No description available.

Application of precision laser spectroscopy and optical clock technology to the ground and metastable, first excited state of the ²²⁹Th nucleus at < 10 eV has significant potential for use in optical frequency metrology and tests of variation of fundamental constants. This work is a report on the development of required technologies to realize such a nuclear optical clock with a single, trapped, laser cooled ²²⁹Th³⁺ ion. Creation, trapping, laser cooling, and precision spectroscopy are developed and refined first with the naturally occurring isotope, ²³²Th. These technologies are then extended to laser cooling and precision laser spectroscopy of the electronic structure of ²²⁹Th³⁺. An efficient optical excitation search protocol to directly observe this transition via the electron bridge is proposed. The extraordinarily small systematic clock shifts are estimated and the likely extraordinarily large sensitivity of the clock to variation of the fine structure constant is discussed.

Electrochromic thin films can effectively regulate the visible and infrared light passing through a window, demonstrating great potential to save energy and offer a comfortable indoor environment in buildings. However, long-term durability is a big issue and the physics behind this is far from clear. This dissertation work concerns two important parts of an electrochromic window: the anodic and cathodic layers. In particular, work focusing on the anodic side develop a new Ni oxide based layers and uncover degradation dynamics in Ni oxide thin films; and work focusing on the cathodic side addresses materials rejuvenation with the aim to eliminate degradation. In the first part of this dissertation work, iridium oxide is found to be compatible with acids, bases and Li+-containing electrolytes, and an anodic layer with very superior long-term durability was developed by incorporating of small amount (7.6 at. %) of Ir into Ni oxide. This film demonstrated sustained cycle-dependent growth of charge density and electrochromic modulation even after 10,000 CV cycles. The (111) and (100) crystal facets in Ni oxide are found to possess different abilities to absorb cation and/or anion, which yields different degrees of coloration and this is very significant for the electrochromic properties. The degradation of charge capacity in Ni oxide has an inevitable rapid decay in the first hundreds of cycles, subsequently combined with a more gradual decay, which is independent of applied potential and film composition. The consistent phenomenon can be very well modeled by power-law or stretched exponential decay; however the two models are indistinguishable in the current stage. Interestingly, in both models, the power-law exponent is 0.2 ≤ p ≤ 0.8, with most of the values around 0.5, in line with normal or anomalous diffusion models. The second part of dissertation work deals with cathodic WO3 and TiO2. WO3 suffers from ion trapping induced degradation of charge capacity and optical modulation upon electrochemical cycling. This speculation is strongly supported by direct evidence from Time-of-Flight Elastic Recoil Detection Analysis (ToF-ERDA). Most importantly, this ion trapping induced degradation can be eliminated by a galvanostatic de-trapping process. Significant ion-trapping takes place when x exceeds ~0.65 in LixWO3. The trapped ions are stable in the host structure, meaning that the ions cannot de-trap without external stimuli. The similar work done on TiO2 significantly complements and extends the work on the recuperation of WO3; the difference is that the trapped ions in host TiO2 seem to be less stable compared with the trapped ions in WO3.     Overall, this dissertation presents a refined conceptual framework for developing superior electrochromic windows in energy efficient buildings.

This thesis is concerned with the development of an intermediate magnetic field "clock-qubit" in ⁴³Ca⁺ at 146G and techniques to manipulate this qubit using microwaves and lasers. While ⁴³Ca⁺ has previously been used as a qubit, its relatively complicated level structure - with a nuclear spin of 7/2 and low-lying D-states -- makes cooling it in the intermediate field an intimidating prospect. As a result, previous experiments have used small magnetic fields of a few gauss where coherence times are limited and off-resonant excitation is a significant source of experimental error. We demonstrate a simple scheme that allows ⁴³Ca⁺ to be cooled in the intermediate field without any additional experimental complexity compared with low fields. Using the clock-qubit, we achieve a coherence time of T^*<sub style='position:relative;left:-.5em;'>2</sub> = 50 (10)s - the longest demonstrated in any single qubit. We also demonstrate a combined state preparation and measurement error of 6.8(6)x 10^-4 - the lowest achieved for a hyperfine trapped ion qubit [NVG⁺13] - and single-qubit logic gates with average errors of 1.0(3) x 10^-6 - more than an order of magnitude better than the previous record [BWC⁺11]. These results represent the state-of-the-art in the field of single-qubit control. Moreover, we achieve them all in a single scalable room-temperature ion trap using experimentally robust techniques and without relying on the use of narrow-linewidth lasers, magnetic field screening or dynamical decoupling techniques. We also present work on a recent scheme [OWC⁺11] to drive two-qubit gates using microwaves. We have constructed an ion trap with integrated microwave circuitry to perform these gates. Using this trap, we have driven motional sideband transitions, demonstrating the spin-motion coupling that underlies the two-qubit gate. We present an analysis of likely sources of experimental error during a future two-qubit gate and the design and preliminary characterisation of apparatus to minimise the main error contributions. Using this apparatus, we hope to perform a two-qubit gate in the near future.

