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Kay, C. W. M. "Magnetic field effects in chemistry and biology." Thesis, University of Oxford, 1993. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.334813.
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Yang, Nan. "Molecules in Sculpted Fields: Magnetic Field Effects and Multipole Transitions." Thesis, Harvard University, 2012. http://dissertations.umi.com/gsas.harvard:10684.
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This thesis describes work related to the theme of sculpted electromagnetic fields - engineered fields with particular spatial patterns - and their interactions with molecules. We are motivated by the following questions: what are ways of detecting spatial patterns in electromagnetic fields? What are possible applications of spatially engineered fields? Are there molecular transitions that are dark to plane waves but that can be probed by sculpted fields? The first part of this thesis is in the area of magnetic field effects in chemistry. We focus on magnetic field modulated fluorescence, which provides a convenient method for imaging magnetic field strength. We proposed and demonstrated a fluorescence technique that allows imaging through strongly scattering media. We achieve this by exploiting the fact that most materials do not scatter magnetic field. This allows us to project a magnetic field pattern beyond the scattering surface. The magnetic field dependent fluorescence then allows us to map out the object of interest. We constructed a setup that demonstrates 2D imaging using this technique. We synthesized new molecular systems to enhance the sensitivity to magnetic field. We characterized and compared these molecules with steady state fluorescence spectroscopy, transient fluorescence and transient absorption measurements. The results reveal patterns that point to directions for engineering chemical systems to further enhance their magnetic field sensing properties. The second portion of this thesis is a theoretical study of the molecular multipole transitions and their couplings to local electromagnetic quantities. Using a semiclassical approach, we performed a multipole expansion of molecular transitions driven by monochromatic radiation. We derived the local electromagnetic quantities that couple to different multipole transitions and observables such as circular dichroism and magnetic circular dichroism. It was observed that certain transitions are dark to plane waves, but could be probed by simple spatial arrangements such as superpositions of plane waves. Experiments for their detection are also proposed.Engineering and Applied Sciences
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Timmel, Christiane Renate. "Magnetic field effects on radical pair reactions." Thesis, University of Oxford, 1998. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.267955.
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Rodgers, Christopher T. "Magnetic field effects in chemical systems." Thesis, University of Oxford, 2007. http://ora.ox.ac.uk/objects/uuid:f5878b88-c5ba-4cbd-83af-857431aef66e.
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Magnetic fields influence the rate and/or yield of chemical reactions that proceed via spin correlated radical pair intermediates. The field of spin chemistry centres around the study of such magnetic field effects (MFEs). This thesis is particularly concerned with the effects of the weak magnetic fields B₀ ~ 1mT relevant in the ongoing debates on the mechanism by which animals sense the geomagnetic field and on the putative health effects of environmental electromagnetic fields. Relatively few previous studies have dealt with such weak magnetic fields. This thesis presents several new theoretical tools and applies them to interpret experimental measurements. Chapter 1 surveys the development and theory of spin chemistry. Chapter 2 introduces the use of Tikhonov and Maximum Entropy Regularisation methods as a new means of analysing MARY field effect data. These are applied to recover details of the diffusive motion of reacting pyrene and N,N-dimethylaniline radicals. Chapter 3 gives a fresh derivation and appraisal of an approximate, semiclassical approach to MFEs. Monte Carlo calculations allow the elucidation of several "rules of thumb" for interpreting MFE data. Chapter 4 discusses recent optically-detected zero-field EPR measurements, adapting the gamma-COMPUTE algorithm from solid state NMR for their interpretation. Chapter 5 explores the role of RF polarisation in producing MFEs. The breakdown in weak fields of the familiar rotating frame approximation is analysed. Chapter 6 reviews current knowledge and landmark experiments in the area of animal magnetoreception. The origins of the sensitivity of European robins Erithacus rubecula to the Earth’s magnetic field are given particular attention. In Chapter 7, Schulten and Ritz’s hypothesis that avian magnetoreception is founded on a radical pair mechanism (RPM) reaction is appraised through calculations in model systems. Chapter 8 introduces quantitative methods of analysing anisotropic magnetic field effects using spherical harmonics. Chapter 9 considers recent observations that European robins may sometimes be disoriented by minuscule RF fields. These are shown to be consistent with magnetoreception via a radical pair with no (effective) magnetic nuclei in one of the radicals.
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Evans, Christopher Riche. "Triplet derived radical pairs in micelles: Decay kinetics and magnetic field effects." Thesis, University of Ottawa (Canada), 1989. http://hdl.handle.net/10393/21399.
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Hamilton, Clive A. "Effects of magnetic and microwave fields on chemical reactions." Thesis, University of Oxford, 1989. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.236269.
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Sheppard, Dean. "Cavity-enhanced detection of biologically relevant magnetic field effects." Thesis, University of Oxford, 2016. https://ora.ox.ac.uk/objects/uuid:69a41655-de81-499d-81fb-e27c3b69280d.
