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.

Light-matter Interactions in Semiconductors and Metals: From Nitride Optoelectronics to Quantum Plasmonics

This thesis puts forth a theory-directed approach coupled with spectroscopy aimed at the discovery and understanding of light-matter interactions in semiconductors and metals.

The first part of the thesis presents the discovery and development of Zn-IV nitride materials.The commercial prominence in the optoelectronics industry of tunable semiconductor alloy materials based on nitride semiconductor devices, specifically InGaN, motivates the search for earth-abundant alternatives for use in efficient, high-quality optoelectronic devices. II-IV-N2 compounds, which are closely related to the wurtzite-structured III-N semiconductors, have similar electronic and optical properties to InGaN namely direct band gaps, high quantum efficiencies and large optical absorption coefficients. The choice of different group II and group IV elements provides chemical diversity that can be exploited to tune the structural and electronic properties through the series of alloys. The first theoretical and experimental investigation of the ZnSnxGe1−xN2 series as a replacement for III-nitrides is discussed here.

The second half of the thesis shows ab−initio calculations for surface plasmons and plasmonic hot carrier dynamics. Surface plasmons, electromagnetic modes confined to the surface of a conductor-dielectric interface, have sparked renewed interest because of their quantum nature and their broad range of applications. The decay of surface plasmons is usually a detriment in the field of plasmonics, but the possibility to capture the energy normally lost to heat would open new opportunities in photon sensors, energy conversion devices and switching. A theoretical understanding of plasmon-driven hot carrier generation and relaxation dynamics in the ultrafast regime is presented here. Additionally calculations for plasmon-mediated upconversion as well as an energy-dependent transport model for these non-equilibrium carriers are shown.

Finally, this thesis gives an outlook on the potential of non-equilibrium phenomena in metals and semiconductors for future light-based technologies.

Embedding quantum simulators

79 p.

Density-potential mapping in the standard and quantum electrodynamical time-dependent density functional theory

131 p.

Magnetotunnelling spectroscopy: an experimental tool for studying chaos in quantum transport

Resonant tunnelling spectroscopy is used to investigate the energy level spectrum of a wide potential well in the presence of a large magnetic field oriented at angles θ between 0° and 90° to the normal to the plane of the well. In the tilted field geometry, the current-voltage characteristics exhibit a large number of quasiperiodic resonant peaks even though the classical motion of electrons in the potential well is chaotic. The voltage range and spacing of the resonances both change dramatically with θ. We give a quantitative explanation for this behaviour by considering the classical period of unstable periodic orbits within the chaotic sea of the potential well.

Larval development of a semi terrestrial mangrove sesarmine crab Chasmagnathus convexus (Crustacea: Decapoda: Brachyura: Grapsidae) reared in laboratory

Four zoeal stages and one megalopal stage were identified in laboratory reared semiterrestrial mangrove sesarmine crab Chasmagnathus convexus. At an average salinity and temperature of 20±1% and 19.2±0.2°C, the megalopa was attained 24 days after hatching. Morphologically, the first zoae of C. convexz1s is very similar to those of other species of the genus Chasmagnathus as well as species of the genus Helice, in that view all share the following characteristics: lateral spine on the carapace, three pairs of setae on the posterior margin of the telson furca, one plus five setae on the endopod of the maxillule, and two plus two setae on the endopod of the maxilla. The differences between the first zoea and megalopa of and those of its congeners are discussed.

