In molecules, electronic state transitions can occur via quantum coupling of the states. If the coupling is due to the kinetic energy of the molecular nuclei, then electronic transitions are best represented in the adiabatic frame. If the coupling is instead facilitated through the potential energy of the nuclei, then electronic transitions are better represented in the diabatic frame. In our study, we modeled these latter transitions, called ``nonadiabatic transitions.'' For one nuclear degree of freedom, we modeled the de-excitation of a diatomic molecule. For two nuclear degrees of freedom, we modeled the de-excitation of an ethane-like molecule undergoing cis-trans isomerization. For both cases, we studied the dependence of the de-excitation on the nuclear configuration and potential energy of the molecule. We constructed a numerical model to solve the time-dependent Schr\"{o}dinger Equation for two coupled wave functions. Our algorithm takes full advantage of the sparseness of the numerical system, leading to a final set of equations that is solved recursively using nothing more than the Tridiagonal Algorithm. We observed that the most effective de-excitation occurred when the molecule transitioned from a stable equilibrium configuration to an unstable equilibrium configuration. This same mechanism is known to drive fast electronic transitions in the adiabatic frame. We concluded that while the adiabatic and diabatic frames are strongly opposed physically, the mathematical mechanism driving electronic transitions in the two frames is in some sense the same.

The growing applications for IoT devices have caused an increase in the study of low power consuming circuit design to meet the requirement of devices to operate for various months without external power supply. Scaling down the conventional CMOS causes various complications to design due to CMOS properties, therefore various non-conventional CMOS design techniques are being proposed that overcome the limitations. This thesis focuses on some of those emerging and novel low power design technique namely Adiabatic logic and low power devices like Magnetic Tunnel Junction (MTJ) and Carbon Nanotube Field Effect transistor (CNFET). Circuits that are used for large computations (multipliers, encryption engines) that amount to maximum part of power consumption in a whole chip are designed using these novel low power techniques.

