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.

Ultrafast temporal pattern generation and recognition

Ultrafast temporal pattern generation and recognition with femtosecond laser technology is presented, analyzed, and experimentally implemented. Ultrafast temporal pattern generation and recognition are realized by taking advantage of two well-known techniques: the space-time conversion technique and the ultrafast pulse measurement technique. Here the temporal pattern for the designed multiple pulses, optimized with a preassumed Gaussian spectral distribution of an ultrashort pulse, is described. With the simulation of a Gaussian spectral distribution, we realize that the uniformity of the generated multiple ultrafast temporal pulses is relevant to the repeated number of modulation periods in the mask in the spectral plane. Moreover, the change of Gaussian spectral phases with the wavelengths in the modulated phase plate is considered. Experiments of ultrafast temporal pattern recognition by the frequency-resolved optical gating (FROG) characterization technique are also given. (C) 2004 Society of Photo-Optical Instrumentation Engineers.

Generation of near-field hexagonal array illumination with a phase grating

A hexagonal array not only is a nature-preferred pattern but also is widely used in optoelectronical materials and devices. We report a simple method of hexagonal array illumination based on the Talbot effect that has a theoretical efficiency of 100%. An experimental efficiency of 90.6% with a binary phase (0, pi) hexagonal grating is given. This method should be highly interesting for applications of hexagonal array illumination in optical devices as well as in other hexagonal cells. (C) 2002 Optical Society of America.

Generation of millimeter-wave in optical pulse carrier by using an apodized Moire fiber grating

A novel scheme is proposed to transform a Gaussian pulse to a millimeter-wave frequency modulation pulse by using an apodized Moire fiber Bragg grating in radio-over-fiber system. The relation between the input and output pulses is analyzed theoretically by Fourier transformation method and the requirements for the proposed fiber grating are presented. An apodized Moire fiber Bragg grating is designed and its characteristics are studied. It is shown that the proposed device is feasible, and the new scheme is believed to be an effective solution for the generation of millimeter-wave sub-carrier in future radio-over-fiber systems. (c) 2006 Elsevier B.V. All rights reserved.

Time domain synthesis of electro-optical birefringent system for optical waveform generation

In this paper is described a novel technique for producing an electro-optical intensity synthesizer which can generate different periodic time domain waveforms through only sine or cosine wave applied-voltages. The synthesizer presented here consists of a series of stages between two polarizers, with each stage consisting of an electro-optic element and a compensator. Every electro-optical element has the same applied-voltage function but different azimuth angles and ratios between the longitudinal and transverse lengths. The main principle is the synthesis of an electro-optic effect and a polarization interference effect in the time domain. This technique is based on an expanded Fourier positive-direction searching algorithm, which can not only simplify the calculation process but also produces many choices of structural parameters for different waveforms generation. A three-stage synthesis of an electro-optical birefringent system for continuous square waveform is undertaken to prove the principle.

Measuring ultrashort optical pulses using multi-shot second harmonic generation frequency resolved optical gating

Frequency resolved optical gating (FROG), is an effective technique for characterizing the ultrafast laser pulses. The multi-shot second harmonic generation (SHG) FROG is the most sensitive one in different FROGs. In this paper we use this technique to measure the femtosecond optical pulses generated by a conventional Ti:sapphire oscillator.

Double-line-density gratings structure for compression and generation of double femtosecond laser pulses

Grating pairs are widely used for pulse compression and stretching. Normally, the two gratings are identical. We propose a very simple structure with double-line-density reflective gratings for pulse compression and generation of double pulses, which has the advantages of no material dispersion, compact in volume, simple in structure, etc. The use of reflective Dammann gratings fully demonstrated the principle of this structure. The output pulses are well verified by a standard frequency-resolved optical gating apparatus. This structure will be highly interesting in ultrashort pulse compression and other more practical applications of femtosecond laser pulses. (c) 2007 Optical Society of America.

Generation of double pulses in-line by using reflective Dammann gratings

Doubled femtosecond laser pulses in-line are needed in the collinear pump-probe technique, collinear second harmonic generation frequency-resolved optical gating (SHG FROG) and the spectral phase interferometry for direct electric-field reconstruction (SPIDER), etc. Normally, it is generated by using a Michelson's structure. In this paper, we proposed a novel structure with two-layered reflective Dammann gratings and the reflective mirrors to generate doubled femtosecond laser pulses in line without transmission optical elements. Angular dispersion and spectral spatial walk-off are both compensated. In addition, this structure can also compress the positive chirped pulse, which cannot be realized with a Michelson's structure. By adopting triangular grating and blazed gratings, the efficiency of the system would in principle be increased as the Michelson's scheme. Experiments demonstrated that this method should be an alternative approach for generation of the double compressed pulses of femtosecond laser for practical applications. (c) 2006 Elsevier GmbH. All rights reserved.

Tsunamis - a model of their generation and propagation

A general solution is presented for water waves generated by an arbitrary movement of the bed (in space and time) in a two-dimensional fluid domain with a uniform depth. The integral solution which is developed is based on a linearized approximation to the complete (nonlinear) set of governing equations. The general solution is evaluated for the specific case of a uniform upthrust or downthrow of a block section of the bed; two time-displacement histories of the bed movement are considered.

An integral solution (based on a linear theory) is also developed for a three-dimensional fluid domain of uniform depth for a class of bed movements which are axially symmetric. The integral solution is evaluated for the specific case of a block upthrust or downthrow of a section of the bed, circular in planform, with a time-displacement history identical to one of the motions used in the two-dimensional model.

Since the linear solutions are developed from a linearized approximation of the complete nonlinear description of wave behavior, the applicability of these solutions is investigated. Two types of non-linear effects are found which limit the applicability of the linear theory: (1) large nonlinear effects which occur in the region of generation during the bed movement, and (2) the gradual growth of nonlinear effects during wave propagation.

A model of wave behavior, which includes, in an approximate manner, both linear and nonlinear effects is presented for computing wave profiles after the linear theory has become invalid due to the growth of nonlinearities during wave propagation.

An experimental program has been conducted to confirm both the linear model for the two-dimensional fluid domain and the strategy suggested for determining wave profiles during propagation after the linear theory becomes invalid. The effect of a more general time-displacement history of the moving bed than those employed in the theoretical models is also investigated experimentally.

The linear theory is found to accurately approximate the wave behavior in the region of generation whenever the total displacement of the bed is much less than the water depth. Curves are developed and confirmed by the experiments which predict gross features of the lead wave propagating from the region of generation once the values of certain nondimensional parameters (which characterize the generation process) are known. For example, the maximum amplitude of the lead wave propagating from the region of generation has been found to never exceed approximately one-half of the total bed displacement. The gross features of the tsunami resulting from the Alaskan earthquake of 27 March 1964 can be estimated from the results of this study.

Compliance verification methodology for renewable generation integration. Application to island power grids

261 p.