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.

Dynamic characterization of micro-particle systems

Ordered granular systems have been a subject of active research for decades. Due to their rich dynamic response and nonlinearity, ordered granular systems have been suggested for several applications, such as solitary wave focusing, acoustic signals manipulation, and vibration absorption. Most of the fundamental research performed on ordered granular systems has focused on macro-scale examples. However, most engineering applications require these systems to operate at much smaller scales. Very little is known about the response of micro-scale granular systems, primarily because of the difficulties in realizing reliable and quantitative experiments, which originate from the discrete nature of granular materials and their highly nonlinear inter-particle contact forces.

In this work, we investigate the physics of ordered micro-granular systems by designing an innovative experimental platform that allows us to assemble, excite, and characterize ordered micro-granular systems. This new experimental platform employs a laser system to deliver impulses with controlled momentum and incorporates non-contact measurement apparatuses to detect the particles’ displacement and velocity. We demonstrated the capability of the laser system to excite systems of dry (stainless steel particles of radius 150 micrometers) and wet (silica particles of radius 3.69 micrometers, immersed in fluid) micro-particles, after which we analyzed the stress propagation through these systems.

We derived the equations of motion governing the dynamic response of dry and wet particles on a substrate, which we then validated in experiments. We then measured the losses in these systems and characterized the collision and friction between two micro-particles. We studied wave propagation in one-dimensional dry chains of micro-particles as well as in two-dimensional colloidal systems immersed in fluid. We investigated the influence of defects to wave propagation in the one-dimensional systems. Finally, we characterized the wave-attenuation and its relation to the viscosity of the surrounding fluid and performed computer simulations to establish a model that captures the observed response.

The findings of the study offer the first systematic experimental and numerical analysis of wave propagation through ordered systems of micro-particles. The experimental system designed in this work provides the necessary tools for further fundamental studies of wave propagation in both granular and colloidal systems.

Effect of absorption on the diffraction efficiency in Fe : LiNbO3 crystal with 90 degrees recording geometry

In this paper the saturated diffraction efficiency has been optimized by considering the effect of the absorption of the recording light on a crossed-beam grating with 90 degrees recording geometry in Fe:LiNbO3 crystals. The dependence of saturated diffraction efficiency on the doping levels with a known oxidation-reduction state, as well as the dependence of saturated diffraction efficiency on oxidation-reduction state with known doping levels, has been investigated. Two competing effects on the saturated diffraction efficiency were discussed, and the intensity profile of the diffracted beam at the output boundary has also been investigated. The results show that the maximal saturated diffraction efficiency can be obtained in crystals with moderate doping levels and modest oxidation state. An experimental verification is performed and the results are consistent with those of the theoretical calculation.

Absorption characteristic and nonvolatile holographic recording in LiNbO3 : Cr : Cu crystals

The absorption characteristic of lithium niobate crystals doped with chromium and copper (Cr and Cu) is investigated. We find that there are two apparent absorption bands for LiNbO3:Cr:Cu crystal doped with 0.14 wt.% Cr2O3 and 0.011 wt.% CuO; one is around 480 nm, and the other is around 660 nm. With a decrease in the doping composition of Cr and an increase in the doping composition of Cu, no apparent absorption band in the shorter wavelength range exists. The higher the doping level of Cr, the larger the absorbance around 660 nm. Although a 633 nm red light is located in the absorption band around 660 nm, the absorption at 633 nm does not help the photorefractive process; i.e., unlike other doubly doped crystals, for example, LiNbO3:Fe:Mn crystal, a nonvolatile holographic recording can be realized by a 633 nm red light as the recording light and a 390 nm UV light as the sensitizing light. For LiNbO3:Cr:Cu crystals, by changing the recording light from a 633 nm red light to a 514 nm green light, sensitizing with a 390 nm UV light and a 488 nm blue light, respectively, a nonvolatile holographic recording can be realized. Doping the appropriate Cr (for example, N-Cr = 2.795 X 10(25)m(-3) and N-Cr/N-Cu = 1) benefits the improvement of holographic recording properties. (c) 2005 Optical Society of America.

