In this thesis, I report on the investigation of the low frequency vibrational modes in a number of different systems using ultrafast spectroscopic techniques. These consist of biological systems, including the enzyme, morphinone reductase (MR) and the related biomolecules, riboflavin (Rb) and flavin mononucleotide (FMN), as well as non-biological systems, including the semiconductor gallium nitride (GaN) and gold nanoparticles (Au NPs). The term low frequency refers to terahertz (THz) frequencies, where vibrational modes exist at the molecular level, with molecular rotations, lattice vibrations and inter- and intra-molecular vibrations occurring in the THz spectral range. These vibrational modes occur on sub-picosecond timescales and therefore ultrafast techniques utilising femtosecond laser pulses provide a means of studying these modes, and are employed throughout this thesis. The two ultrafast techniques of transient absorption (TA) spectroscopy and terahertz time-domain spectroscopy (THz-TDS) were used. Firstly, a high-repetition rate transient absorption (HRRTA) spectrometer was commissioned to perform pump-probe measurements with an ultraviolet pump and broadband visible probe. The performance of the HRRTA spectrometer was benchmarked using Au NPs and used to investigate the existence of a promoting vibration in MR contributing to the catalysis process, predicted to occur at THz frequencies. Weak oscillations were detected in the charge-transfer absorption band of MR bound to the non-reactive cofactor 1,4,5,6-tetra-hydro-nicotinamide adenine dinucleotide (NADH4), with a frequency of approximately 1.5 THz and provide evidence of the first direct observation of a promoting vibration in an enzyme. To complement the TA measurements, THz-TDS was also used to obtain direct measurements of the absorption at THz frequencies. Due to the challenge of studying water-based biological samples, an initial investigation was performed on a wurtzite GaN wafer, which exhibited optical phonon modes in the THz frequency range that were found to determine the dielectric response of the semi-insulating semiconductor wafer. Use of a non-polar m-plane wafer allowed the anisotropic nature to be observed and values of 9.22 ± 0.02 and 10.32 ± 0.03 for the static dielectric constants were obtained for the THz electric field polarised both perpendicular and parallel to the c-axis of the wurtzite GaN wafer, respectively. Finally, biological studies using THz-TDS were performed with measurements on Rb pellets and films revealing vibrational modes in the THz region. The sharp absorption features were not observed in FMN, despite a small difference in molecular content from Rb, and dehydration was required to reveal small amplitude absorption features. Final measurements on MR and MR-NADH4 films were carried out and evidence of absorption features in the THz frequency range were observed, however further work is required to determine the precise origin of these features.

I have used the Embedded Atom Method (EAM) to investigate the vibrational behaviors of a large number of metallic systems. The systems examined are the bulk bcc metals Li, Na, K, Rb, Cs, Nb, Ta, Mo, W, and Fe, the bulk fcc metals Ni, Cu, and Al, the (100), (110), (111), and (211) surfaces of the Li, Na, K, Rb, and Cs, and the (100), (110), and (111) surfaces of Ni and Cu. I have conducted a more detailed and extensive review of existing EAM models and their ability to characterize bulk vibrational behavior than has ever previously been reported. I show the ability of an EAM model to quantitatively predict the vibrational properties of the bulk alkali metals in excellent agreement with experiment. The present work remedies a lack of computational investigation into bcc metallic surfaces by performing lattice dynamics calculations of the (110), (100), (111), and (211) alkali metal surfaces. Additionally, I present lattice dynamics calculations on the (111), (100), and (110) surfaces of Cu and Ni. An accurate set of surface Debye temperatures for these metal surfaces has been calculated. The extensive number of metals and planar geometries studied has enabled the identification and clarification of general relationships between surface phonons, surface coordination, and atomic density. The changes in vibrational behavior due to the truncation of the bulk near a surface can be understood by the consideration of three things: the vibrational behavior of a 1-D chain of harmonic oscillators, the bulk dispersion relation in the direction perpendicular to a surface, and the atomic coordination of near surface atoms. In general, relaxation causes force constants between atoms to stiffen, resulting in higher vibrational frequencies. The impact of stiffening on the vibrational characteristics depends largely on the surface geometry, as well as the particular properties of the metal. It can cause new surface modes and resonances, or cause surface vibrations to be more strongly coupled to the vibrations of bulk atoms.