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Magnetoreception is the ability of some animals to use the weak magnetic field of the Earth for navigation over long-distance migrations. It is a well-known phenomenon, but its underlying biophysical mechanisms remain poorly understood. One proposal involves light-induced, magnetically sensitive chemical reactions occurring within cryptochrome proteins, rationalised via the radical pair mechanism (Chapter 1). The absence of evidence in support of this hypothesis is in part due to the lack of sufficiently sensitive techniques to measure magnetic field effects (MFEs) in biological samples. Cavity-enhanced detection, most commonly in the form of cavity ring-down spectroscopy (CRDS) or cavity-enhanced absorption spectroscopy (CEAS), is widely used in the gas phase to provide significant sensitivity gains over traditional single-pass measurements (Chapter 2). However, successful studies in the condensed phase are less prevalent due to the additional background losses inherent to the sample. This thesis reports on the application of broadband (i.e. monitoring > 100nm) variants of CRDS and CEAS to the study of MFEs on the radical recombination reactions of flavin-based systems in solution. The broadband CRDS (BBCRDS) instrument employed in Chapter 4 is able to monitor the spectral changes induced by magnetic fields with submicrosecond time resolution. However, the need to scan both the probe wavelength and time delay to construct time-resolved spectra leads to prohibitively long acquisition times, and hence exposure of sensitive samples to high numbers of photons. The broadband CEAS (BBCEAS) studies reported in Chapter 5 combine the high irradiance and spectral coverage of a supercontinuum radiation (SCR) source with a CCD detector to simultaneously acquire absorption spectra across the visible region (480â700nm). The CW nature of this technique precludes the possibility of following radical pair kinetics in real time. In an effort to combine the respective advantages of these two instruments, which individually have represented powerful advances in capability, a new cavity-enhanced technique is reported for the first time (Chapter 6). The result, optical cavity-enhanced transient absorption spectroscopy (OCTAS), is able to simultaneously monitor spectral evolution and associated MFEs on the microsecond timescale, with comparable sensitivity to the existing techniques. Magnetic responses in animal cryptochrome proteins have successfully been recorded using all three techniques, lending considerable weight to the hypothesis that these molecules are at the heart of the magnetic sense in animals.
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Curtis, Ailsa F. "A theoretical study of magnetic field effects on radical recombination reactions." Thesis, University of Oxford, 2002. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.249386.
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Hontz, Eric Richard. "Electronic processes in organic optoelectronics : insights gained through modeling and magnetic field effects." Thesis, Massachusetts Institute of Technology, 2015. http://hdl.handle.net/1721.1/98794.
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Thesis: Ph. D. in Physical Chemistry, Massachusetts Institute of Technology, Department of Chemistry, 2015.Cataloged from PDF version of thesis.
Includes bibliographical references (pages 185-232).
Organic photovoltaics (OPVs) and organic light-emitting diodes (LEDs) are organic optoelectronics offering a number of unique benefits that may play an important role in the future of clean energy generation and efficient energy consumption. In this thesis, we explore key electronic processes in OPVs and OLEDs, with a major focus on quantum-mechanical kinetic modeling of magnetic field effects (MFEs) that probe underlying subprocesses. Certain organics are capable of dividing excited states in a process termed singlet fission, which can increase the maximum theoretical efficiency of an OPV by a factor of nearly 1/3. The MFEs on photocurrent measurements from our collaborators are combined with theoretical models to determine optimal device architectures for singlet fission OPVs, allowing us to exceed the conventional limit of one electron per photon. We also use MFEs to determine the spin of charge transfer states most efficient at generating photocurrent and demonstrate microscopic insight into the mechanism of their diffusion, offering new design principles for the engineering of donor-acceptor interfaces in OPVs. Thermally activated delayed fluorescence (TADF) is becoming an increasingly important OLED technology that extracts light from non-emissive triplet states via reverse intersystem crossing (RISC) to the bright singlet state. We use MFEs to prove a rather surprising finding that in TADF materials composed of donor-acceptor bends, the electron-hole distance fluctuates as a function of time, resulting in spontaneous cycling between states that are advantageous to fluorescence at one moment and then advantageous to RISC at another. Combined with additional topics in the fields of metal organic frameworks and reaction pathfinding methods, the work in this thesis provides insight into how to achieve optimal performance in OPV and OLED devices, which may serve an important role in the future of our energy landscape.
by Eric Richard Hontz.
Ph. D. in Physical Chemistry
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Pinkerton, Tim D. "Fundamental studies of the effect of electric fields on water-surface chemistry /." Thesis, Connect to this title online; UW restricted, 1998. http://hdl.handle.net/1773/9900.
