This examines the interplay of structure and local electrostatic fields in protein-protein and protein-solvent interactions. The partial charges of the protein amino acids and the polarization of the surrounding solvent create a complex system of electrostatic fields at protein-protein and protein-solvent interfaces. An approach incorporating vibrational Stark effect (VSE) spectroscopy, dissociation constant measurements, and molecular dynamics (MD) simulations was used to investigate the electrostatic interactions in these interfaces. Proteins p21Ras (Ras) and Rap1A (Rap) have nearly identical amino acid sequences and structures along the effector-binding region but bind with different affinities to Ral guanine nucleotide dissociation stimulator (RalGDS). A charge reversion mutation at position 31 alters the binding affinity of Ras and Rap with RalGDS from 0.1 [mu]M and 1 [mu]M, to 1 [mu]M and 0.5 [mu]M, respectively. A spectral probe was placed at various locations along the binding interface on the surface of RalGDS as it was docked with Ras and Rap single (position 30 or 31) and double mutants (both positions). By comparing the probes' absorption energies with the respective wild-type (WT) analogs, VSE spectroscopy was able to measure molecular-level electrostatic events across the protein-protein interface. MD simulations provided a basis for deconvoluting the structural and electrostatic changes observed by the probes. The mutation at position 31 was found to be responsible for both structural and electrostatic changes compared to the WT analogs. Furthermore, previous identification of positions N27 and N29 on RalGDS as "hot spots" that help discriminate between structurally similar GTPases was supported. The RalGDS probe-containing variants and three model compounds were placed in aqueous solvents with varying dielectric constants to measure changes in absorption energy. We investigated the ability of the Onsager solvent model to describe the solvent induced changes in absorption energy, while MD simulations were employed to determine the location and solvation of the probes at the protein-solvent interface. The solvent accessible-surface area, a measure of hydration, was determined to correlate well with the change in magnitude of the probe's absorption energy and the displaced solvent by the probe. / text

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

Functional heterojunctions in organic electronic devices are interfaces formed either between a conducting electrode and an organic semiconductor or between two different organic semiconductors in blended and multilayered structures. This thesis is primarily concerned with the energy level alignment and the interfacial electronic structures at functional heterojunctions encountered in electronic devices made with solution-processable semiconducting polymers. Investigations on the electronic structures across these heterointerfaces are performed with the combined use of electromodulation and photoemission spectroscopic techniques. Electromodulation and ultraviolet photoemission spectroscopic techniques enable direct determination of the surface work functions of electrodes at the electrode/semiconducting polymer interfaces. We overcame the inherent problems faced by electromodulation spectroscopy, which undermine accurate determination of interfacial electronic structures, by performing electroabsorption (EA) measurements at reduced temperatures. We showed in this thesis that low-temperature EA spectroscopy is a surface sensitive technique that can determine the interface electronic structures in electrode/polymer semiconductor/electrode diodes. Using this technique, we demonstrated that the energy level alignments in these solution-processed organic electronic devices are determined by the surface work functions of passivated metals rather than by those of clean metals encountered in ultrahigh vacuum. This thesis also discloses our studies on the electronic structures in polymeric diodes with type II donor-acceptor heterojunctions using the EA spectroscopy. We showed that minimising meausurement temperature and attenuating EA illumination intensity enable accurate determinations of the electronic structures in these devices. We demonstrated that the electronic structures and the performance characteristics of multilayered polymer light-emitting diodes are also determined by the surface work functions of passivated metals. Our investigations confirm that electronic doping of the organic active layers, rather than minimisation of the Schottky barriers at electrode/polymer contacts, holds the key in realising high-performance organic light-emitting devices.