The present work, briefly described below, consists of implementation of several quantum algorithms in an NMR Quantum Information Processor. Game theory gives us mathematical tools to analyze situations of conflict between two or more players who take decisions that influence their welfare. Classical game theory has been applied to various fields such as market strategy, communication theory, biological processes, foreign policies. It is interesting to study the behaviour of the games when the players share certain quantum correlations such as entanglement. Various games have been studied under the quantum regime with the hope of obtaining some insight into designing new quantum algorithms. Chapter 2 presents the NMR implementation of three such algorithms. Experimental NMR implementation given in this chapter are: (i) Three qubit ‘Dilemma’ game with corrupt sources’. The Dilemma game deals with the situation where three players have to choose between going/not going to a bar with a seating capacity of two. It is seen that in the players have a higher payoff if they share quantum correlations. However, the pay-off falls rapidly with increasing corruption in the source qubits. Here we report the experimental NMR implementation of the quantum version of the Dilemma game with and without corruption in the source qubits. (ii) Two qubit ‘Ulam’s game’. This is a two player game where one player has to find out the binary number thought by the other player. This problem can be solved with one query if quantum resources are used. This game has been implemented in a two qubit system in an NMR quantum information processor. (iii) Two qubit ‘Battle of Sexes’ game. This game deal with a situation where two players have conflicting choices but a deep desire to be together. This leads to a dilemma in the classical case. Quantum mechanically this dilemma is resolved and a unique solution emerges. The NMR implementation of the quantum version of this game is also given in this chapter. Quantum adiabatic algorithm is a method of solving computational problems by evolving the ground state of a slowly varying Hamiltonian. The technique uses evolution of the ground state of a slowly varying Hamiltonian to reach the required output state. In some cases, such as the adiabatic versions of Grover’s search algorithm and Deutsch-Jozsa algorithm, applying the global adiabatic evolution yields a complexity similar to their classical algorithms. However, if one uses local adiabatic evolutions, their complexity is of the order √N (where N=2n) [37, 38]. In Chapter 3, the NMR implementation of (i) the Deutsch-Jozsa and the (ii) Grover’s search algorithm using local adiabatic evolution has been presented. In adiabatic algorithm, the system is first prepared in the equal superposition of all the possible states which is the ground state of the beginning Hamiltonian. The solution is encoded in the ground state of the final Hamiltonian. The system is evolved under a linear combination of the beginning and the final Hamiltonian. During each step of the evolution the interpolating Hamiltonian slowly changes from the beginning to the final Hamiltonian, thus evolving the ground state of the beginning Hamiltonian towards the ground state of the final Hamiltonian. At the end of the evolution the system is in the ground state of the final Hamiltonian which is the solution. The final Hamiltonian, for each of the two cases of adiabatic algorithm described in this chapter, are constructed depending on the problem definition. Adiabatic algorithms have been proved to be equivalent to standard quantum algorithms with respect to complexity [39]. NMR implementation of adiabatic algorithms in homonuclear spin systems face problems due to decoherence and complicated pulse sequences. The decoherence destroys the answer as it causes the final state to evolve to a mixed state and in homonuclear systems there is a substantial evolution under the internal Hamiltonian during the application of the soft pulses which prevents the initial state to converge to the solution state. The resolution of these issues are necessary before one can proceed for the implementation of an adiabatic algorithm in a large system. Chapter 4 demonstrates that by using ‘strongly modulated pulses’ for creation of interpolating Hamiltonian, one can circumvent both the problems and thus successfully implement the adiabatic SAT algorithm in a homonuclear three qubit system. The ‘strongly modulated pulses’ (SMP) are computer optimized pulses in which the evolution under the internal Hamiltonian of the system and RF inhomogeneities associated with the probe is incorporated while generating the SMPs. This results in precise implementation of unitary operators by these pulses. This work also demonstrates that the strongly modulated pulses tremendously reduce the time taken for the implementation of the algorithm, can overcome problems associated with decoherence and will be the modality in future implementation of quantum information processing by NMR. Quantum search algorithm, involving a large number of qubits, is highly sensitive to errors in the physical implementation of the unitary operators. This can put an upper limit to the size of the data base that can be practically searched. The lack of robustness of the quantum search algorithm for a large number of qubits, arises from the fact that stringent ‘phase-matching’ conditions are imposed on the algorithm. To overcome this problem, a modified operator for the search algorithm has been suggested by Tulsi [40]. He has theoretically shown that even when there are errors in implementation of the unitary operators, the search algorithm with his modified operator converges to the target state while the original Grover’s algorithm fails. Chapter 5, presents the experimental NMR implementation of the modified search algorithm with errors and its comparison with the original Grover’s search algorithm. We experimentally validate the theoretical predictions made by Tulsi that the introduction of compensatory Walsh-Hadamard and phase-flip operations refocuses the errors. Experimental Quantum Information Processing is in a nascent stage and it would be too early to predict its future. The excitement on this topic is still very prevalent and many options are being explored to enhance the hardware and software know-how. This thesis endeavors in this direction and probes the experimental feasibility of the quantum algorithms in an NMR quantum information processor.