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Ferguson, Kelly-Anne. "An investigation of isotropic and anisotropic magnetic field effects in fluorescent systems." Thesis, University of Oxford, 2014. http://ora.ox.ac.uk/objects/uuid:12a062e9-7bc7-414f-84e6-d65717b6c120.
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Interest into the effects of weak static magnetic fields on chemical reactions involving spin correlated radical pairs has increased over the last few decades, particularly as scientists have become more curious about the mechanisms by which animals can sense and respond to small variations in the Earth's weak (50 µT) magnetic field. The magnetosensitivity of radical pairs, as dictated by the radical pair mechanism, lies at the heart of the most heavily supported hypothesis of this magnetoreception phenomenon. This thesis is concerned with the spectroscopic investigations of isotropic and anisotropic magnetic field effects in fluorescent systems. First of all, an introduction to spin chemistry and magnetoreception is presented. In chapter 3, the effects of weak radiofrequency oscillating fields when applied in combination with weak static fields are explored in isotropic solutions. The validity of the high-field model, typically used to describe spin dynamics in magnetic resonance, is tested and the effects of orientation and field strength on magnetic field effects are discussed in detail. In Chapter 4, a range of exciplex systems are studied by fluorescence methods and their energetics are explored. The factors which determine the formation of an exciplex, i.e. the complex equilibrium between the exciplex and the spin-correlated radical pair,are considered and used to assess the existence and magnitude of MFEs. Radical pair systems investigated, using MARY spectroscopy, with respect to their potential to act as model chemical compasses are introduced in chapter 5. Solid-state media are used to align the exciplex systems to detect any magnetic field direction dependence. Finally, in chapter 6, AMELIA, an experiment which can directly measure the anisotropic magnetic field response of a system, is presented and applied successfully to systems to detect directly the anisotropic field response of a photoexcited anthracene crystal.
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Knoche, Krysti Lynn. "Density gradient films, lanthanide electrochemistry, and magnetic field effects on hydrogen evolution, oxygen reduction, and lanthanide electrochemistry." Diss., University of Iowa, 2015. https://ir.uiowa.edu/etd/3124.
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Electroanalytical techniques are used to investigate mass transport through density gradient films; lanthanide triflate reduction and oxidation in a Nafion/acetonitrile matrix; and magnetic field effects on hydrogen evolution reaction (HER), oxygen reduction reaction (ORR), and lanthanide electrochemistry.
Graded density films are more dense at the electrode surface and become less dense out into solution due to a brush polymer structure. Fick's second law expands to account for a diffusion coefficient that varies with distance x normal to the electrode surface. Confocal microscopy, cyclic voltammetry, and computer simulations are used to investigate density graded Ficoll® films. Mass transport approaches steady state (scan rate independence) at slow scan rates where the diffusion length samples the entire film. The use of Ficoll to template an ion exchange polymer is explored by casting Nafion® Ficoll composites.
Lanthanide electrochemistry is enabled in acetonitrile at a Nafion modified platinum electrode in the presence of triflate ligands. Formal potentials are shifted into the voltage window of acetonitrile accessible due to triflate complexation. The Nafion further solubilizes the compounds. The mechanism (ECEC) is studied with cyclic voltammetry and x-ray photoelectron spectroscopy.
Magnetic field effects on electrochemical systems have been of interest to researchers for the past 65 years. Mass transport effects, such as magnetohydrodynamics and magnetic field gradient effects have been reported, but the Leddy group focuses on electron transfer effects. Electrode surfaces are modified with composite films of magnetic microparticles suspended in ion exchange polymer Nafion. Effects are verified to be electron transfer related and due to the magnetization of chemically inert microparticles. The magnets catalyze the rates of important electron transfer reactions such as hydrogen evolution and oxygen reduction.
Magnetic field effects on HER at various noncatalytic metal electrodes are explored with linear scan voltammetry. There is a correlation between the magnetic susceptibility of the electrode metals and the HER exchange currents (reaction rates). Exchange currents are 103× larger for a paramagnetic metal electrode than a diamagnetic one with the same work function. The overpotential at diamagnetic electrodes is decreased by modification with a Nafion + magnetic microparticle composite film. A decrease in overpotential of ∼70 % for all electrodes except platinum is observed. The overpotential decrease correlates with the magnetic susceptibility of the particles.
Magnets can enhance differences between lanthanide cyclic voltammograms by shifting current densities at a given potential and enhancing current based on the number of 4f electrons and magnetic moment of each lanthanide ion.
Magnetic field effects on ORR in acetonitrile are investigated with cyclic voltammetry. In aprotic solvents, ORR proceeds by a one electron transfer reaction to paramagnetic O2.–. Enhanced reversibility and electron transfer kinetics are observed as well as a decrease in overpotential of ∼100 mV. Magnetic field effects on ORR in a lanthanide triflate solution are also examined. Electron transfer kinetics and reversibility are further enhanced in the presence of lanthanide triflate.