Trapped cold ions are tools which we used to approach two very disparate areas of physics, strong coupling between Ba+ ions and optical resonators, and investigations of a low-energy nuclear isomer of 229-Th. The first part of this thesis describes our progress towards the integration of a miniature Paul (rf) ion trap with a high finesse (F=30000) optical cavity. Ba+ ions were trapped and cooled for long periods and a new scheme for isotope selective photoionization was developed. The second part of this thesis describes our progress towards controlled excitation of the low energy nuclear isomer of 229-Th, which may provide a bridge between the techniques of cold atomic and nuclear physics. As a step towards this goal, 232-Th3+ ions were confined in rf ions traps and cooled via collisions with a buffer gas of helium. A sophisticated scanning program was developed for controlling ion trap loading, tuning lasers, and running a CCD camera to look for fluorescence. The low-lying electronic transitions of Th3+ at 984 nm, 690 nm and 1087 nm were observed via laser fluorescence.

In recent years there has been much progress in the field of cold and ultracold molecular physics and a variety of experimental techniques for producing cold matter now exist. In particular, the generation of trapped molecular ions at mK temperatures has been achieved by sympathetic-cooling with laser-cooled atomic ions. By implementing schemes to selectively prepare and control the internal quantum state of molecular ions, and developing detection techniques, it will be increasingly possible to study cold state-selected chemical collisions in an ion-trap. Most molecular species produced in a selected rovibrational state have a lifetime of a few seconds, before the population is redistributed across numerous rovibrational states by interaction with the ambient blackbody radiation (BBR). Consequently, the investigation of state-selected reaction dynamics at low temperatures in experiments where long time scales (minutes to hours) are required, is hindered. This thesis looks into developing strategies that maintain state selection in molecular ions, allowing one to observe state-selected reactions in cold environments, in particular the state-selected reaction between C₂H⁺₂ and ND₃. Examining reactive ion molecule collisions under cold conditions provides insight into fundamental reaction dynamics, which are thermally averaged out at higher temperatures. A theoretical model is used to investigate laser-driven, blackbody-mediated, rotational cooling schemes for several ¹&Sigma; and ²Π diatomic species. The rotational cooling is particularly effective for DCl⁺ and HCl⁺, for which 92&percnt; and >99&percnt; (respectively) of the population can be driven into the rovibrational ground state. For the other systems a broadband optical pumping source is found to enhance the population that can be accumulated in the rovibrational ground state by up to 29&percnt; more than that achieved when exciting a single transition. The influence of the rotational constant, dipole moments and electronic state of the diatomics on the achievable rotational cooling is also studied. This approach is extended to consider the BBR interaction and rotational cooling of a linear polyatomic ion, C₂H⁺₂, which has a ²&Pi; electronic ground state. The (1-0) band of the &nu;₅ cis-bending mode is infrared active and strongly overlaps the 300 K blackbody spectrum. Hence the lifetimes of state-selected rotational levels are found to be short compared to the typical timescale of ion trapping experiments. Laser cooling schemes are proposed that could be experimentally viable, which involves simultaneous pumping of a set of closely spaced Q-branch transitions on the ²&Delta;_5/2-²&Pi;_3/2 band together with two ²&Sigma;⁺– ²&Pi;_1/2 lines. It is shown that this should lead to >70&percnt; of total population in the lowest rotational level at 300 K and over 99&percnt; at 77 K. In order to identify states of the acetylene ion that could be trapped sufficiently long enough for state-selected reactions in the ion trap with decelerated ND3, the theoretical work has been complemented by experimental investigations into the production of C₂H⁺₂ in selected states, and ion trapping of the same using sinusoidal and digital trapping voltages. Appropriate (2+1) REMPI (Resonance Enhanced Multiphoton Ionization) schemes are used to produce C₂H⁺₂ in different quantum states, with (1+1) Resonance Enhanced Multiphoton Dissociation (REMPD) employed to detect the ion thus produced. The concept of digital ion trapping for ejection onto MCPs is introduced. A comprehensive comparison between sinusoidal and digital trapping fields has been performed with respect to trap depth and stability regions. Programs have been developed to calculate the stability regions for different ions under varying experimental conditions. The trap depth has been derived for both digital and sinusoidal trapping fields. It is observed that as &tau; increases, the trap depth of a digital trap increases. For &tau; = 0.293, the trap depth and stability diagram for both sinusoidal and digital trapping fields would be equivalent. The trap depth at which the sinusoidal trap operates experimentally in our research group is ~1.36 eV. In contrast, the experimental parameters at which the digital trap operates generates a trap depth of 1.21 eV. Ca⁺ Coulomb crystals have been formed, stably trapped and stored for extended periods of time in both sinusoidally and digitally time-varying trapping fields. The sympathetic cooling of a diverse range of ions into Ca⁺ Coulomb crystals is demonstrated, again using both sinusoidal and digital trapping fields. Mass spectrometric detection of ionic reaction products using a novel ejection scheme has been developed, where ejection is achieved by switching off the trapping voltage and converting the quadrupole trap into an extractor-repeller pair by providing the ion trap electrodes with appropriate ejection pulses. This technique is developed using a digital trapping voltage rather than the sinusoidal trapping voltage, as ejection with sinusoidal trapping voltages is not clean (resonance circuitry used in the electronics induces ringing after switching off the trapping voltage). Coulomb crystals, both pure Ca⁺ and multi-component crystals, are ejected from the ion trap and the TOF trace obtained is recorded on an oscilloscope. When the integrated, base-line subtracted TOF peak is plotted against the number of ions in a Ca+ crystal and sympathetically-cooled Ca⁺ – CaF⁺ crystal, a linear relationship is obtained. This technique is found to be well mass-resolved, with the signal arising from CaOH⁺ (57 amu) and CaOD⁺ (58 amu) resolvable on the TOF trace. This technique would enable one to monitor a reaction in a Coulomb crystal where the reactant and product species are both either lighter or heavier than calcium, such as the reaction between C₂H⁺₂ and ND₃, something which has not been previously possible. It is, also, potentially a very important technique for reactions with many product channels.