Active steering of a tractor-semi-trailer

This paper develops a path-following steering control strategy for an articulated heavy goods vehicle. The controller steers the axles of the semi-trailer so that its rear end follows the path of the fifth wheel coupling: for all paths and all speeds. This substantially improves low-speed manoeuvrability, off-tracking, and tyre scrubbing (wear). It also increases high-speed stability, reduces 'rearward amplification', and reduces the propensity to roll over in high-speed transient manoeuvres. The design of a novel experimental heavy goods vehicle with three independent hydraulically actuated steering axles is presented. The path-following controller is tested on the experimental vehicle, at low and high speeds. The field test results are compared with vehicle simulations and found to agree well. The benefits of this steering control approach are quantified. In a low-speed 'roundabout' manoeuvre, low-speed off-tracking was reduced by 73 per cent, from 4.25 m for a conventional vehicle to 1.15 m for the experimental vehicle; swept-path width was reduced by 2 m (28 per cent); peak scrubbing tyre forces were reduced by 83 per cent; and entry tail-swing was eliminated. In an 80 km/h lane-change manoeuvre, peak path error for the experimental vehicle was 33 per cent less than for the conventional vehicle, and rearward amplification of the trailer was 35 per cent less. Increasing the bandwidth of the steering actuators improved the high-speed dynamic performance of the vehicle, but at the expense of increased oil flow.

Comparison of quantum chemistry calculation methods of nucleic acid base-quartets

Nine base-quartets were calculated by six semi-empirical methods and ab initio Hartree-Fork method using STO-3G basis set. The results showed that PM3 method can be use to calculate base quartets, the results of PM3 calculations are close to the ab initio

Gaussian Approximation Potential: an interatomic potential derived from first principles Quantum Mechanics

Simulation of materials at the atomistic level is an important tool in studying microscopic structure and processes. The atomic interactions necessary for the simulation are correctly described by Quantum Mechanics. However, the computational resources required to solve the quantum mechanical equations limits the use of Quantum Mechanics at most to a few hundreds of atoms and only to a small fraction of the available configurational space. This thesis presents the results of my research on the development of a new interatomic potential generation scheme, which we refer to as Gaussian Approximation Potentials. In our framework, the quantum mechanical potential energy surface is interpolated between a set of predetermined values at different points in atomic configurational space by a non-linear, non-parametric regression method, the Gaussian Process. To perform the fitting, we represent the atomic environments by the bispectrum, which is invariant to permutations of the atoms in the neighbourhood and to global rotations. The result is a general scheme, that allows one to generate interatomic potentials based on arbitrary quantum mechanical data. We built a series of Gaussian Approximation Potentials using data obtained from Density Functional Theory and tested the capabilities of the method. We showed that our models reproduce the quantum mechanical potential energy surface remarkably well for the group IV semiconductors, iron and gallium nitride. Our potentials, while maintaining quantum mechanical accuracy, are several orders of magnitude faster than Quantum Mechanical methods.

Investigating the link between well-being and energy use; an explorative case study between passive and active domestic energy management systems

The aim of this study was to explore how the remote control of appliances/lights (active energy management system) affected household well-being, compared to in-home displays (passive energy management system). A six-week exploratory study was conducted with 14 participants divided into the following three groups: active; passive; and no equipment. The effect on well-being was measured through thematic analysis of two semi-structured interviews for each participant, administered at the start and end of the study. The well-being themes were based on existing measures of Satisfaction and Affect. The energy demand for each participant was also measured for two weeks without intervention, and then compared after four weeks with either the passive or active energy management systems. These measurements were used to complement the well-being analysis. Overall, the measure of Affect increased in the passive group but Satisfaction decreased; however, all three measures on average decreased in the active group. The measured energy demand also highlighted a disconnect between well-being and domestic energy consumption. The results point to a need for further investigation in this field; otherwise, there is a risk that nationally implemented energy management solutions may negatively affect our happiness and well-being. © 2013 Elsevier Ltd.

Determinantal Clustering Processes - A Nonparametric Bayesian Approach to Kernel Based Semi-Supervised Clustering

Semi-supervised clustering is the task of clustering data points into clusters where only a fraction of the points are labelled. The true number of clusters in the data is often unknown and most models require this parameter as an input. Dirichlet process mixture models are appealing as they can infer the number of clusters from the data. However, these models do not deal with high dimensional data well and can encounter difficulties in inference. We present a novel nonparameteric Bayesian kernel based method to cluster data points without the need to prespecify the number of clusters or to model complicated densities from which data points are assumed to be generated from. The key insight is to use determinants of submatrices of a kernel matrix as a measure of how close together a set of points are. We explore some theoretical properties of the model and derive a natural Gibbs based algorithm with MCMC hyperparameter learning. The model is implemented on a variety of synthetic and real world data sets.

