Pulse NMR in solids : chemical shift, lead fluoride and thorium hydride

Part one of this thesis consists of two sections. In the first section the fluorine chemical shift of a single crystal CaF_2 has been measured as a function of external pressure up to 4 kilobar at room temperature using multiple pulse NMR techniques. The pressure dependence of the shift is found to be -1.7 ± 1 ppm/kbar, while a theoretical calculation using an overlap model predicts a shift of -0.46 ppm/kbar. In the second section a separation of the chemical shift tensor into physically meaningful "geometrical" and "chemical" contributions is presented and a comparison of the proposed model calculations with recently reported data on hydroxyl proton chemical shift tensors demonstrates, that for this system, the geometrical portion accounts for the qualitative features of the measured tensors.

Part two of the thesis consists of a study of fluoride ion motion in β-PbF_2 doped with NaF by measurement of the ^(19)F transverse relaxation time (T_2), spin lattice relaxation time (T_1) and the spin lattice relaxation time in the rotating frame (T_(1r)). Measurements over the temperature range of -50°C to 160°C lead to activation energies for T_1, T_(1r) and T_2 of 0.205 ± 0.01, 0.29 + 0.02 and 0.27 ± 0.01 ev/ion, and a T_(1r) minimum at 56°C yields a correlation time of 0.74 μsec. Pressure dependence of T_1 and T_2 yields activation volumes of <0.2 cm^3/g-mole and 1.76 ± 0.05 cm^3/g-mole respectively. These data along with the measured magnetic field independence of T_1 suggest that the measured T_1's are not caused by ^(19)F motion, but by thermally excited carriers.

Part three of the thesis consists of a study of two samples of Th_4H_(15), prepared under different conditions but both having the proper ratio of H/Th (to within 1%). The structure of the Th_4H_(15) as suggested by X-ray measurements is confirmed through a moment analysis of the rigid lattice line shape. T_1 and T_2 measurements above 390 K furnish activation energies of 16.3 ± 1.2 kcal/mole and 18.0 ± 3.0 kcal/mole, respectively. Below 350 K, T_(1r) measurements furnish an activation energy of 10.9 ± 0.7 kcal/mole, indicating most probably more than a single mechanism for proton motion. A time-temperature hysteresis effect of the proton motion was found in one of the two samples and is strongly indicative of a phase change. T_1 at room temperature and below is dominated by relaxation due to conduction electrons with the product T_1T being 180 ± 10 K-sec. Using multiple pulse techniques to greatly reduce homonuclear dipolar broadening, a temperature-dependent line shift was observed, and the chemical shift anisotropy is estimated to be less than 16 ppm.

A study of a new electromechanical energy conversion process using superconducting frequency modulated resonators

Experimental demonstrations and theoretical analyses of a new electromechanical energy conversion process which is made feasible only by the unique properties of superconductors are presented in this dissertation. This energy conversion process is characterized by a highly efficient direct energy transformation from microwave energy into mechanical energy or vice versa and can be achieved at high power level. It is an application of a well established physical principle known as the adiabatic theorem (Boltzmann-Ehrenfest theorem) and in this case time dependent superconducting boundaries provide the necessary interface between the microwave energy on one hand and the mechanical work on the other. The mechanism which brings about the conversion is another known phenomenon - the Doppler effect. The resonant frequency of a superconducting resonator undergoes continuous infinitesimal shifts when the resonator boundaries are adiabatically changed in time by an external mechanical mechanism. These small frequency shifts can accumulate coherently over an extended period of time to produce a macroscopic shift when the resonator remains resonantly excited throughout this process. In addition, the electromagnetic energy in s ide the resonator which is proportional to the oscillation frequency is al so accordingly changed so that a direct conversion between electromagnetic and mechanical energies takes place. The intrinsically high efficiency of this process is due to the electromechanical interactions involved in the conversion rather than a process of thermodynamic nature and therefore is not limited by the thermodynamic value.