In recent times, application of aluminum alloys is favored in the transportation sectors such as the aerospace and automobile industries where reduced fuel consumption and greenhouse gas emission are major priorities. In these applications, these alloys can be exposed to dynamic shock loading conditions as in the case of car crash and birds’ collision during aircraft’s take-off or landing. This study therefore focused on the deformation and damage mechanisms in AA 2017, AA 2024 and AA 2624 aluminum alloys under both quasi-static and dynamic impact loading conditions. Cylindrical specimens of the selected aluminum alloys were investigated under both quasi-static loading at 3.2 x10-3 s-1 using an Instron R5500 mechanical testing machine and dynamic impact loading using the split Hopkinson pressure bar at strain rates ranging between 2000 and 8000 s-1. The effects of strain rate and temper condition on the microstructural evolution in the alloys during mechanical loading were studied. The electron backscatter diffraction (EBSD) technique was used to investigate the texture of the naturally-aged AA 2017 and AA 2624 alloys before and after dynamic shock loading. The contributions of the major alloying elements such as copper, magnesium and silicon to the microstructural evolution and deformation behavior of the alloys under the dynamic shock loading condition were also studied using the energy dispersive spectroscopy (EDS) technique. Results showed that the morphology and atomic distribution of particles in the investigated alloys are functions of the temper condition. The hardness of all the three alloys was higher in the age-hardened conditions than the annealed ones. Although deformation of the alloy under quasi-static compressive loading was dominated by strain hardening, flow softening leading to strain localization and formation of shear bands occurred once certain critical strain values were reached. Under both quasi-static and dynamic loading, the alloys with low Cu:Mg ratio (AA 2024 and AA 2624) showed higher mechanical strength in age-hardened condition than that with high Cu:Mg ratio (AA 2017). All the alloys in the annealed condition exhibited an enhanced plasticity and formability. Intense strain localization leading to formation of adiabatic shear bands (ASBs) was the principal contributor to failure in the alloys under dynamic impact loading. Both deformed and transformed bands were observed, with cracking occurring mainly along the transformed shear bands. The tendency for formation of adiabatic shear bands is observed to be a function of the alloy composition, temper condition, strain, strain rate and strain hardening rate. In the natural aging condition, AA 2024 showed the highest susceptibility to formation of ASBs followed by AA 2624 and AA 2017 in that order. On the other hand, AA 2024 has the least susceptibility in the artificially-aged condition. Occurrence of bifurcation of transformed bands in dynamic impacted specimens is dependent on temper condition, strain and strain rate. The mechanism of fracture of the precipitation hardened samples is typical of ductile fracture occurring sequentially by nucleation, growth, and coalescence of micro-voids processes within transformed band. Elongated grains were observed to arrest propagating shear band depending on the angle the band makes with elongated grains. The higher the angle of inclination of a shear band to the grain on its path, the higher the tendency of the grain to stop its propagation. Texture analysis of the impacted specimens of AA 2017-T451 and AA 2624-T351 shows that the former has a higher tendency for the evolution of ultra-fine DRX grains within the transformed shear band. High strain rate led to the development of CD//<111> orientations at the expense of CD//<110> orientations. Schmid factor calculations performed on few different orientations in the starting microstructure shows that CD//<110> is less susceptible to slip deformation and consequently underwent rotation to CD//<111>.

The 20th century saw the first revolution of quantum mechanics, setting the rules for our understanding of light, matter, and their interaction. The 21st century is focused on using these quantum mechanical laws to develop technologies which allows us to solve challenging practical problems. One of the directions is the use quantum devices which promise to surpass the best computers and best known classical algorithms for solving certain tasks. Crucial to the design of realistic devices and technologies is to account for the open nature of quantum systems and to cope with their interactions with the environment. In the first part of this dissertation, we show how to tackle classical optimization problems of interest in the physical sciences within one of these quantum computing paradigms, known as quantum annealing (QA). We present the largest implementation of QA on a biophysical problem (six different experiments with up to 81 superconducting quantum bits). Although the cases presented here can be solved on a classical computer, we present the first implementation of lattice protein folding on a quantum device under the Miyazawa-Jernigan model. This is the first step towards studying optimization problems in biophysics and statistical mechanics using quantum devices. In the second part of this dissertation, we focus on the problem of excitonic energy transfer. We provide an intuitive platform for engineering exciton transfer dynamics and we show that careful consideration of the properties of the environment leads to opportunities to engineer the transfer of an exciton. Since excitons in nanostructures are proposed for use in quantum information processing and artificial photosynthetic designs, our approach paves the way for engineering a wide range of desired exciton dy- namics. Finally, we develop the theory for a two-dimensional electronic spectroscopic technique based on fluorescence (2DFS) and challenge previous theoretical results claiming its equivalence to the two-dimensional photon echo (2DPE) technique which is based on polarization. Experimental realization of this technique confirms our the- oretical predictions. The new technique is more sensitive than 2DPE as a tool for conformational determination of excitonically coupled chromophores and o↵ers the possibility of applying two-dimensional electronic spectroscopy to single-molecules.

