction on flow fields and hydrodynamic forces

A fifth-order theory for solving the problem of interaction between Stokes waves and exponential profile currents is proposed. The calculated flow fields are compared with measurements. Then the errors caused by the linear superposition method and approximate theory are discussed. It is found that the total wave-current field consists of pure wave, pure current and interaction components. The shear current not only directly changes the flow field, but also indirectly does sx, by changing the wave parameters due to wave-current interaction. The present theory can predict the wave kinematics on shear currents satisfactorily. The linear superposition method may give rise to more than 40% loading error in extreme conditions. When the apparent wave period is used and the Wheeler stretching method is adopted to extrapolate the current, application of the approximate theory is the best.

On Ultrafast Time-Domain TeraHertz Spectroscopy in the Condensed Phase: Linear Spectroscopic Measurements of Hydrogen-Bond Dynamics of Astrochemical Ice Analogs and Nonlinear TeraHertz Kerr Effect Measurements of Vibrational Quantum Beats

Much of the chemistry that affects life on planet Earth occurs in the condensed phase. The TeraHertz (THz) or far-infrared (far-IR) region of the electromagnetic spectrum (from 0.1 THz to 10 THz, 3 cm^-1 to 300 cm^-1, or 3000 μm to 30 μm) has been shown to provide unique possibilities in the study of condensed-phase processes. The goal of this work is to expand the possibilities available in the THz region and undertake new investigations of fundamental interest to chemistry. Since we are fundamentally interested in condensed-phase processes, this thesis focuses on two areas where THz spectroscopy can provide new understanding: astrochemistry and solvation science. To advance these fields, we had to develop new instrumentation that would enable the experiments necessary to answer new questions in either astrochemistry or solvation science. We first developed a new experimental setup capable of studying astrochemical ice analogs in both the TeraHertz (THz), or far-Infrared (far-IR), region (0.3 - 7.5 THz; 10 - 250 cm^-1) and the mid-IR (400 - 4000 cm^-1). The importance of astrochemical ices lies in their key role in the formation of complex organic molecules, such as amino acids and sugars in space. Thus, the instruments are capable of performing variety of spectroscopic studies that can provide especially relevant laboratory data to support astronomical observations from telescopes such as the Herschel Space Telescope, the Stratospheric Observatory for Infrared Astronomy (SOFIA), and the Atacama Large Millimeter Array (ALMA). The experimental apparatus uses a THz time-domain spectrometer, with a 1750/875 nm plasma source and a GaP detector crystal, to cover the bandwidth mentioned above with ~10 GHz (~0.3 cm^-1) resolution.

Using the above instrumentation, experimental spectra of astrochemical ice analogs of water and carbon dioxide in pure, mixed, and layered ices were collected at different temperatures under high vacuum conditions with the goal of investigating the structure of the ice. We tentatively observe a new feature in both amorphous solid water and crystalline water at 33 cm^-1 (1 THz). In addition, our studies of mixed and layered ices show how it is possible to identify the location of carbon dioxide as it segregates within the ice by observing its effect on the THz spectrum of water ice. The THz spectra of mixed and layered ices are further analyzed by fitting their spectra features to those of pure amorphous solid water and crystalline water ice to quantify the effects of temperature changes on structure. From the results of this work, it appears that THz spectroscopy is potentially well suited to study thermal transformations within the ice.

To advance the study of liquids with THz spectroscopy, we developed a new ultrafast nonlinear THz spectroscopic technique: heterodyne-detected, ultrafast THz Kerr effect (TKE) spectroscopy. We implemented a heterodyne-detection scheme into a TKE spectrometer that uses a stilbazoiumbased THz emitter, 4-N,N-dimethylamino-4-N-methyl-stilbazolium 2,4,6-trimethylbenzenesulfonate (DSTMS), and high numerical aperture optics which generates THz electric field in excess of 300 kV/cm, in the sample. This allows us to report the first measurement of quantum beats at terahertz (THz) frequencies that result from vibrational coherences initiated by the nonlinear, dipolar interaction of a broadband, high-energy, (sub)picosecond THz pulse with the sample. Our instrument improves on both the frequency coverage, and sensitivity previously reported; it also ensures a backgroundless measurement of the THz Kerr effect in pure liquids. For liquid diiodomethane, we observe a quantum beat at 3.66 THz (122 cm^-1), in exact agreement with the fundamental transition frequency of the υ4 vibration of the molecule. This result provides new insight into dipolar vs. Raman selection rules at terahertz frequencies.

