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.

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.

Detection of Brillouin scattering temperature signal in Brillouin optical time-domain reflectometer sensing system based on instantaneous frequency measurement technology

We present a simple and practical method for the single-ended distributed fiber temperature measurements using microwave (11-GHz) coherent detection and the instantaneous frequency measurement (IFM) technique to detect spontaneous Brillouin backscattered signal in which a specially designed rf bandpass filter at 11 GHz is used as a frequency discriminator to transform frequency shift to intensity fluctuation. A Brillouin temperature signal can be obtained at 11 GHz over a sensing length of 10 km. The power sensitivity dependence on temperature induced by frequency shift is measured as 2.66%/K. (c) 2007 Society of Photo-Optical Instrumentation Engineers.

Detection of Brillouin scattering temperature signal in Brillouin optical time-domain reflectometer sensing system based on instantaneous frequency measurement technology

abstract {We present a simple and practical method for the single-ended distributed fiber temperature measurements using microwave (11-GHz) coherent detection and the instantaneous frequency measurement (IFM) technique to detect spontaneous Brillouin backscattered signal in which a specially designed rf bandpass filter at 11 GHz is used as a frequency discriminator to transform frequency shift to intensity fluctuation. A Brillouin temperature signal can be obtained at 11 GHz over a sensing length of 10 km. The power sensitivity dependence on temperature induced by frequency shift is measured as 2.66%/K. © 2007 Society of Photo-Optical Instrumentation Engineers.}

On the domain decomposition and transmission line modelling finite element method for time-domain induction motor analysis

This paper demonstrates how a finite element model which exploits domain decomposition is applied to the analysis of three-phase induction motors. It is shown that a significant gain in cpu time results when compared with standard finite element analysis. Aspects of the application of the method which are particular to induction motors are considered: the means of improving the convergence of the nonlinear finite element equations; the choice of symmetrical sub-domains; the modelling of relative movement; and the inclusion of periodic boundary conditions. © 1999 IEEE.