A highly reentrant superconducting resonator resonating in the range of 90 to 160 MHz was used for demonstrating this new conversion technique. The resonant frequency was mechanically modulated at a rate of two kilohertz. Experimental results showed that the time evolution of the electromagnetic energy inside this frequency modulated (FM) superconducting resonator indeed behaved as predicted and thus demonstrated the unique features of this process. A proposed usage of FM superconducting resonators as electromechanical energy conversion devices is given along with some practical design considerations. This device seems to be very promising in producing high power (~10W/cm^3) microwave energy at 10 - 30 GHz.

Weakly coupled FM resonator system is also analytically studied for its potential applications. This system shows an interesting switching characteristic with which the spatial distribution of microwave energies can be manipulated by external means. It was found that if the modulation was properly applied, a high degree (>95%) of unidirectional energy transfer from one resonator to the other could be accomplished. Applications of this characteristic to fabricate high efficiency energy switching devices and high power microwave pulse generators are also found feasible with present superconducting technology.

Energy spectrum of two-component Bose-Einstein condensates in optical lattices

With the method of Green's function, we investigate the energy spectra of two-component ultracold bosonic atoms in optical lattices. We End that there are two energy bands for each component. The critical condition of the superfluid-Mott insulator phase transition is determined by the energy band structure. We also find that the nearest neighboring and on-site interactions fail to change the structure of energy bands, but shift the energy bands only. According to the conditions of the phase transitions, three stable superfluid and Mott insulating phases can be found by adjusting the experiment parameters. We also discuss the possibility of observing these new phases and their transitions in further experiments.

Molecular Antennas and Photoactive Nanomaterials based on Energy Transfer Processes

110 p.

Mechanisms of Yb3+ sensitization to Tm3+ for blue upconversion luminescence in fluorophosphate glass

The sensitization mechanisms of Yb3+ to Tm3+ for the blue upconversion luminescence in fluorophosphate glass were studied. Two different mechanisms exist in the sensitization. One is the sequential sensitization that Tm3+ is excited from H-3(6) to (1)G(4) through absorbing three photons transferred from Yb3+ one by one. Another is the cooperative sensitization that two Yb3+ ions form a couple cluster firstly, and then the couple cluster Yb3+ ions transfer their energy to Tm3+ and excite it to (1)G(4). With the increment of the concentration of Yb3+ ions, the sequential sensitization becomes weak and the cooperative sensitization becomes intense, and the transformation trend of sensitization mechanism with the increment of Yb3+ concentration can be clarified by the introduction of Th3+ ions in the glass. (c) 2006 Elsevier B.V. All rights reserved.

Energy transfer and infrared-to-visible upconversion luminescence of Er3+/Yb3+-codoped halide modified tellurite glasses

We report on the energy transfer and frequency upconversion spectroscopic properties of Er3+-doped and Er3+/Yb3+-codoped TeO2-ZnO-Na2O-PbCl2 halide modified tellurite glasses upon excitation with 808 and 978 nm laser diode. Three intense emissions centered at around 529, 546 and 657 nm, alongwith a very weak blue emission at 4 10 nm have clearly been observed for the Er3+/Yb3+-codoped halide modified tellurite glasses upon excitation at 978 nm and the involved mechanisms are explained. The quadratic dependence of fluorescence on excitation laser power confirms the fact that the two-photon contribute to the infrared to green-red upconversion emissions. And the blue upconversion at 410 nm involved a sequential three-photon absorption process. (c) 2005 Elsevier Ltd. All rights reserved.

Blue upconversion Luminescence in Tm3+/Yb3+-Codoped New Oxyfluoride Tellurite Glass

The thermal stability, Raman spectrum and upconversion properties of Tm^(3+)/Yb^(3+) co-doped new oxyfluoride tellurite glass are investigated. The results show that Tm^(3+)/Yb^(3+) co-doped oxyfluoride tellurite glass possesses good thermal stability, lower phonon energy, and intense upconversion blue luminescence. Under 980-nm laser diode (LD) excitation, the intense blue (475 nm) emission and weak red (649 nm) emission corresponding to the 1G4 -> 3H6 and 1G4 -> 3F4 transitions of Tm^(3+) ions respectively, were simultaneously observed at room temperature. The possible upconversion mechanisms are evaluated. The intense blue upconversion luminescence of Tm^(3+)/Yb^(3+) co-doped oxyfluoride tellurite glass can be used as potential host material for the development of blue upconversion optical devices.