Quantum Confinement Effects and Electronic Properties of SnO2 Quantum Wires and Dots

On the basis of the density functional theory (DFT) within local density approximations (LDA) approach, we calculate the band gaps for different size SnO2 quantum wire (QWs) and quantum dots (QDs). A model is proposed to passivate the surface atoms of SnO2 QWs and QDs. We find that the band gap increases between QWs and bulk evolve as Delta E-g(wire) = 1.74/d(1.20) as the effective diameter d decreases, while being Delta E-g(dot) = 2.84/d(1.26) for the QDs. Though the similar to d(1.2) scale is significantly different from similar to d(2) of the effective mass result, the ratio of band gap increases between SnO2 QWs and QDs is 0.609, very close to the effective mass prediction. We also confirm, although the LDS calculations underestimate the band gap, that they give the trend of band gap shift as much as that obtained by the hybrid functional (PBE0) with a rational mixing of 25% Fock exchange and 75% of the conventional Perdew-Burke-Ernzerhof (PBE) exchange functional for the SnO2 QWs and QDs. The relative deviation of the LDA calculated band gap difference Lambda E-g compared with the corresponding PBE0 results is only within 5%. Additionally, it is found the states of valence band maximum (VBM) and conduction band minimum (CBM) of SnO2 QWs or QDs have a mostly p- and s-like envelope function symmetry, respectively, from both LDA and PBE0 calculations.

Rashba electron transport in one-dimensional quantum waveguides

The properties of Rashba wave function in the planar one-dimensional waveguide are studied, and the following results are obtained. Due to the Rashba effect, the plane waves of electron with the energy E divide into two kinds of waves with the wave vectors k(1)=k(0)+k(delta) and k(2)=k(0)-k(delta), where k(delta) is proportional to the Rashba coefficient, and their spin orientations are +pi/2 (spin up) and -pi/2 (spin down) with respect to the circuit, respectively. If there is gate or ferromagnetic contact in the circuit, the Rashba wave function becomes standing wave form exp(+/- ik(delta)l)sin[k(0)(l-L)], where L is the position coordinate of the gate or contact. Unlike the electron without considering the spin, the phase of the Rashba plane or standing wave function depends on the direction angle theta of the circuit. The travel velocity of the Rashba waves with the wave vector k(1) or k(2) are the same hk(0)/m*. The boundary conditions of the Rashba wave functions at the intersection of circuits are given from the continuity of wave functions and the conservation of current density. Using the boundary conditions of Rashba wave functions we study the transmission and reflection probabilities of Rashba electron moving in several structures, and find the interference effects of the two Rashba waves with different wave vectors caused by ferromagnetic contact or the gate. Lastly we derive the general theory of multiple branches structure. The theory can be used to design various spin polarized devices.

Electrically controllable RKKY interaction in semiconductor quantum wires

We demonstrate in theory that it is possible to all-electrically manipulate the RKKY interaction in a quasi-one-dimensional electron gas embedded in a semiconductor heterostructure, in the presence of Rashba and Dresselhaus spin-orbit interaction. In an undoped semiconductor quantum wire where intermediate excitations are gapped, the interaction becomes the short-ranged Bloembergen-Rowland superexchange interaction. Owing to the interplay of different types of spin-orbit interaction, the interaction can be controlled to realize various spin models, e.g., isotropic and anisotropic Heisenberg-like models, Ising-like models with additional Dzyaloshinsky-Moriya terms, by tuning the external electric field and designing the crystallographic directions. Such controllable interaction forms a basis for quantum computing with localized spins and quantum matters in spin lattices.

Quantum tunneling through graphene nanorings

We investigate theoretically quantum transport through graphene nanorings in the presence of a perpendicular magnetic field. Our theoretical results demonstrate that the graphene nanorings behave like a resonant tunneling device, contrary to the Aharonov-Bohm oscillations found in conventional semiconductor rings. The resonant tunneling can be tuned by the Fermi energy, the size of the central part of the graphene nanorings and the external magnetic field.