Equivalent differential equations for nonlinear dynamical systems

A technique for obtaining approximate periodic solutions to nonlinear ordinary differential equations is investigated. The approach is based on defining an equivalent differential equation whose exact periodic solution is known. Emphasis is placed on the mathematical justification of the approach. The relationship between the differential equation error and the solution error is investigated, and, under certain conditions, bounds are obtained on the latter. The technique employed is to consider the equation governing the exact solution error as a two point boundary value problem. Among other things, the analysis indicates that if an exact periodic solution to the original system exists, it is always possible to bound the error by selecting an appropriate equivalent system.

Three equivalence criteria for minimizing the differential equation error are compared, namely, minimum mean square error, minimum mean absolute value error, and minimum maximum absolute value error. The problem is analyzed by way of example, and it is concluded that, on the average, the minimum mean square error is the most appropriate criterion to use.

A comparison is made between the use of linear and cubic auxiliary systems for obtaining approximate solutions. In the examples considered, the cubic system provides noticeable improvement over the linear system in describing periodic response.

A comparison of the present approach to some of the more classical techniques is included. It is shown that certain of the standard approaches where a solution form is assumed can yield erroneous qualitative results.

Experimental study of nonlinear switching characteristics of conventional 2×2 fused tapered couplers

The nonlinear switching characteristics of fused fiber directional couplers were studied experimentally. By using femtosecond laser pulses with pulse width of 100 fs and wavelength of about 1550 nm from a system of Ti:sapphire laser and optical parametric amplifier (OPA), the nonlinear switching properties of a null coupler and a 100% coupler were measured. The experimental results were coincident with the simulations based on nonlinear propagation equations in fiber by using super-mode theory. Nonlinear loss in fiber was also measured to get the injected power at the coupler. After deducting the nonlinear loss and input efficiency, the nonlinear switching critical peak powers for a 100% and a null fused couplers were calculated to be 9410 and 9440 W, respectively. The nonlinear loss parameter P_(N) in an expression of α_(NL)=αP/P_(N) was obtained to be P_(N)=0.23 W.

A study of nonlinear phenomena in the propagation of electromagnetic waves in a weakly ionized gas

This thesis is a study of nonlinear phenomena in the propagation of electromagnetic waves in a weakly ionized gas externally biased with a magnetostatic field. The present study is restricted to the nonlinear phenomena rising from the interaction of electromagnetic waves in the ionized gas. The important effects of nonlinearity are wave-form distortion leads to cross modulation of one wave by a second amplitude-modulated wave.

The nonlinear effects are assumed to be small so that a perturbation method can be used. Boltzmann’s kinetic equation with an appropriate expression for the collision term is solved by expanding the electron distribution function into spherical harmonics in velocity space. In turn, the electron convection current density and the conductivity tensors of the nonlinear ionized gas are found from the distribution function. Finally, the expression for the current density and Maxwell’s equations are employed to investigate the effects of nonlinearity on the propagation of electromagnetic waves in the ionized gas, and also on the reflection of waves from an ionized gas of semi-infinite extent.

Geometrical effects on the resonance absorption of neutrons

An investigation was conducted to estimate the error when the flat-flux approximation is used to compute the resonance integral for a single absorber element embedded in a neutron source.

The investigation was initiated by assuming a parabolic flux distribution in computing the flux-averaged escape probability which occurs in the collision density equation. Furthermore, also assumed were both wide resonance and narrow resonance expressions for the resonance integral. The fact that this simple model demonstrated a decrease in the resonance integral motivated the more detailed investigation of the thesis.

An integral equation describing the collision density as a function of energy, position and angle is constructed and is subsequently specialized to the case of energy and spatial dependence. This equation is further simplified by expanding the spatial dependence in a series of Legendre polynomials (since a one-dimensional case is considered). In this form, the effects of slowing-down and flux depression may be accounted for to any degree of accuracy desired. The resulting integral equation for the energy dependence is thus solved numerically, considering the slowing down model and the infinite mass model as separate cases.

From the solution obtained by the above method, the error ascribable to the flat-flux approximation is obtained. In addition to this, the error introduced in the resonance integral in assuming no slowing down in the absorber is deduced. Results by Chernick for bismuth rods, and by Corngold for uranium slabs, are compared to the latter case, and these agree to within the approximations made.