The quantum confined Stark effect (QCSE) and ultrafast absorption dynamics near the bandedge have been investigated in p-i-n waveguides comprising quantum confined heterostructures grown on GaAs substrates, for emission at 1.3um. The materials are; isolated InAs/InGaAs dot-in-a-well (DWELL) quantum dots (QD), bilayer InAs quantum dots and GaInNAs multiple quantum wells (MQW). The focus was to investigate these dynamics in a planar waveguide geometry, for the purpose of large scale integration in optical systems. Initial measurements of the QCSE using photocurrent measurements showed a small shift for isolated QDs whilst a significant shift of 40nm (at 1340nm) was demonstrated for bilayer dots, comparable to that of GaInNAs MWQ (30nm at 1300nm). These are comparable to InP based quaternary multiple quantum wells used in modulator devices. With the use of a broadband continuum source the isolated quantum dots exhibit both a small QCSE (15nm at 1280nm) and minimal broadening which is desirable for saturable absorbers used in monolithic modelocked semiconductor lasers (MMSL). A robust experimental set-up was developed for characterising waveguide modulators whilst the electroabsorption and electro-refraction was calculated (dn=1.5x10⠻³) using the Kramers-Kronig dispersion relation. Pump probe measurements were performed at room temperature using 250fs pulses from an optical parametric oscillator (OPO) on the three waveguide samples. For the isolated QDs ultrafast absorption recovery was recorded from 62ps (0V) to 700fs (-10V and the shortest times shown to be due to tunneling. Additionally we have shown good agreement of the temperature dependence of these dots and the pulse width durations from a modelocked semiconductor laser using the same material. Bilayer QDs are shown to exhibit ultrafast absorption recovery from 119ps (0V) to 5ps (-10V) offering potential for applications as modelocking elements. The GaInNAs multiple quantum wells show absorption recovery of 55ps (0V), however under applied reverse bias they exhibit long lived field screening transients. These results are explained qualitatively by the spatial separation of electrons and holes at heterobarrier interfaces.

Resonant cavity controlled klystron frequency stabilization circuits and quartz-crystal oscillator frequency stabilization circuits were investigated for reflex klystrons operating at frequencies in the X-band range. The crystal oscillator circuit employed achieved better than 2 parts in 10 in frequency stability. A test of the functional properties of the frequency standard was made using the Stark effect in molecules.

La photo-isomérisation par ouverture de cycle du benzopyrane a été étudiée à l'aide de la méthode MCTDH (Multi-Configuration Time-Dependent Hartree). Nous avons introduit différentes stratégies pour contrôler la conversion du benzopyrane en mérocyanine à l'aide d'impulsions laser. Nous avons utilisé un modèle pour le potentiel électronique à six dimensions développé dans le cadre d'un travail antérieur. Le modèle repose sur une généralisation des Hamiltoniens modèles standards pour les couplages vibroniques et utilise les six coordonnées les plus importantes pour le processus. Le principal objectif est de fournir des stratégies de contrôle qui pourront être utilisées par les expérimentateurs par la suite. Plus précisément, nous avons proposé: (i) une technique de type pompe-sonde pour contrôler la photostabilité, (ii) une stratégie en deux étape avec une préexcitation vibrationnel du système,(iii) une stratégie reposant sur un contrôle par effet Stark induit par un laser non-résonant. / The ring-opening photoisomerization of benzopyran, which occurs via a photochemical route involving a conical intersection,has been studied with quantum dynamics calculations using the multi-configuration time-dependent Hartree method (MCTDH). We introduce a mechanistic strategy to control the conversion of benzopyran to merocyanine with laser pulses. We use asix-dimensional model developed in a previous work for the potential energy surfaces (PES) based on an extension of thevibronic-coupling Hamiltonian model (diabatization method by ansatz), which depends on the most active degrees of freedom. The main objective of these quantum dynamics simulations is to provide a set of strategies that could help experimentalists tocontrol the photoreactivity vs. photostability ratio (selectivity). In this work we present:(i) a pump-dump technique used tocontrol the photostability, (ii) a two-step strategy to enhance the reactivity of the system: first, a pure vibrational excitation inthe electronic ground state that prepares the system and, second, an ultraviolet excitation that brings the system to the firstadiabatic electronic state; (iii) finally the effect of a non-resonant pulse (Stark effect) on the dynamics.

