The widespread pollution of mercury motivates research into its atmospheric chemistry and transport. Gaseous elemental mercury (Hg(0)) dominates mercury emission to the atmosphere, but the rate of its oxidation to mercury compound (Hg(II)) plays a significant role in controlling where and when mercury deposits to ecosystems. Atomic bromine is regarded as the main oxidant for Hg(0) oxidation, known to initiate the oxidation via a two-step process in the atmosphere – formation of BrHg (R1) and subsequent reactions of BrHg with abundant free radicals Y, i.e., NO2, HOO, etc. (R2), where the reaction of BrHg +Y could also lead to the reduction of Hg(I) to Hg(0) (R3). A different oxidation pathway of BrHg + O3 (R4) is currently regarded as the dominant Hg(II) oxidation pathway in the atmosphere. Hg + Br + M → BrHg + M (R1) BrHg + Y + M → BrHgY + M (R2) BrHg + Y → BrY +Hg (R3) BrHg + O3 → BrHgO + O2 (R4) While the rate constants of R1 have been experimentally measured a decade ago, this research focuses on the experimental kinetic studies on the reaction of R2-R4 to better assist the efforts to predict how emission reductions impact the spatial distribution of mercury entry into ecosystems. The kinetic studies of BrHg redox chemistry are conducted by utilizing laser photolysis-laser induced fluorescence-cavity ringdown spectroscopy (LP-LIF-CRDS) systems, where BrHg radicals are generated via laser photolysis and monitored in the reaction via LIF and CRDS measurements. We report mainly on our experimental kinetic studies of the redox reactions of BrHg with relatively abundant trace gases such as NO2, NO, O3, O2, and VOCs, especially on the temperature and pressure dependence of the reaction rate constants using our LP-LIF system. We present the development and the characterization of a novel LP-CRDS system, which is a powerful tool to study reactions during which fluorescence quenching interferes with LIF measurement, and to study the spectroscopy of Hg(I) and Hg(II) compounds.

<p>Dipole-dipole interactions are ubiquitous fundamental physical phenomena that govern physical effects such as Casimir Forces, van der Waals forces, collective Lamb shifts, cooperative decay, and resonance energy transfer. These interactions are associated with real and virtual photon exchange between the interacting emitters. Such interactions are crucial in realizing quantum memories, novel super-radiant light sources, and light-harvesting devices. Owing to this, the control and modification of dipole-dipole interactions have been a longstanding theme. The electromagnetic environment plays a crucial role in enhancing the range and strength of the interactions. This work focuses on modifying the nanophotonic environment near interacting emitters to enhance dipole-dipole interactions instead of spontaneous emission. To this end, we focus on engineering the nanophotonic environment to enhance the strength and range of dipole-dipole interactions between an ensemble of emitters. We explore ordered and disordered nanophotonic structures. We experimentally demonstrate long-range dipole-dipole interactions mediated by surface lattice resonances in a periodic plasmonic nanoparticle lattice. Further, the modified electromagnetic environment reduces the apparent dimensionality of the interacting system compared to non-resonant in-homogeneous and homogeneous environments. We also develop a spectral domain inverse design technique for the accelerated discovery of disordered metamaterials with unique spectral features. </p> <p>Further, we explore the novel regimes of light localization at near-zero-index in such disordered media. The disordered near-zero-index medium reveals enhanced localization and near-field chirality. This work paves the way to engineer the electromagnetic nanophotonic environment to realize enhanced long-range dipole-dipole interactions.</p>

<p>One of the fundamental predictions of quantum mechanics is the occurrence of random fluctuations which can induce a measurable force between neutral objects, known as the Casimir effect. Casimir effect has attracted a lot of interest in both theoretical and practical work since the first prediction in 1948 because it is the most accessible evidence of quantum electromagnetic fluctuations in vacuum. Besides, it has prospective applications for nanotechnology and for studying fundamental physical theories beyond the standard model. In this dissertation, we report the experimental and theoretical progress towards realizing Casimir-based devices and long sought-after vacuum friction. </p> <p><br></p> <p>First, we propose and experimentally realize the first Casimir diode system that can regulate energy transfer along one direction through quantum vacuum fluctuations. This is the first experimental demonstration of non-reciprocal energy transfer by Casimir effects. We develop a dual-cantilever vacuum system which can be used to measure the Casimir force at separations from 50 nm to 1000 nm.  Parametric coupling scheme is applied to the system to couple two cantilevers with different resonant frequencies by Casimir interaction. By controlling the system near the exceptional point, we are able to break the time reversal symmetry and observe the non-reciprocal energy transfer. </p> <p><br></p> <p>The description of the Casimir diode system is followed by an experimental demonstration of the Casimir transistor system where we achieve the first measurement of Casimir interaction between three macroscopic objects. Three cantilevers can be coupled through quantum vacuum fluctuations by the parametric coupling scheme. Moreover, we have realized the first three-terminal Casimir transistor system that can switch and amplify quantum vacuum mediated energy transfer. These two Casimir-based devices will have potential applications in sensing and information processing.  </p> <p><br></p> <p>Subsequently, the first observation of Casimir mediated non-contact friction is demonstrated experimentally. When two parallel surfaces are moving with a relative velocity, they will experience quantum vacuum friction force which tries to slow down the relative motion because of quantum vacuum fluctuations. The quantum vacuum friction comes from the exchange of virtual photons between two moving bodies.  We have designed a novel method to detect the Casimir force mediated non-contact friction force between two harmonic oscillators. The non-contact friction comes from the interaction of virtual photons and phonons. We have experimentally detected the effect of non-contact friction and successfully measured the friction force at different velocities. </p> <p><br></p> <p>In the latter part of this thesis, two theoretical proposals about detecting the Casimir torque and rotational quantum vacuum friction torque by a levitated optomechanical system are discussed. The optically levitated nanoparticle system is a good candidate for precision measurements because it can achieve an ultrahigh mechanical quality factor due to the well isolation from the thermal environment. The calculation of the Casimir torque on a levitated nanorod near a birefringent plate is demonstrated. The calculation of the rotational quantum vacuum friction torque on a rotating nanosphere near a plate is also presented. By comparing these small torques to the sensitivity of our levitation system, we show that it is feasible to detect the Casimir torque and the rotational quantum vacuum friction torque under realistic conditions in the near future. </p> <p><br></p>

Lorsqu'ils sont soumis à des pulses laser courts et intenses, des atomes peuvent perdre des électrons. Plusieurs canaux sont impliqués dans la double ionisation, comme la NSDI et le scénario associé de la recollision. La recollision est maintenant vue comme la “pierre d'angle de la physique en champ fort” pour les éclairages qu'elle donne dans l'organisation de la matière et en ce qu'elle constitue l'une des manifestations les plus flagrantes de la corrélation électron-électron dans la nature. Dans ce manuscrit, une analyse théorique des mécanismes de double ionisation est menée en utilisant la mécanique classique. Cette description complémente les modèles quantiques en observant la dynamique depuis un cadre de travail différent et avec l'éclairage de la dynamique nonlinéaire. L'analyse, menée dans l'espace des phases, permet l'identification des structures organisatrices qui régulent les différents mécanismes d'ionisation. Pour des champs laser polarisés linéairement, le mécanisme de la recollision est complété par l'image de l'électron interne. L'électron interne donne accès à une description fine de la dynamique de recollision et explique les différentes routes pour la double ionisation. Il permet également de faire des prédictions telles que l'intensité du coude dans la probabilité de double ionisation et explique complètement la RESI. En polarisation circulaire, il est communément cru que la recollision n'est pas possible, en dépit de résultats expérimentaux contradictoires. En fait, l'analyse de l'espace des phases montre que la recollision est possible mais pas accessible à tous les atomes, réconciliant par conséquent les contradictions expérimentales précédentes. / When subjected to strong and short laser pulses, atoms may lose electrons. Several ionization channels are involved in such double ionization events, like nonsequential double ionization (NSDI) and its associated recollision scenario. Recollision is now seen as the “keystone of strong field physics”, for its insights into the organization of matter, and is one of the most dramatic manifestations of electron-electron correlation in nature. In this manuscript a theoretical analysis of the double ionization mechanisms is carried out using classical mechanics. This description complements quantum treatments by observing the dynamics from a different framework, with the light of nonlinear dynamics, as both frameworks exhibit the main ingredient, i.e., strong electron-electron correlation. The analysis, carried out in phase space (e.g., through reduced models) enables the identification of the organizing structures that regulate the ionization channels. For linearly polarized lasers, the recollision mechanism is completed by the picture of the “inner” electron. The inner electron gives access to a fine description of the recollision dynamics and explains the routes to double ionization. It also enables verifiable predictions such as the location of the characteristic knee shape in the double ionization yield versus laser intensity and fully explains delayed ionizations like RESI. For circular polarization, it is commonly believed that recollision is not possible, despite apparently contradictory experimental results. In fact, the phase space analysis shows that recollision is possible but not accessible to all atoms, thus reconciling the previous experimental results.