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Li, Xiang. "Organic Molecules for Field Effect Transistors and Redox Flow Batteries." University of Akron / OhioLINK, 2020. http://rave.ohiolink.edu/etdc/view?acc_num=akron1601396172154889.
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Irugulapati, Harista. "Fused Arenes-Based Molecular and Polymeric Materials for Organic Field Effect Transistors." TopSCHOLAR®, 2013. http://digitalcommons.wku.edu/theses/1255.
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In the past decade, tremendous progress has been made in organic field effecttransistors. Fused oligothiophenes and anthracene molecules are fascinatingmacromolecules having unique optoelectronic properties. These compounds are successfully employed as active components in optoelectronic devices including field effect transistors. Our goal is to design and synthesize conjugated molecular materials, which are highly functionalized through structural modifications in order to enhance their electronic, photonic, and morphological properties. The main desire is to synthesize novel organic fused-arenes having efficient charge carrier mobilities, as well as to optimize optical properties for organic field effect transistors (OFETs). Novel series of fused arene molecules of 9,10-di(thiophen-3-yl)anthracene (1), trans-2,5-(dianthracene-9- vinyl)thiophene (2), trans-5,5’-(dianthracene-9-yl)vinyl)- 2,2’-bithiophene (3), 5,5’-di(2 thiophene)-2,2’-bithiophene (4) , 9,10-(divinyl)anthracene core with 1- phenylcarboxypyrene (6) and polymers of poly(anthracene-co-bithiophene) (5) and poly(anthracene) (7) have been synthesized as promising materials for organic field effect transistors (OFETs). These compounds were confirmed and characterized by 1H-NMR, FT-IR, and elemental analysis. Their optical, thermal, and electronic properties were investigated using UV-Vis and photoluminescence spectroscopy, and thermogravimetric analysis respectively. Future studies will focus on evaluating OFETs performance of these material.
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Zola, Rafael S. "Effects of electric field, surface alignment and guest materials in cholesteric liquid crystals." Kent State University / OhioLINK, 2012. http://rave.ohiolink.edu/etdc/view?acc_num=kent1332428717.
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Jin, Jiyang. "Synthesis of Novel Hydrogen-Bonding Unit for Organic Field-Effect Transistors." University of Akron / OhioLINK, 2016. http://rave.ohiolink.edu/etdc/view?acc_num=akron1460047707.
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Granger, Devin B. "ACENES, HETEROACENES AND ANALOGOUS MOLECULES FOR ORGANIC PHOTOVOLTAIC AND FIELD EFFECT TRANSISTOR APPLICATIONS." UKnowledge, 2017. http://uknowledge.uky.edu/chemistry_etds/76.
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Polycyclic aromatic hydrocarbons composed of benzenoid rings fused in a linear fashion comprise the class of compounds known as acenes. The structures containing three to six ring fusions are brightly colored and possess band gaps and charge transport efficiencies sufficient for semiconductor applications. These molecules have been investigated throughout the past several decades to assess their optoelectronic properties. The absorption, emission and charge transport properties of this series of molecules has been studied extensively to elucidate structure-property relationships. A wide variety of analogous molecules, incorporating heterocycles in place of benzenoid rings, demonstrate similar properties to the parent compounds and have likewise been investigated.
Functionalization of acene compounds by placement of groups around the molecule affects the way in which molecules interact in the solid state, in addition to the energetics of the molecule. The use of electron donating or electron withdrawing groups affects the frontier molecular orbitals and thus affects the optical and electronic gaps of the molecules. The use of bulky side groups such as alkylsilylethynyl groups allows for crystal engineering of molecular aggregates, and changing the volume and dimensions of the alkylsilyl groups affects the intermolecular interactions and thus changes the packing motif.
In chapter 2, a series of tetracene and pentacene molecules with strongly electron withdrawing groups is described. The investigation focuses on the change in energetics of the frontier molecular orbitals between the base acene and the nitrile and dicyanovinyl derivatives as well as the differences between the pentacene and tetracene molecules. The differences in close packing motifs through use of bulky alkylsilylethynyl groups is also discussed in relation to electron acceptor material design and bulk heterojunction organic photovoltaic characteristics.
Chapter 3 focuses on molecular acceptor and donor molecules for bulk heterojunction organic photovoltaics based on anthrathiophene and benzo[1,2-b:4,5-b’]dithiophene central units like literature molecules containing fluorene and dithieno[2,3-b:2’,3’-d]silole cores. The synthetic strategies of developing reduced symmetry benzo[1,2-b:4,5-b’]dithiophene to study the effect of substitution around the central unit is also described. The optical and electronic properties of the donors and acceptors are described along with the performance and characteristics of devices employing these molecules.