Ce travail de thèse porte sur l’étude des propriétés optiques et électroniques des puits quantiques de GaN / AlGaN grâce à des techniques classiques de réflectivité résolue en angle et de photoluminescence, ainsi qu’avec la technique de photoluminescence résolue temporellement. Les expériences de photoluminescence en régime continu ont permis d’estimer les énergies des transitions excitoniques qui sont également accessibles en réflectivité. Ces techniques ont ainsi permis de mettre en évidence l’effet Stark dans les puits quantiques GaN / AlGaN. L’effet Stark sur les énergies de transition est cohérent avec la théorie des fonctions enveloppes. Les spectres de réflectivité permettent d’accéder à la force d’oscillateur des excitons grâce à leur modélisation par le formalisme des matrices de transfert, prenant en compte les phénomènes d’élargissement homogène et inhomogènes des transitions optiques. Enfin, les mesures de photoluminescence résolue en temps en fonction de la température, ont également permis d’extraire la force d’oscillateur qui est inversement proportionnelle au temps de recombinaison radiative. Cette étude a également permis de mettre en évidence l’effet Stark responsable de la diminution de la force d’oscillateur en fonction de l’épaisseur du puits quantique mais aussi en fonction de la composition d’aluminium. L’augmentation de l’épaisseur du puits entraîne une diminution du recouvrement des fonctions d’onde, et une augmentation de la composition d’aluminium intensifie le champ électrique et diminue également le recouvrement des fonctions d’onde. / This work deals with the study of optical and electronic properties of GaN / AlGaN quantum wells, by classical techniques of spectroscopy including angle resolved reflectivity or photoluminescence, but also by time resolved photoluminescence. The continuous wave photoluminescence experiments allowed estimating the energies of the excitonic transitions, which are also available through reflectivity. These techniques highlighted the Stark effect in GaN / AlGaN quantum wells. The influence of the Stark effect on the energies of the excitonic transitions is well reproduced by envelop functions theory. Reflectivity spectra give access to the oscillator strength via their fitting by transfer matrix formalism, taking in account both homogeneous and inhomogeneous broadenings of the optical transitions. Finally, time resolved photoluminescence measurements as a function of temperature were performed to extract the oscillator strength, which is proportional to the inverse of the radiative recombination time. This technique also highlighted the Stark effect which is responsible of the vanishing of the oscillator strength with the thickness of the well and the aluminium composition. Increasing of the quantum well’s thickness induces decreasing of wave functions overlap, as well as an increasing of the aluminium composition which intensifies the electric field and splits the wave functions.

Energy from the sun can be converted to low cost electricity using dye-sensitized solar cells (DSCs). Dye molecules adsorbed to the surface of mesoporous TiO2 absorb light and inject electrons into the semiconductor. They are then regenerated by the reduced redox species from an electrolyte, typically consisting of the iodide/tri-iodide redox couple in an organic solvent. In a solid state version of the DSC, the liquid electrolyte is replaced by an organic hole conductor. Solid state DSCs using 2,2'7,7'-tetrakis-(N,N-di-p-methoxyphenyl-amine)-9,9'-spirobifluorene (spiro-MeOTAD) have reached conversion efficiencies of up to 6 %, which is about half of the efficiency of the best iodide/tri-iodide cells.   Measurement techniques, such as spectroelectrochemistry and photo-induced absorption spectroscopy (PIA), were developed and applied to study the working mechanism of organic dyes in solid state DSCs under solar cell operating conditions. The energy alignment of the different solar cell components was studied by spectroelectrochemistry and the results were compared to photoelectron spectroscopy. PIA was used to study the injection and regeneration processes. For the first time, it was shown here that the results of PIA are influenced by an electric field due to the electrons injected into the TiO2. This electric field causes a shift in the absorption spectrum of dye molecules adsorbed to the TiO2 surface due to the Stark effect.   Taking the Stark effect into consideration during the data analysis, mechanistic differences between solid state and conventional DSCs were found. A perylene dye, ID176, was only able to efficiently inject electrons into the TiO2 in presence of lithium ions and in absence of a solvent. As a result, the sensitiser worked surprisingly well in solid state DSCs but not in liquid electrolyte ones. Regeneration of oxidised dye molecules by spiro-MeOTAD was found to be fast and efficient and spiro-MeOTAD could even reduce excited dye molecules.