SteelConverter and Caltech VirtualShaker: Rapid Nonlinear Cloud-Based Structural Model Conversion and Analysis

STEEL, the Caltech created nonlinear large displacement analysis software, is currently used by a large number of researchers at Caltech. However, due to its complexity, lack of visualization tools (such as pre- and post-processing capabilities) rapid creation and analysis of models using this software was difficult. SteelConverter was created as a means to facilitate model creation through the use of the industry standard finite element solver ETABS. This software allows users to create models in ETABS and intelligently convert model information such as geometry, loading, releases, fixity, etc., into a format that STEEL understands. Models that would take several days to create and verify now take several hours or less. The productivity of the researcher as well as the level of confidence in the model being analyzed is greatly increased.

It has always been a major goal of Caltech to spread the knowledge created here to other universities. However, due to the complexity of STEEL it was difficult for researchers or engineers from other universities to conduct analyses. While SteelConverter did help researchers at Caltech improve their research, sending SteelConverter and its documentation to other universities was less than ideal. Issues of version control, individual computer requirements, and the difficulty of releasing updates made a more centralized solution preferred. This is where the idea for Caltech VirtualShaker was born. Through the creation of a centralized website where users could log in, submit, analyze, and process models in the cloud, all of the major concerns associated with the utilization of SteelConverter were eliminated. Caltech VirtualShaker allows users to create profiles where defaults associated with their most commonly run models are saved, and allows them to submit multiple jobs to an online virtual server to be analyzed and post-processed. The creation of this website not only allowed for more rapid distribution of this tool, but also created a means for engineers and researchers with no access to powerful computer clusters to run computationally intensive analyses without the excessive cost of building and maintaining a computer cluster.

In order to increase confidence in the use of STEEL as an analysis system, as well as verify the conversion tools, a series of comparisons were done between STEEL and ETABS. Six models of increasing complexity, ranging from a cantilever column to a twenty-story moment frame, were analyzed to determine the ability of STEEL to accurately calculate basic model properties such as elastic stiffness and damping through a free vibration analysis as well as more complex structural properties such as overall structural capacity through a pushover analysis. These analyses showed a very strong agreement between the two softwares on every aspect of each analysis. However, these analyses also showed the ability of the STEEL analysis algorithm to converge at significantly larger drifts than ETABS when using the more computationally expensive and structurally realistic fiber hinges. Following the ETABS analysis, it was decided to repeat the comparisons in a software more capable of conducting highly nonlinear analysis, called Perform. These analyses again showed a very strong agreement between the two softwares in every aspect of each analysis through instability. However, due to some limitations in Perform, free vibration analyses for the three story one bay chevron brace frame, two bay chevron brace frame, and twenty story moment frame could not be conducted. With the current trend towards ultimate capacity analysis, the ability to use fiber based models allows engineers to gain a better understanding of a building’s behavior under these extreme load scenarios.

Following this, a final study was done on Hall’s U20 structure [1] where the structure was analyzed in all three softwares and their results compared. The pushover curves from each software were compared and the differences caused by variations in software implementation explained. From this, conclusions can be drawn on the effectiveness of each analysis tool when attempting to analyze structures through the point of geometric instability. The analyses show that while ETABS was capable of accurately determining the elastic stiffness of the model, following the onset of inelastic behavior the analysis tool failed to converge. However, for the small number of time steps the ETABS analysis was converging, its results exactly matched those of STEEL, leading to the conclusion that ETABS is not an appropriate analysis package for analyzing a structure through the point of collapse when using fiber elements throughout the model. The analyses also showed that while Perform was capable of calculating the response of the structure accurately, restrictions in the material model resulted in a pushover curve that did not match that of STEEL exactly, particularly post collapse. However, such problems could be alleviated by choosing a more simplistic material model.

Role of absorption in grating erasure

In this paper, we have investigated the grating erasure of a reduced LiNbO3:Fe crystal with different erasing wavelengths. The overall hologram evolution in the process of grating erasure is nonexponential due to strong absorption which is contrary to the mono-exponential law. The hologram in the rear part of the crystal can persist for a long time in the grating erasure due to weak erasing light intensity by strong absorption, which can enlarge the erasure time constant. From the erasure experiments, the global absorption ad 5 can be taken as the optimum absorption to acquire a good trade-off between the sensitivity and hologram strength in the crystal. (c) 2006 Elsevier GmbH. All rights reserved.