Spin and charge density fluctuations are important excitations in the strongly correlated systems, especially in the recently discovered high temperature superconductors. Several different theories on high temperature superconductors have been proposed based on spin fluctuations. However, experiments have also shown the existence of strong charge fluctuations. It is, therefore, desirable to investigate the physical consequences of the coexistence of strong spin and charge density fluctuations. As a first step toward a full understanding of both spin and charge excitations, a self-consistent theory is established. In this self-consistent theory, there are three important quantities, the spin susceptibility, the charge susceptibility, and the phonon Green's function. These three quantities are coupled together by the electron-phonon and phonon-spin fluctuation interactions. The phonon-spin fluctuation interaction is derived by making use of the spin-orbital coupling. For a strongly correlated system, the spin and charge density excitations have to be considered self-consistently. They are intimately related. The effects of antiparamagnons on phonons are also investigated. Antiparamagnons can have dramatic effects on phononic properties. It is found that new modes are formed in the presence of antiferromagnetic spin fluctuations. The de Haas-van Alphen effect in marginal and nearly antiferromagnetic Fermi liquids is studied. It is found that the de Haas-van Alphen frequency is unaffected by the anomalous response functions of the marginal and nearly antiferromagnetic Fermi liquids due to the absence of real parts of self-energies on the imaginary frequency axis. / Graduation date: 1993

For the past decade interest in skutterudites has been significant as a potentially viable material for thermoelectrics. One way to improve the effectiveness of these materials is to lower their thermal conductivity. Lattice thermal conductivity of a series of La- and Yb-filled skutterudite antimonides (with varying filling fraction) has been modeled with different phonon scattering parameters using the debye approximation. It was found that filler atoms both increase point defect scattering and resonance scattering. Subsequently, the thermal conductivity of partially-filled skutterudites AxCo4Sb12, where A = La, Eu and Yb, is analyzed using the Debye model in order to correlate the data with the type of filler atom in evaluating the role of the filler atom in affecting the thermal conductivity. Partial void filling has resulted in relatively high thermoelectric figures of merit at moderately high temperatures. This idea is extended as new materials were synthesized with the intention of filling the voids in the CoGe1.5Se1.5 skutterudite, and analyzing the transport of these novel materials. Results of the analysis of this material are interesting and may indicate an amorphous phase of skutterudite present. Further work is needed to explore fully the implications of this new skutterudite and to fully understand its properties.