To conclude we discuss future directions for the nonlinear THz spectroscopy in the Blake lab. We report the first results from an experiment using a plasma-based THz source for nonlinear spectroscopy that has the potential to enable nonlinear THz spectra with a sub-100 fs temporal resolution, and how the optics involved in the plasma mechanism can enable THz pulse shaping. Finally, we discuss how a single-shot THz detection scheme could improve the acquisition of THz data and how such a scheme could be implemented in the Blake lab. The instruments developed herein will hopefully remain a part of the groups core competencies and serve as building blocks for the next generation of THz instrumentation that pushes the frontiers of both chemistry and the scientific enterprise as a whole.

The effect of an electric field on the nonlinear response of InAs/GaAs quantum dots

The refractive nonlinearities of InAs/GaAs quantum dots under a dc electric field at photon energies above its band gap energy have been studied using the reflection Z-scan technique. The effect of the dc electric field on the nonlinear response of InAs/GaAs quantum dots showed similar linear and quadratic electro-optic effects as in the linear response regime at low fields. This implies that the electro-optic effect in the nonlinear regime is analogous to the response in the linear regime for semiconductor quantum dots. Our experimental results show the potential for voltage tunability in InAs quantum dot-based nonlinear electro-optic devices.

Effect of the electrostatic interactions of chromophores on the macroscopic second-order nonlinear optical properties of the polymer films

The polyetherketone (PEK-c) guest-host system thin films doped with 3-(1,1-dicyanothenyl)-1-phenyl-4,5-dihydro-1H-pryazole (DCNP) were prepared. Their second-order nonlinear optical (NLO) coefficients chi(33)((2)) were measured by using Maker fringe method for the polymer films doped with different weight percents of DCNP. Experimental results indicate that the second-order NLO properties of the poled polymer films could decrease with the chromophore loading increasing when the chromophore loading reaches a fairly high level. In this paper, the relationship between the macroscopic second-order NLO coefficient and the chromophore number density was modified under considering the role of the electrostatic interactions of chromophores in the polymer film. According to the modified relationship, the macroscopic second-order NLO coefficient is no longer in direct proportion with the chromophore number density in the polymer film. The effect of the electrostatic interactions of chromophores on second-order NLO properties was discussed. The attenuation of the macroscopic second-order NLO activity can be demonstrated by the role of the chromophore electrostatic interactions at high loading of chromophore in the polymer systems.

The effect of stoichiometry on nonlinear optical properties of LiNbO3

From the chemical bond viewpoint, second-order nonlinear optical (NLO) tensor coefficients of LiNbO3 have been investigated. The single-bond contributions to the second-order NLO susceptibility and the linear susceptibility were determined. The tensor values thus calculated are in good agreement with experimental data. Based on theoretical results of LiNbO3 with Li/Nb = 1, we also have calculated linear and nonlinear optical properties of nonstoichiometric samples with Li/Nb < 1. In the calculation, we find that the Li-O bond is an important type of chemical bond in these LiNbO3 samples, which have large NLO contributions to the total nonlinearities. The refractive indices and second-order NLO tensor coefficients have been determined as a function of the stoichiometry.

Nonlinear numerical modelling of lightning strike effect on composite panels with temperature dependent material properties

This paper presents a physics based modelling procedure to predict the thermal damage of composite material when struck by lightning. The procedure uses the Finite Element Method with non-linear material models to represent the extreme thermal material behaviour of the composite material (carbon/epoxy) and an embedded copper mesh protection system. Simulation predictions are compared against published experimental data, illustrating the potential accuracy and computational cost of virtual lightning strike tests and the requirement for temperature dependent material modelling. The modelling procedure is then used to examine and explain a number of practical solutions to minimize thermal material damage. © 2013 Elsevier Ltd.

NONLINEAR NUMERICAL MODELLING OF LIGHTENING STRIKE EFFECT ON COMPOSITE PANELS WITH TEMPERATURE DEPENDANT MATERIAL PROPERTIES

Lightning strike is one of the challenges that the aerospace industry is facing in an effort to increase the percentage of composite materials used in aircraft structures. Lightning strike damage is due to high orthotropic electric resistivity of the composite panels, which leads to high thermal loads that cause decomposition of the epoxy and delimitations of the laminates. Yet, experimental testing of lightning strike on aircraft panels is expensive due to the large number of design parameters that can control the inflicted damage. A coupled thermal-electrical finite element analysis is used to investigate the design variables space that can affect lightning strike damage on epoxy/graphite composite panels. The contribution of this study is modeling the composite panels’ material properties as temperature dependent, which was excluded by other researchers. A number of practical solutions to minimize the damage effect are proposed. Two set of experimental results are used to verify the numerical ones. One experimental set for plain composite panel, and second one for composite panels with joints