Ce travail de thèse porte sur l’étude des propriétés optiques et électroniques des puits quantiques de GaN / AlGaN grâce à des techniques classiques de réflectivité résolue en angle et de photoluminescence, ainsi qu’avec la technique de photoluminescence résolue temporellement. Les expériences de photoluminescence en régime continu ont permis d’estimer les énergies des transitions excitoniques qui sont également accessibles en réflectivité. Ces techniques ont ainsi permis de mettre en évidence l’effet Stark dans les puits quantiques GaN / AlGaN. L’effet Stark sur les énergies de transition est cohérent avec la théorie des fonctions enveloppes. Les spectres de réflectivité permettent d’accéder à la force d’oscillateur des excitons grâce à leur modélisation par le formalisme des matrices de transfert, prenant en compte les phénomènes d’élargissement homogène et inhomogènes des transitions optiques. Enfin, les mesures de photoluminescence résolue en temps en fonction de la température, ont également permis d’extraire la force d’oscillateur qui est inversement proportionnelle au temps de recombinaison radiative. Cette étude a également permis de mettre en évidence l’effet Stark responsable de la diminution de la force d’oscillateur en fonction de l’épaisseur du puits quantique mais aussi en fonction de la composition d’aluminium. L’augmentation de l’épaisseur du puits entraîne une diminution du recouvrement des fonctions d’onde, et une augmentation de la composition d’aluminium intensifie le champ électrique et diminue également le recouvrement des fonctions d’onde. / This work deals with the study of optical and electronic properties of GaN / AlGaN quantum wells, by classical techniques of spectroscopy including angle resolved reflectivity or photoluminescence, but also by time resolved photoluminescence. The continuous wave photoluminescence experiments allowed estimating the energies of the excitonic transitions, which are also available through reflectivity. These techniques highlighted the Stark effect in GaN / AlGaN quantum wells. The influence of the Stark effect on the energies of the excitonic transitions is well reproduced by envelop functions theory. Reflectivity spectra give access to the oscillator strength via their fitting by transfer matrix formalism, taking in account both homogeneous and inhomogeneous broadenings of the optical transitions. Finally, time resolved photoluminescence measurements as a function of temperature were performed to extract the oscillator strength, which is proportional to the inverse of the radiative recombination time. This technique also highlighted the Stark effect which is responsible of the vanishing of the oscillator strength with the thickness of the well and the aluminium composition. Increasing of the quantum well’s thickness induces decreasing of wave functions overlap, as well as an increasing of the aluminium composition which intensifies the electric field and splits the wave functions.

abstract: This dissertation aims to study and understand relevant issues related to the electronic, spin and valley transport in two-dimensional Dirac systems for different given physical settings. In summary, four key findings are achieved. First, studying persistent currents in confined chaotic Dirac fermion systems with a ring geometry and an applied Aharonov-Bohm flux, unusual whispering-gallery modes with edge-dependent currents and spin polarization are identified. They can survive for highly asymmetric rings that host fully developed classical chaos. By sustaining robust persistent currents, these modes can be utilized to form a robust relativistic quantum two-level system. Second, the quantized topological edge states in confined massive Dirac fermion systems exhibiting a remarkable reverse Stark effect in response to an applied electric field, and an electrically or optically controllable spin switching behavior are uncovered. Third, novel wave scattering and transport in Dirac-like pseudospin-1 systems are reported. (a), for small scatterer size, a surprising revival resonant scattering with a peculiar boundary trapping by forming unusual vortices is uncovered. Intriguingly, it can persist in arbitrarily weak scatterer strength regime, which underlies a superscattering behavior beyond the conventional scenario. (b), for larger size, a perfect caustic phenomenon arises as a manifestation of the super-Klein tunneling effect. (c), in the far-field, an unexpected isotropic transport emerges at low energies. Fourth, a geometric valley Hall effect (gVHE) originated from fractional singular Berry flux is revealed. It is shown that gVHE possesses a nonlinear dependence on the Berry flux with asymmetrical resonance features and can be considerably enhanced by electrically controllable resonant valley skew scattering. With the gVHE, efficient valley filtering can arise and these phenomena are robust against thermal fluctuations and disorder averaging. / Dissertation/Thesis / Doctoral Dissertation Electrical Engineering 2017