Blue-yellow ZnO homostructural light-emitting diode realized by metalorganic chemical vapor deposition technique

We report on the realization of ZnO homojunction light-emitting diodes (LEDs) fabricated by metalorganic chemical vapor deposition on (0001) ZnO bulk substrate. The p-type ZnO epilayer was formed by nitrogen incorporation using N2O gas as oxidizing and doping sources. Distinct electroluminescence (EL) emissions in the blue and yellow regions were observed at room temperature by the naked eye under forward bias. The EL peak energy coincided with the photoluminescence peak energy of the ZnO epilayer, suggesting that the EL emissions emerge from the ZnO epilayer. In addition, the current-voltage and light output-voltage characteristics of ZnO homojunction LEDs have also been studied. (c) 2006 American Institute of Physics.

The effects of oxygen partial pressure on the optical absorption edge and the UV emission energy of ZnO films

The optical absorption edge and ultraviolet (UV) emission energy of ZnO films deposited by direct current (DC) reactive magnetron sputtering at room temperature have been investigated. With the oxygen ratio increasing, the structure of films changes from zinc and zinc oxide coexisting phase to single-phase ZnO and finally to the highly (002) orientation. Both the grain size and the stress of ZnO film vary with the oxygen partial pressure. Upon increasing the oxygen partial pressure in the growing ambient, the visible emission in the room-temperature photoluminescence spectra was suppressed without sacrificing the band-edge emission intensity in the ultraviolet region. The peaks of photoluminescence spectra were located at 3.06---3.15 eV. From optical transmittance spectra of ZnO films, the optical band gap edge was observed to shift towards shorter wavelength with the increase of oxygen partial pressure.

Effects of El Niño events on energy demand and egg production of rockfish (Scorpaenidae: Sebastes): a bioenergetics approach

Fish bioenergetics models estimate relationships between energy budgets and environmental and physiological variables. This study presents a generic rockfish (Sebastes) bioenergetics model and estimates energy consumption by northern California blue rockf ish (S. mystinus) under average (baseline) and El Niño conditions. Compared to males, female S. mystinus required more energy because they were larger and had greater reproductive costs. When El Niño conditions (warmer temperatures; lower growth, condition, and fecundity) were experienced every 3−7 years, energy consumption decreased on an individual and a per-recruit basis in relation to baseline conditions, but the decrease was minor (<4% at the individual scale, <7% at the per-recruit scale) compared to decreases in female egg production (12−19% at the individual scale, 15−23% at the per-recruit scale). When mortality in per-recruit models was increased by adding fishing, energy consumption in El Niño models grew more similar to that seen in the baseline model. However, egg production decreased significantly — an effect exacerbated by the frequency of El Niño events. Sensitivity analyses showed that energy consumption estimates were most sensitive to respiration parameters, energy density, and female fecundity, and that estimated consumption increased as parameter uncertainty increased. This model provides a means of understanding rockfish trophic ecology in the context of community structure and environmental change by synthesizing metabolic, demographic, and environmental information. Future research should focus on acquiring such information so that models like the bioenergetics model can be used to estimate the effect of climate change, community shifts, and different harvesting strategies on rockfish energy demands.

Feeding on protists and particulates by the leptocephali of the worm eels Myrophis spp. (Teleostei: Anguilliformes: Ophichthidae), and the potential energy contribution of large aloricate protozoa

The food sources of the leptocephali of the teleostean superorder Elopomorpha have been controversial, yet observations on the leptocephali of the worm eels, Myrophis spp. (family Ophichthidae) collected in the northern Gulf of Mexico indicate active, not passive, feeding. Leptocephali had protists in their alimentary canals. Estimates of the physiological energetics of worm eels indicate that large aloricate protozoa including ciliates could provide substantial energy to these leptocephali toward the end of the premetamorphic and metamorphic stages, given the low energy requirements of metamorphosing leptocephali. Global ocean warming will likely force a shift in oceanic food webs; a shift away from large protozoa toward smaller protists is possible. Such a disruption of the oceanic food webs could further compromise the survival of leptocephali.