The concept of Berry phase, since its proposition in 1984, has found numerous applications and appears in almost every branch of physics today. In this work, we study several physical effects in ferromagnetic metal materials which are manifestations of the Berry phase. We first show that when a domain wall in a ferromagnetic nanowire is undergoing precessional motion, it pumps an electromotive force which follows a universal Josephson-type relation. We discover that the integral of the electromotive force over one pumping cycle is a quantized topological invariant equal to integer multiples of h/e, which does not depend on the domain wall geometry nor its detailed dynamic evolution. In particular, when a domain wall in a nanowire is driven by a constant magnetic field, we predict that the generated electromotive force is proportional to the applied field with a simple coefficient consisting of only fundamental constants. Our theoretical prediction has been successfully confirmed by experiments. Similar effect known as spin pumping occurs in magnetic multilayer heterostructures, where a precessing free magnetic layer pumps a spin current into its adjacent normal metal layers. Based on this effect, we propose two magnetic nanodevices that can be useful in future spintronics applications: the magnetic Josephson junction and the magneto-dynamic battery. The magnetic Josephson junction has a drastic increase in resistance when the applied current exceeds a critical value determined by the magnetic anisotropy. The magneto-dynamic battery acts as a conventional charge battery in a circuit with well-defined electromotive force and internal resistance. We investigate the condition under which the power output and efficiency of the battery can be optimized. Finally we study the side jump contribution in the anomalous Hall effect of a uniformly magnetized ferromagnetic metal. The side jump contribution, although arises from disorder scattering, was believed to be independent of both the scattering strength and the disorder density. Nevertheless, we find that it has a sensitive dependence on the spin structure of the disorder potential. We therefore propose a classification scheme of disorder scattering according to their spin structures. When two or more classes of disorders are present, the value of side jump is no longer fixed but depends on the relative disorder strength between classes. Due to this competition, the side jump contribution could flow from one class dominated limit to another class dominated limit when certain system control parameter changes. Our result indicates that the magnon scattering plays a role distinct from the normal impurity scattering and the phonon scattering in the anomalous Hall effect, because they belong to different scattering classes. / text

Superoxide, the product of the one-electron reduction of dioxygen, is a molecule of enormous importance. It participates in a variety of critical physiological processes and is also an important component of fuel cells where it is an intermediate in the cathodic reaction. However, the electrochemical behavior of superoxide, mainly its reduction, is not well understood. Here, the electrochemical behavior of superoxide has been investigated in acetonitrile on glassy carbon electrodes, through cyclic voltammetry experiments. By stabilizing the electrogenerated superoxide, aprotic solvents afford an opportunity to study its electrochemical reactions further. Superoxide was generated electrochemically from dioxygen at the first voltammetric peak. In the presence of hydrogen-bond donors (water, methanol, 2-propanol), the superoxide forms a complex with the donor resulting in a positive shift in the formal potential which can be analyzed to obtain formation constants for these complexes. Stronger acids (2,2,2- trifluoroethanol, 4-tert-butylphenol) result in protonation of superoxide followed by reduction to produce HO₂-. On scanning to more negative potentials a second peak is observed which is irreversible and extremely drawn out along the potential axis indicating a small value of the transfer coefficient α. Addition of hydrogenbond donors, HA, brings about a positive shift in this peak, without a noticeable change in shape. The reaction occurring at the second peak is a concerted proton-coupled electron transfer (PCET) in which the electron is transferred to superoxide and a proton is transferred from HA to superoxide forming HO₂- and A- in a concerted process. We estimate the standard potential for this reaction for the case of water as the donor. This value suggests that the reaction at the second peak occurs at very high driving forces. Kinetic simulations using both Butler-Volmer and Marcusian schemes were performed to estimate the kinetic parameters. The unusually low rate constants obtained suggest high nonadiabaticity for this PCET reaction. The reaction was also found to proceed with an unusually large reorganization energy. Consistent with a PCET, a kinetic isotope effect, HA vs. DA, was detected for the three hydrogen-bond donors.