The final two data chapters focus on new nitrogen containing polycyclic hydrocarbons containing indolizine and (2.2.2) cyclazine units. The optical, electronic and other physical properties of these molecules are explored, in addition to the synthetic strategies for incorporating the indolizine and cyclazine units. By use of alkylsilylethynyl groups, crystal engineering was investigated for the benzo[2,3-b:5,6-b’]diindolizine chromophore described in chapter 4 to target the 2-D “brick-work” packing motif for application in field effect transistor devices. Optical and electronic properties of the cyclazine end-capped acene molecules described in chapter 5 were investigated and described in relation to the base acene molecules. In both cases, density functional theory calculations were conducted to better understand unexpected optical properties of these molecules, which are like the linear acene series despite the non-linear attachment.
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Dzenitis, John M. "Soil chemistry effects and flow prediction in remediation of soils by electric fields." Thesis, Massachusetts Institute of Technology, 1996. http://hdl.handle.net/1721.1/10973.
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Lee, Heung Chan. "Magnetic field effects on electron transfer reactions: heterogeneous photoelectrochemical hydrogen evolution and homogeneous self exchange reaction." Diss., University of Iowa, 2010. https://ir.uiowa.edu/etd/2562.
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Magnetic field effects (MFE) on electrochemical systems have been of interest to researchers for the past 60 years. MFEs on mass transport, such as magnetohydrodynamics and magnetic field gradients effects are reported, but MFEs on electron transfer kinetics have been rarely investigated. Magnetic modification of electrodes enhances electron transfer kinetics under conditions of high concentrations and low physical diffusion conditions, as shown by Leddy and coworkers. Magnetic microparticles embedded in an ion exchange polymer (e.g., Nafion) applied to electrode surfaces. Rates of electron transfer reactions to diffusing redox probes and to adsorbates are markedly enhanced.
This work reports MFEs on hydrogen evolution on illuminated p-Si; MFEs on hydrogen evolution on noncatalytic electrodes; a model for MFEs on homogeneous self-exchange reactions; and a convolution based voltammetric method for film modified electrodes.
First, a MFE on the photoelectrochemical hydrogen evolution reaction (HER) at p-Si semiconductors is demonstrated. The HER is an adsorbate reaction. Magnetic modification reduces the energetic cost of the HER by 400 - 500 mV as compared to Nafion modified electrodes and by 1200 mV as compared to unmodified p-Si. Magnetically modified p-Si achieves 6.2 % energy conversion efficiency. Second, from HER on noncatalytic electrodes, the MFE on photoelectrochemical cells arises from improved heterogeneous electron transfer kinetics. On glassy carbon electrodes, magnetic modification improves heterogeneous electron transfer rate constant, k₀,for HER 80,000 fold. Third, self exchange reaction rates are investigated under magnetic modification for various temperatures, outersphere redox probes, and magnetic particles. Arrhenius analyses of the rate constants collected from the experiments show a 30 - 40 % decrease in activation energy at magnetically modified electrodes. A kinetic model is established based on transition state theory. The model includes pre-polarization and electron nuclear spin polarization steps and characterizes a majority of the experimental results. Lastly, a convolution technique for modified with uniform films electrodes is developed and coded in Matlab (mathematical software) for simple and straightforward analysis of Nafion modified electrodes.
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Hogben, Hannah J. "Coherent spin dynamics of radical pairs in weak magnetic fields." Thesis, University of Oxford, 2011. http://ora.ox.ac.uk/objects/uuid:61c4ab7e-406f-4193-949a-b5a70f43e3e1.
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The outcome of chemical reactions proceeding via radical pair (RP) intermediates can be influenced by the magnitude and direction of applied magnetic fields, even for interaction strengths far smaller than the thermal energy. Sensitivity to Earth-strength magnetic fields has been suggested as a biophysical mechanism of animal magnetoreception and this thesis is concerned with simulations of the effects of such weak magnetic fields on RP reaction yields. State-space restriction techniques previously used in the simulation of NMR spectra are here applied to RPs. Methods for improving the efficiency of Liouville-space spin dynamics calculations are presented along with a procedure to form operators directly into a reduced state-space. These are implemented in the spin dynamics software Spinach. Entanglement is shown to be a crucial ingredient for the observation of a low field effect on RP reaction yields in some cases. It is also observed that many chemically plausible initial states possess an inherent directionality which may be a useful source of anisotropy in RP reactions. The nature of the radical species involved in magnetoreception is investigated theoretically. It has been shown that European Robins are disorientated by weak radio-frequency (RF) fields at the frequency corresponding to the Zeeman splitting of a free electron. The potential role of superoxide and dioxygen is investigated and the anisotropic reaction yield in the presence of a RF-field, without a static field, is calculated. Magnetic field effect data for Escherichia coli photolyase and Arabidopsis thaliana cryptochrome 1, both expected to be magnetically sensitive, are satisfactorily modelled only when singlet-triplet dephasing is included. With a view to increasing the reaction yield anisotropy of a RP magnetoreceptor, a brief study of the amplification of the magnetic field experienced by a RP from nearby magnetite particles is presented. Finally in a digression from RPs, Spinach is used to determine the states expected to be immune from relaxation and therefore long-lived in NMR experiments on multi-spin systems.