This dissertation reports the results of optical studies of epitaxial (e), polycrystalline (p) and amorphous (a) Ge2Sb2Te5 (GST) thin films. The dynamic properties of GST films in all three (e/p/a) phases were investigated by a time-resolved optical pump-probe technique in which a femtosecond pump pulse of 55 fs duration was used to excite the sample. The intensity and polarization of the reflected probe beam respectively provide information about the transient reflectance (R) and anisotropic reflectance (AR) induced in the sample, that in turn provide the information about the crystal structure, phonon spectrum, and ultimately phase transitions within the sample. The study of an epitaxial sample provides an opportunity to explore the character of the modes within the phonon spectrum. The epitaxial GST film was grown upon a homoepitaxial layer of GaSb grown upon a GaSb wafer. We observed a 6.7 THz coherent optical phonon (COP) in GaSb(001). The dependence of the signal strength upon the pump and probe polarization was explained in terms of a model that considered both Transient stimulated Raman Scattering (TSRS) and the action of a Surface Space-Charge (SSC) field. The presence of the 6.7 THz transverse COP in the AR channel and its four fold dependence on pump and probe polarization suggests a three-dimensional T2 character. The COP amplitude was maximum when the probe was polarized parallel to the cube edge (GaSb[100]) and the pump polarization was set parallel to a face diagonal (GaSb[110]). The results were fully understood using a microscopic model of selective bond breaking. The AR response of e-GST/GaSb(001) reveals the presence of a 3D 3.4 THz transverse optical phonon. The mode amplitude was independent of pump polarization indicating that the mode is excited by a SSC field. This SSC field could exist within the GST, if the distorted rock-salt structure of GST lacks inversion symmetry, or GaSb, which has the non-centrosymmetric zincblende structure, leading to impulsive excitation of phonons at the GST/GaSb interface. The mode in GST was inferred to be T2-like. The observation of a T2-like phonon mode confirms that GST is cubic in structure and challenges previous studies where 1D or 2D character was assigned to the 3.4 THz mode. While pump-probe measurements displayed the presence of a 3D 3.4 THz mode in the AR response of e-GST/GaSb(001), a 4.5 THz mode was observed in both R and AR channels for p-GST(37 nm)/Si(001) and a-GST(57 nm)/Si(001). The mode character was identified to be either of A or E type by comparing the frequency with frequencies reported in the literature. Additional Raman microscope measurements confirmed the presence of the modes observed in the pump-probe measurements and also revealed additional frequencies. The differences in the frequencies observed from the different samples are quite small suggesting the presence of similar bonds that are modified to some extent by the different structural environment found within each sample. After exposure to high pump fluence the original modes disappeared and were replaced by new modes with frequencies at 4.2 THz and 3.1 THz in e-GaSb, 4.2 THz in e-GST, 3.5 THz in p-GST and 3.6 THz in a-GST. The difference in the final frequencies observed for p and a-GST sample may result from the difference in stack structure affecting the time-dependent temperature profile in each sample. The dependence of the temperature profile on the sample stack was understood from an experimental study of the phase transition between the amorphous and crystalline states induced by exposure to a series of amplified laser pulses. The dependence of the crystalline area and its reflectivity upon the number of pulses and fluence was described using a simple algebraic model. The results justify the assumption of one-dimensional heat flow. The growth velocity of the crystalline region was calculated to be 7-9 m/s. Apparatus and methods were developed to extend the time-resolved optical studies described previously. Firstly, an apparatus was constructed for the measurement of the wavelength dependent sample reflectance with a white-light pulse. A reference arm was employed to allow normalization and hence removal of the intensity noise arising in the laser regenerative amplifier system. Secondly an electrical measurement apparatus was constructed to allow combined electro-optical measurements in future. Switching of GST vertical memory cells was successfully demonstrated. The cells were fabricated on a borosilicate substrate with TiW top and bottom electrodes. A DC voltage of 4.5 to 6 V was required to induce switching, while in pulsed measurements, the device demonstrated switching in response to a pulse with minimum duration of 100 ns.

We use normal mode decomposition to obtain phonon properties from quasi-harmonic lattice dynamics calculations and classical molecular dynamics simulations in unstrained Lennard-Jones argon superlattices with perfect and mixed interfaces. Debye scaling of phonon lifetimes at low frequencies in both perfect and mixed superlattices and Rayleigh scaling for intermediate frequencies in mixed superlattices is observed. For short period mixed superlattices, lifetimes below the Ioffe-Regel limit are observed. The relaxation-time approximation of the Boltzmann transport equation is used to predict cross-plane and in-plane thermal conductivity. We find that using a dispersion relation which includes the secondary periodicity is required to predict thermal conductivity. The assumption of perturbative disorder, where Tamura elastic mass defect scattering theory can be applied, was found to be valid for predicting cross-plane thermal conductivities but not in-plane thermal conductivities in mixed superlattices.

We use normal mode decomposition to obtain phonon properties from quasi-harmonic lattice dynamics calculations and classical molecular dynamics simulations in unstrained Lennard-Jones argon superlattices with perfect and mixed interfaces. Debye scaling of phonon lifetimes at low frequencies in both perfect and mixed superlattices and Rayleigh scaling for intermediate frequencies in mixed superlattices is observed. For short period mixed superlattices, lifetimes below the Ioffe-Regel limit are observed. The relaxation-time approximation of the Boltzmann transport equation is used to predict cross-plane and in-plane thermal conductivity. We find that using a dispersion relation which includes the secondary periodicity is required to predict thermal conductivity. The assumption of perturbative disorder, where Tamura elastic mass defect scattering theory can be applied, was found to be valid for predicting cross-plane thermal conductivities but not in-plane thermal conductivities in mixed superlattices.

Thesis (Ph. D.)--University of Washington, 2007. / Vita. Includes bibliographical references (p. 102-114).

Thesis (Ph. D.)--University of Missouri-Columbia, 1996. / Typescript. Vita. Includes bibliographical references (leaves 169-175). Also available on the Internet.

Thesis (Ph. D.)--University of Missouri-Columbia, 1996. / Typescript. Vita. Includes bibliographical references (leaves 169-175). Also available on the Internet.