Despite enormous efforts and investments, the efficiency of InGaN-based green and yellow-green light emitters remains relatively low, and that limits progress in developing full color display, laser diodes, and bright light sources for general lighting. The low efficiency of light emitting devices in the green-to-yellow spectral range, also known as the “Green Gap”, is considered a global concern in the LED industry. The polar c-plane orientation of GaN, which is the mainstay in the LED industry, suffers from polarization-induced separation of electrons and hole wavefunctions (also known as the “quantum confined Stark effect”) and low indium incorporation efficiency that are the two main factors that contribute to the Green Gap phenomenon. One possible approach that holds promise for a new generation of green and yellow light emitting devices with higher efficiency is the deployment of nonpolar and semi-polar crystallographic orientations of GaN to eliminate or mitigate polarization fields. In theory, the use of other GaN planes for light emitters could also enhance the efficiency of indium incorporation compared to c-plane. In this thesis, I present a systematic exploration of the suitable GaN orientation for future lighting technologies. First, in order to lay the groundwork for further studies, it is important to discuss the analysis of processes limiting LED efficiency and some novel designs of active regions to overcome these limitations. Afterwards, the choice of nonpolar orientations as an alternative is discussed. For nonpolar orientation, the (1-100)-oriented (m-plane) structures on patterned Si (112) and freestanding m-GaN are studied. The semi-polar orientations having substantially reduced polarization field are found to be more promising for light-emitting diodes (LEDs) owing to high indium incorporation efficiency predicted by theoretical studies. Thus, the semi-polar orientations are given close attention as alternatives for future LED technology. One of the obstacles impeding the development of this technology is the lack of suitable substrates for high quality materials having semi-polar and nonpolar orientations. Even though the growth of free-standing GaN substrates (homoepitaxy) could produce material of reasonable quality, the native nonpolar and semi-polar substrates are very expensive and small in size. On the other hand, GaN growth of semi-polar and nonpolar orientations on inexpensive, large-size foreign substrates (heteroepitaxy), including silicon (Si) and sapphire (Al2O3), usually leads to high density of extended defects (dislocations and stacking faults). Therefore, it is imperative to explore approaches that allow the reduction of defect density in the semi-polar GaN layers grown on foreign substrates. In the presented work, I develop a cost-effective preparation technique of high performance light emitting structures (GaN-on-Si, and GaN-on-Sapphire technologies). Based on theoretical calculations predicting the maximum indium incorporation efficiency at θ ~ 62º (θ being the tilt angle of the orientation with respect to c-plane), I investigate (11-22) and (1-101) semi-polar orientations featured by θ = 58º and θ = 62º, respectively, as promising candidates for green emitters. The (11-22)-oriented GaN layers are grown on planar m-plane sapphire, while the semi-polar (1-101) GaN are grown on patterned Si (001). The in-situ epitaxial lateral overgrowth techniques using SiNx nanoporous interlayers are utilized to improve the crystal quality of the layers. The data indicates the improvement of photoluminescence intensity by a factor of 5, as well as the improvement carrier lifetime by up to 85% by employing the in-situ ELO technique. The electronic and optoelectronic properties of these nonpolar and semi-polar planes include excitonic recombination dynamics, optical anisotropy, exciton localization, indium incorporation efficiency, defect-related optical activities, and some challenges associated with these new technologies are discussed. A polarized emission from GaN quantum wells (with a degree of polarization close to 58%) with low non-radiative components is demonstrated for semi-polar (1-101) structure grown on patterned Si (001). We also demonstrated that indium incorporation efficiency is around 20% higher for the semi-polar (11-22) InGaN quantum wells compared to its c-plane counterpart. The spatially resolved cathodoluminescence spectroscopy demonstrates the uniform distribution of indium in the growth plane. The uniformity of indium is also supported by the relatively low exciton localization energy of Eloc = 7meV at 15 K for these semi-polar (11-22) InGaN quantum wells compared to several other literature reports on c-plane. The excitons are observed to undergo radiative recombination in the quantum wells in basal-plane stacking faults at room temperature. The wurtzite/zincblende electronic band-alignment of BSFs is proven to be of type II using the time-resolved differential transmission (TRDT) method. The knowledge of band alignment and degree of carrier localization in BSFs are extremely important for evaluating their effects on device properties. Future research for better understanding and potential developments of the semi-polar LEDs is pointed out at the end.