Terahertz time domain spectroscopy of amino acids and sugars

A time-domain spectrometer for use in the terahertz (THz) spectral range was designed and constructed. Due to there being few existing methods of generating and detecting THz radiation, the spectrometer is expected to have vast applications to solid, liquid, and gas phase samples. In particular, knowledge of complex organic chemistry and chemical abundances in the interstellar medium (ISM) can be obtained when compared to astronomical data. The THz spectral region is of particular interest due to reduced line density when compared to the millimeter wave spectrum, the existence of high resolution observatories, and potentially strong transitions resulting from the lowest-lying vibrational modes of large molecules.

The heart of the THz time-domain spectrometer (THz-TDS) is the ultrafast laser. Due to the femtosecond duration of ultrafast laser pulses and an energy-time uncertainty relationship, the pulses typically have a several-THz bandwidth. By various means of optical rectification, the optical pulse carrier envelope shape, i.e. intensity-time profile, can be transferred to the phase of the resulting THz pulse. As a consequence, optical pump-THz probe spectroscopy is readily achieved, as was demonstrated in studies of dye-sensitized TiO₂, as discussed in chapter 4. Detection of the terahertz radiation is commonly based on electro-optic sampling and provides full phase information. This allows for accurate determination of both the real and imaginary index of refraction, the so-called optical constants, without additional analysis. A suite of amino acids and sugars, all of which have been found in meteorites, were studied in crystalline form embedded in a polyethylene matrix. As the temperature was varied between 10 and 310 K, various strong vibrational modes were found to shift in spectral intensity and frequency. Such modes can be attributed to intramolecular, intermolecular, or phonon modes, or to some combination of the three.

Identification of thermally-tagged coherent structures in the zero pressure gradient turbulent boundary layer

A zero pressure gradient boundary layer over a flat plate is subjected to step changes in thermal condition at the wall, causing the formation of internal, heated layers. The resulting temperature fluctuations and their corresponding density variations are associated with turbulent coherent structures. Aero-optical distortion occurs when light passes through the boundary layer, encountering the changing index of refraction resulting from the density variations. Instantaneous measurements of streamwise velocity, temperature and the optical deflection angle experienced by a laser traversing the boundary layer are made using hot and cold wires and a Malley probe, respectively. Correlations of the deflection angle with the temperature and velocity records suggest that the dominant contribution to the deflection angle comes from thermally-tagged structures in the outer boundary layer with a convective velocity of approximately 0.8U∞. An examination of instantaneous temperature and velocity and their temporal gradients conditionally averaged around significant optical deflections shows behavior consistent with the passage of a heated vortex. Strong deflections are associated with strong negative temperature gradients, and strong positive velocity gradients where the sign of the streamwise velocity fluctuation changes. The power density spectrum of the optical deflections reveals associated structure size to be on the order of the boundary layer thickness. A comparison to the temperature and velocity spectra suggests that the responsible structures are smaller vortices in the outer boundary layer as opposed to larger scale motions. Notable differences between the power density spectra of the optical deflections and the temperature remain unresolved due to the low frequency response of the cold wire.

High frequency wave propagation in the earth: theory and observation

The wave-theoretical analysis of acoustic and elastic waves refracted by a spherical boundary across which both velocity and density increase abruptly and thence either increase or decrease continuously with depth is formulated in terms of the general problem of waves generated at a steady point source and scattered by a radially heterogeneous spherical body. A displacement potential representation is used for the elastic problem that results in high frequency decoupling of P-SV motion in a spherically symmetric, radially heterogeneous medium. Through the application of an earth-flattening transformation on the radial solution and the Watson transform on the sum over eigenfunctions, the solution to the spherical problem for high frequencies is expressed as a Weyl integral for the corresponding half-space problem in which the effect of boundary curvature maps into an effective positive velocity gradient. The results of both analytical and numerical evaluation of this integral can be summarized as follows for body waves in the crust and upper mantle:

1) In the special case of a critical velocity gradient (a gradient equal and opposite to the effective curvature gradient), the critically refracted wave reduces to the classical head wave for flat, homogeneous layers.

2) For gradients more negative than critical, the amplitude of the critically refracted wave decays more rapidly with distance than the classical head wave.

3) For positive, null, and gradients less negative than critical, the amplitude of the critically refracted wave decays less rapidly with distance than the classical head wave, and at sufficiently large distances, the refracted wave can be adequately described in terms of ray-theoretical diving waves. At intermediate distances from the critical point, the spectral amplitude of the refracted wave is scalloped due to multiple diving wave interference.

These theoretical results applied to published amplitude data for P-waves refracted by the major crustal and upper mantle horizons (the Pg, P*, and Pn travel-time branches) suggest that the 'granitic' upper crust, the 'basaltic' lower crust, and the mantle lid all have negative or near-critical velocity gradients in the tectonically active western United States. On the other hand, the corresponding horizons in the stable eastern United States appear to have null or slightly positive velocity gradients. The distribution of negative and positive velocity gradients correlates closely with high heat flow in tectonic regions and normal heat flow in stable regions. The velocity gradients inferred from the amplitude data are generally consistent with those inferred from ultrasonic measurements of the effects of temperature and pressure on crustal and mantle rocks and probable geothermal gradients. A notable exception is the strong positive velocity gradient in the mantle lid beneath the eastern United States (2 x 10^-3 sec^-1), which appears to require a compositional gradient to counter the effect of even a small geothermal gradient.

New seismic-refraction data were recorded along a 800 km profile extending due south from the Canadian border across the Columbia Plateau into eastern Oregon. The source for the seismic waves was a series of 20 high-energy chemical explosions detonated by the Canadian government in Greenbush Lake, British Columbia. The first arrivals recorded along this profile are on the Pn travel-time branch. In northern Washington and central Oregon their travel time is described by T = Δ/8.0 + 7.7 sec, but in the Columbia Plateau the Pn arrivals are as much as 0.9 sec early with respect to this line. An interpretation of these Pn arrivals together with later crustal arrivals suggest that the crust under the Columbia Plateau is thinner by about 10 km and has a higher average P-wave velocity than the 35-km-thick, 62-km/sec crust under the granitic-metamorphic terrain of northern Washington. A tentative interpretation of later arrivals recorded beyond 500 km from the shots suggests that a thin 8.4-km/sec horizon may be present in the upper mantle beneath the Columbia Plateau and that this horizon may form the lid to a pronounced low-velocity zone extending to a depth of about 140 km.