A novel apparatus, combining buffer-gas cooling, electrostatic velocity selection and ion trapping, has been constructed and characterised. This apparatus is designed to investigate cold ion-molecule chemistry in the laboratory, at a variable translational and internal (rotational) temperature. This improves on previous experiments with translationally cold but rotationally hot molecule sources. The ability to vary the rotational temperature of cold molecules will allow for the experimental investigation of post-Langevin capture theories.

No description available.

This thesis describes the development of a new experimental technique for studying tunable-collision-energy, quantum state-selected, low-temperature ion-molecule reactions. This has been achieved through the combination of a Stark decelerator for neutral dipolar molecules, and a linear Paul ion trap. The Stark deceleration process for ND₃ was examined in detail, through the analysis of experimental data in combination with newly written molecular dynamics simulation programs. In order to prepare a sample of molecules appropriate for collision studies, additional beamline components were introduced after the decelerator. These components were: two hexapoles, to provide transverse focussing, maximising the molecular density; a molecular buncher, providing increased longitudinal velocity resolution; and a fast-opening shutter, to separate decelerated molecules from undecelerated molecules. The sympathetic-cooling of Xe⁺ ions and ND⁺₃ ions by laser-cooled, Coulomb crystallised ⁴⁰Ca⁺ ions with the ion trap was also studied. In particular, the stable trapping of Xe⁺ was demonstrated for the first time, and the experimental developments that led to this are discussed. The work in this thesis represents significant progress towards studying the reaction of tunable-energy ND₃ in the |j,mk> = |1,−1> quantum state with cold Xe⁺ ions. Ion-molecule reactions utilising ND₃ molecules electrostatically guided through the Stark decelerator were performed. It was observed that the main source of error in these experiments was in the calculation of the initial number of Xe⁺ ions that had been sympathetically cooled into the Coulomb crystal. The sensitivity of the crystal morphology to the number of Xe⁺ ions was evaluated using molecular dynamics simulations. Strategies have been developed to reduce this uncertainty in future studies. In addition to experimental work, the theory of low temperature ion-molecule reactions has been developed further. The temperature at which classical and quantum mechanical calculations diverge due to purely statistical effects has been investigated using different model intermolecular potentials, for closed-shell and open-shell species, and in the ground and rotationally excited states. From the results of these calculations, several promising candidate reactions have been suggested that might exhibit statistical quantum behaviour at experimentally achievable temperatures.

In the normal operation of quadrupole ion trap mass spectrometers, the trapped ions are ejected symmetrically through both the upper (detector) and lower(source) endcap electrodes during mass selective boundary ejection experiment. This reduces the sensitivity of the instrument by almost 50%. In this preliminary study, we altered the geometry parameters of the quadrupole ion traps to introduce asymmetry. The asymmetry displaced the ion cloud towards the detector endcap which resulted in a preferential ejection through this endcap, thus imparting directionality to the ejected ions and hence to the sensitivity enhancement. Two symmetrical mass analyzers have been taken up for numerical study. They include the Paul trap(QIT) and the cylindricaliontrap(CIT). Asymmetry to these geometries is introduced in two ways, one by varying the upper endcap hole radius alone and in other by stretching the trap along the upper endcap only. The escape velocity plots and mass selective boundary ejection simulations are used to demonstrate the directionality of ion ejection for these geometries. The simulations revealed a significant increase in the number of ions getting ejected in the direction of asymmetry.