Effect of inclusion of blue-green algae meal on growth and accumulation of microcystins in gibel carp (Carassius auratus gibelio)

Six isonitrogenous (crude protein content: 38%) and isoenergetic (gross energy content: 17 kJ g(-1)) diets were formulated to investigate the effects of inclusion of blue-green algae meal on gibel carp (Carassius auratus gibelio). In each diet, 15% of the protein was supplied by fishmeal; the remainder was supplied by soybean meal and blue-green algae meal. Diet 1 was used as control with no blue-green algae meal whereas the content in diets 2-6 was 15.15, 29.79, 44.69, 59.58 and 74.48%, respectively. Each diet was fed to five groups of gibel carp for 12 weeks in a flow-through system. Final body weight and specific growth rate (SGR) of fish fed diet 5 were significantly lower than the control diet (P < 0.05). Mortality of gibel carp increased with increase in algae meal inclusion (P < 0.05), but there was no significant difference between fish fed diets 3-6 (P > 0.05). Feed conversion efficiency (FCE) decreased with the increase in algae meal inclusion (P < 0.05). Fish-fed diet 6 showed the highest feeding rate (P < 0.05), while there were no significant differences among the other groups (P > 0.05). Apparent digestibility coefficient of dry matter, protein, and energy decreased with increasing algae meal inclusion in the diets (P < 0.05). Aspartate aminotransferase (GOT) activity in the liver was not significantly different among groups (P > 0.05). Liver alanine aminotransferase (GPT) activity of fish-fed diets 4, 5 and 6 was significantly lower than the control diet (diet 1; P < 0.05). Microcystins in the muscle, liver, gallbladder, and spleen increased with increasing algae inclusion (P < 0.05).

STUDIES ON MIXED MASS CULTIVATION OF ANABAENA SPP (NITROGEN-FIXING BLUE-GREEN-ALGAE, CYANOBACTERIA) ON A LARGE-SCALE

Studies on mixed mass cultivation of Anabaena spp. on a large scale (5170 m2) were conducted continuously for 3 years. Under the continental monsoon climate in northern subtropics (30-degrees-N, 115-degrees-E), 7-11 g dry weight m-2 day-1 of microalgal biomass on average was harvested in simple plastic greenhouses in the effective growth days during the warmer seasons. The maximum productivity was 22 g m-2 day-1 in the middle of summer. Observations on the productive properties of strains of Anabaena spp. indicated that they were different from and could compensate for each other in their productivities and adaptations to the seasonal changes. With different lining materials (PVC sheets, concrete, sand and soil) in the culture ponds, no significant variation of productivity was found, but bubbling with biogas in the middle of the day and the application of some growth regulating substances (2,4-D, NaHSO3 and extracts of oyster mushroom spawn) was able to improve the production. The cost of microalgal biomass in this way was around 0.75-1.0 US dollar(s) per kilogram.

Blue-green optically pumped GaN-based vertical cavity surface emitting laser

Blue-green GaN-based vertical cavity surface emitting lasers (VCSELs) were fabricated with two dielectric Ta2O5/SiO2 distributed Bragg reflectors. Lasing action was observed at a wavelength of 498.8 nm at room temperature under optical pumping. Threshold energy density and emission linewidth were 189 mJ/cm(2) and 0.15 nm, respectively. The result demonstrates that blue-green VCSELs can be realised using III-nitride semiconductors.

Photoluminescence energy and fine structure splitting in single quantum dots by uniaxial stress

We report a photoluminescence (PL) energy red-shift of single quantum dots (QDs) by applying an in-plane compressive uniaxial stress along the [110] direction at a liquid nitrogen temperature. Uniaxial stress has an effect not only on the confinement potential in the growth direction which results in the PL shift, but also on the cylindrical symmetry of QDs which can be reflected by the change of the full width at half maximum of PL peak. This implies that uniaxial stress has an important role in tuning PL energy and fine structure splitting of QDs.