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Yi, Congwen. "Reliability study of enhancement-mode AIGaN/GaN HEMT fabricated with fluorine plasma treatment technology /." View abstract or full-text, 2008. http://library.ust.hk/cgi/db/thesis.pl?ECED%202008%20YI.
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Shafiei, Alavijeh Mohammadmahdi. "Water Dynamics and the Effect of Static and Alternating Electric Fields." VCU Scholars Compass, 2018. https://scholarscompass.vcu.edu/etd/5640.
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Having a net dipole moment, water molecules tend to align with an external electric field. The re-orientation of water molecules to align with the field direction can result in structural and dynamic changes in liquid water. Studying these changes can help us to understand the role of an E-field in many biological systems, chemical reactions, and many technological advancements.
In short, the application of static electric fields causes molecules to stay aligned with the field, so, fewer hydrogen bonds break, and molecules have slower dynamics. This type of field can be used when the mobility of water molecules needs to be reduced, like in electroporation. Alternating electric fields, on the other hand, cause continuous re-orientation of dipole moments, which results in more H bond breaking, water is less structured, and molecules have faster motion.
Water under static and alternating electric fields have several applications in science and technology. Although many of the interesting usages of the application of electric fields to water happen at surfaces, the response of hydrogen bonding of water molecules to an E-field is still not fully understood even in bulk. For instance, the rate of hydrogen bond breaking, the re-orientation of water molecules, and the random walk of water molecules under the restrictions of the static electric field have not been thoroughly assessed. The static electric field limits the re-orientation of water molecules, but the translation reduces at the same time, this is clear evidence of roto-translational coupling, and the static electric field is a great groundwork for studying this coupling which is generated by the hydrogen bonds.
For studying the effects of an E-field on H-bonding dynamics in depth, we need a model of hydrogen bonding. There are a few models for dynamics of H-bonding and reorientation of water molecules, including Luzar and Chandler model, published in 1996, and the Laage and Hynes jump model, published in 2006, which are described in the introduction chapter. The two models are related but have different perspectives, so it would be very interesting to look for a more general framework of hydrogen bonding by combining these two models, with the help of the influence of external electric fields. We also explain the relation of the random walk diffusion of water molecules and the hydrogen bonding.
Since the external electric field can change the dipole moment of water molecules, for a more realistic picture, we need do the simulations with sophisticated polarizable water models to obtain a better estimate of the behavior of experimental water in an electric field.
In this thesis, we introduce our generalized hydrogen bond framework; then we assess this framework, as well as other static and dynamic properties of water under static and alternating electric fields.
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Petty, Anthony Joseph II. "DESIGN AND SYNTHESIS OF FUNCTIONAL ORGANIC MATERIALS." UKnowledge, 2018. https://uknowledge.uky.edu/chemistry_etds/105.
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Control of solid state ordering in conjugated small molecules is paramount to the continued development and implementation of organic materials in electronic devices. However, there exists no reliable method on which to predicatively determine how a change to the molecular structure will impact the solid-state packing. As such, the molecule must be synthesized before its solid-state packing can be definitively evaluated. However, once the packing structure of a material is known there exist both qualitative structure- function relationships derived from the literature, as well as quantitative computational methods that can be employed to suggest if a material will perform well in a given device. This type of bottom-up strategy is used in Chapter 2 to design and synthesize a high performance material for organic field effect transistors. A core molecule is synthesized, and through rigorous optimization of pendant and solubilizing groups a material with exceptional solid-state packing is developed and its performance in an organic field effect transistor is discussed.
Chapter 3 discusses the use of conjugated organic molecules in conjunction with inorganic materials to develop hybrid organic/inorganic materials. A scalable synthesis is developed so derivatives can be rapidly synthesized and their properties evaluated. Two classes of materials are developed and synthesized: tetracene-based ligands for quantum dots and diammonium-substituted anthracene and tetracene derivatives for 2D-perovskites. Initial results for both classes of materials are presented. Chapter 4 discusses the topochemical photopolymerization of heptacene [4+4] dimers. Multiple derivatives were synthesized in order to give the ideal alignment of molecules in the crystal, followed by irradiation of crystals to give crystal templated polymerization. In Chapter 5, triarylmethane derivatives are synthesized and their performance as radiochromic sensors is evaluated. Chapter 6 involves the development of a robust synthetic scheme toward a difficult to attain π- extended regioisomer of pyrene. Photophysical characterization reveals that the direction of π-extension from the pyrene core has a profound effect on electron delocalization.