Theoretical investigation of the dynamics of adiabatic quantum mechanics in two different, highly polar systems has been made. The systems were chosen for their fundamental scientific interest, as they represent atoms and molecules with exaggerated properties, as well as ease of experimental study as such highly polar systems are easier to manipulate using readily-available electric fields. A model two-level system is used to derive one approach for maximizing the probability of adiabatic passage through an avoided crossing and this is compared with the classic Landau-Zener result, and the commonly encountered spin-flip problem of a particle with spin located in a rotating magnetic field. This approach is applied to the avoided crossing between the n = 13, n1 − n2 = 11 (dipole moment of 532 D) and the n = 14, n1 − n2 = −12 (dipole moment of -657 D) highly polar Stark states of the lithium atom at 447 kV/m. Ion-pair formation from two neutral lithium atoms, one in the 2s ground state and the other in an excited state, is also investigated. The cross section σ(v) for free ion-pairs is calculated for the initial colliding pairs of atomic states located below the ion-pair threshold. Li(2s) + Li(3d) is seen to possess the largest cross section (σ(v0) = 569.2 a.u.) at its threshold velocity. The implications of this for bound ion-pair, i.e. heavy Rydberg system, production are briefly discussed. Furthermore, experimental progress towards the production of these atomic and molecular systems from a beam of lithium is presented. / Thesis (Master, Physics, Engineering Physics and Astronomy) -- Queen's University, 2009-12-09 16:49:41.184

Hazard communication is an essential part of a comprehensive safety plan, especially for those facilities that contain reactive chemicals. There are a variety of means of communicating a chemical hazard, but one of the most prevalent in the United States is the Instability Rating found in the NFPA 704 standard. While the NFPA 704 identifies hazards associated with exothermically decomposing compounds, it neglects compounds that decompose endothermicly to form large quantities of gas. Such compounds have been known to cause accidents due to pressure buildup, such as in the BP Amoco Polymers explosion in 2001. In this work, twenty-five compounds were examined via an APTAC to determine their pressure and temperature profiles. These profiles were then used to determine the amount of gas generated, the gas generation rate, the gas generation product, the onset temperature, and the instantaneous power density. These properties were analyzed to determine those that best represented the instability hazard of the chemical. Ultimately, the molar gas generation rate and onset temperature were chosen to rate the selected chemicals, and new cut-offs were established to divide the chemicals into revised instability groupings. Compounds that did not decompose in the temperature range examined were given the rating of zero. Compounds with low onset temperatures and high gas generation rates were assigned the rating of 4, while chemicals with high T_onset and low dn/dt_maxn were assigned a value of 1. Chemicals with high onset temperatures and high gas generation rates were grouped into rating 3. Group 2 included low onset temperature compounds with low gas generation rates. The cut-offs used to define these regions were 130 degrees C for the onset temperature and 0.01 (1/min) for the gas generation rate. The ratings were found to be comparable to the current NFPA system, but improved upon it by providing a valid rating (group 1) for the chemicals that endothermically generated gas. Detailed plots of the data are provided as well as suggestions for future work.

High strain rate plastic deformation of metals results in the formation of localized zones of severe shear strain known as adiabatic shear bands (ASBs), which are a precursor to shear failure. The formation of ASBs in a high-strength low alloy steel, namely AISI 4340, was examined based on prior heat treatments (using different austenization and tempering temperatures), testing temperatures, and impact strain rates in order to map out grain size and grain deformation behaviour during the formation of ASBs. In the current experimental investigation, ASB formation was shown to be a microstructural phenomenon which depends on microstructural properties such as grain size, shape, orientation, and distribution of phases and hard particles—all controlled by the heat treatment process. Each grain is unique and its material properties are heterogeneous (based on its size, shape, and the complexity of the microstructure within the grain). Using measurements of grain size at various heat treatments as well as dynamic stress-strain data, a finite element model was developed using Matlab and explicit dynamic software LSDYNA to simulate the microstructural deformation of grains during the formation of ASBs. The model simulates the geometrical grain microstructure of steel in 2D using the Voronoi Tessellation algorithm and takes into account grain size, shape, orientation, and microstructural material property inhomogeneity between the grains and grain boundaries. The model takes advantage of the Smooth Particle Hydrodynamics (SPH) meshless method to simulate highly localized deformation as well as the Johnson-Cook Plasticity material model for defining the behavior of the steel at various heat treatments under high strain rate deformation.The Grain Model provides a superior representation of the kinematics of ASB formation on the microstructural level, based on grain size, shape and orientation. It is able to simulate the microstructural mechanism of ASB formation and grain refinement in AISI 4340 steel, more accurately and realistically than traditional macroscopic models, for a wide range of heat treatment and testing conditions.