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Wang, Huan, and Huan Wang. "Flow Field Penetration in Thin Nanoporous Polymer Films under Laminar Flow by Förster Resonance Energy Transfer Coupled with Total Internal Reflectance Fluorescence Microscopy." Diss., The University of Arizona, 2015. http://hdl.handle.net/10150/565916.
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Tethered polymer layers at solid-fluid interfaces are used widely in a variety of surface science applications. Although many of these applications require exposure to dynamic flow conditions, flow field penetration into densely grafted polymer brushes, is still a question open to debate despite the fact that it is a fundamental process crucial to mass transport through these polymer films. Although most theoretical work has indicated flow field penetration into polymer films, with varying predicted penetration depths predicted, the limited experimental attempts to investigate this phenomenon have resulted in inconsistent conclusions due to lack of a proper analytical method. To help resolve this controversy, in this Dissertation, a new spectroscopic method, FRET-TIRFM, based on a combination of Förster resonance energy transfer (FRET) and total internal reflectance fluorescence microscopy (TIRFM), is developed to provide the first direct, quantitative measurements on flow field penetration by measuring linear diffusion coefficients of small molecules through densely grafted, thin poly(N-isopropylacryl-amide) (pNIPAM) films. Decay curves from FRET of the acceptor with a donor covalently attached at the substrate surface were fit to a combined Taylor-Aris-Fickian diffusion model to obtain apparent linear diffusion coefficients of the acceptor molecules for different flow rates. These values can then be used to obtain quantitative estimates of flow field penetration depths. For a pNIPAM surface of 110 nm dry thickness, with a 0.6 chain/nm² grafting density, apparent diffusion coefficients ranging from 1.9-9.1 × 10-12 cm²/s were observed for flow rates ranging from 100 to 3000 μL/min. This increase in apparent diffusion coefficient with applied fluid flow rate is indicative of flow field penetration of the polymer film. The depth of penetration of the flow field is estimated to range from ~6% of the polymer film thickness to ~57% of the film thickness in going from 100 to 3000 μL/min flow rate of a good solvent. Factors other than flow rate that may impact flow field penetration were also investigated using this new FRET-TIRFM method. Solvent quality and polymer brush grafting density are the two most important parameters due to the fact that they influence changes in tethered polymer chain conformation. This work demonstrates that polymer films are most penetrable in a good solvent and least penetrable in a poor solvent under identical flow conditions. These findings are consistent with polymer chain conformational changes going from extended brushes to compact globules. For flow rates ranging from 100 to 3000 μL/min, flow field penetration depth ranges from ~6% of the film thickness to ~57% of film thickness for a good solvent compared to ~4% to ~19% for a poor solvent. Thus, by simply changing solvent quality from good to poor, flow field penetration decreases by about 38%. Grafting density has a less pronounced effect than solvent quality on penetration depth, probably due to the small range of grafting densities chosen for study. However, a roughly 10-20% difference in penetration depth was observed between high density (0.60 chain/nm²) and low density (0.27 chain/nm²) pNIPAM surfaces in the same solvent. Changes in grafting density have a less significant impact in a good solvent compared to a poor solvent. This is most likely caused by the fact that grafting density impacts polymer chain conformation mainly through polymer-polymer repulsion, which becomes less significant in a solvent that better solvates the polymer. For the two extreme cases studied here at flow rates ranging from 100 to 3000 μL/min, the penetration depth is estimated to range from ~4-19% of the original solvent-swollen film thickness for high density pNIPAM films in a poor solvent and from ~7-67% for low density films in a good solvent. One important assumption that underlies all of this work is that the dominant mass transport mechanism for small molecules in dense polymer brushes is diffusion. This assumption was further validated through the use of two different small molecule quenchers, RhB and 2-nitrobenzylalcohol. These molecules are significantly different in size, charge, and structure, and operate by different quenching mechanisms. Despite these differences, the results for flow field penetration are statistically the same for both. These observations validate the assumption of diffusive mass transport in these films.
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Polander, Lauren E. "Organic charge-transport materials based on oligothiophene and naphthalene diimide: towards ambipolar and air-stable n-channel organic field-effect transistors." Diss., Georgia Institute of Technology, 2011. http://hdl.handle.net/1853/45849.
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To better understand the physical and electronic properties of donor and acceptor-based structures used in organic electronic applications, a variety of oligothiophene and naphthalene diimide-based small conjugated molecules were designed, synthesized, and characterized. The materials were initially synthesized using oxidative copper-chloride coupling reactions, palladium-catalyzed amination reactions, Friedal-Crafts acylations, Negishi coupling reactions, and Stille coupling reactions. Once isolated, the physical properties of the compounds were characterized through a combination of X-ray crystal structure, thermogravimetric analysis, differential scanning calorimetry, UV-vis. absorption spectroscopy, cyclic voltammetry, and differential pulse voltammetry, along with comparison to quantum-chemical calculations. In some cases, the radical cations or radical anions were generated by chemical oxidation and analyzed by vis-NIR spectroscopy. Furthermore, the electronic properties of the materials were investigated through incorporation as solution-processed active layers in organic field-effect transistors. Multiple examples exhibited hole- and / or electron-transport properties with electron mobility values of up to 1.5 cm²V⁻¹s⁻¹, which is among the highest yet reported for an n-channel OFET based on a solution-processed small molecule.
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Lim, Sang-Hyun. "Characterization of p-type wide band gap transparent oxide for heterojunction devices." Amherst, Mass. : University of Massachusetts Amherst, 2009. http://scholarworks.umass.edu/dissertations/AAI3359903/.
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Jiang, Jinyue. "Design, Synthesis, and Properties of New Derivatives of Pentacene and New Blue Emitters." Bowling Green State University / OhioLINK, 2006. http://rave.ohiolink.edu/etdc/view?acc_num=bgsu1145645147.
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Ma, Hui. "Nanomaterials for Biological Applications: Drug Delivery and Bio-sensing." ScholarWorks@UNO, 2013. http://scholarworks.uno.edu/td/1647.
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The idea of utilizing nanomaterials in bio-related applications has been extensively practiced during the recent decades. Magnetic nanoparticles (MPs), especially superparamagnetic iron oxide nanoparticles have been demonstrated as promising candidates for biomedicine. A protective coating process with biocompatible materials is commonly performed on MPs to further enhance their colloidal and chemical stability in the physiological environment. Mesoporous hollow silica is another class of important nanomaterials that are extensively studied in drug delivery area for their ability to carry significant amount of guest molecules and release in a controlled manner.
In this study, different synthetic approaches that are able to produce hybrid nanomaterials, constituting both mesoporous hollow silica and magnetite nanoparticles, are described. In a two-step approach, pre-synthesized magnetite nanoparticles are either covalently conjugated to the surface of polystyrene beads and coated with silica or embedded/enclosed in the porous shell during a nanosized CaCO3 templated condensation of silica precursors, followed by acid dissolution to generate the hollow structure. It was demonstrated that the hollow interior is able to load large amount of hydrophobic drugs such as ibuprofen while the mesoporous shell is capable of prolonged drug. In order to simplify the fabrication procedure, a novel in-situ method is developed to coat silica surface with magnetite nanoparticles. By refluxing the iron precursor with mesoporous hollow silica nanospheres in polyamine/polyalcohol mixed media, one is able to directly form a high density layer of magnetite nanoparticles on silica surface during the synthesis, leaving reactive amine groups for further surface functionalization such as fluorescence conjugation. This approach provides a convenient synthesis for silica nanostructures with promising potential for drug delivery and multimodal imaging.
In addition to nanoparticles, nanowires also benefit the research and development of instruments in clinical diagnosis. Semiconductive nanowires have demonstrated their advantage in the fabrication of lab-on-a-chip devices to detect many charge carrying molecules such as antibody and DNA. In our study, In2O3 and silicon nanowire based field effect transistors were fabricated through bottom-up and top-down approaches, respectively, for ultrasensitive bio- detection of toxins such as ricin. The specific binding and non-specific interaction of nanowires with antibodies were also investigated.
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AL-SHADEEDI, AKRAM. "LATERAL AND VERTICAL ORGANIC TRANSISTORS." Kent State University / OhioLINK, 2017. http://rave.ohiolink.edu/etdc/view?acc_num=kent1492441683969202.
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Woodward, J. R. "The effect of magnetic fields in chemistry and biology." Thesis, University of Oxford, 1997. http://ora.ox.ac.uk/objects/uuid:2a881ed6-77a9-4e5f-95de-9974ac9e18e7.
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This thesis is concerned with the effect of static and oscillatory magnetic fields on the yield of radical recombination reactions and the proposal that such effects may constitute a possible mechanism for the interaction of environmental electromagnetic fields with biological systems. A brief overview of research pertaining to the biological effects of environmental electromagnetic fields is presented. Next, the concept of the radical pair is introduced and the theory of its behaviour in solution is examined in order to illustrate the mechanism by which magnetic fields can affect its probability of separation. Three different experimental systems involving the attack of free-radicals on DNA are presented. The extent of DNA damage is assayed in the presence and absence of a static magnetic field. These systems involve the killing of yeast cells as observed by the growth of subsequent colonies, direct observation of strand breaks to DNA, in vitro, by gel electrophoresis and the direct observation of intra- nuclear DNA damage by microgel analysis. In all systems, magnetic field effects are observed but are difficult to reproduce consistently. The design of novel apparatus for the observation of resonant radiofrequency effects is described. The application of a 30-40 MHz oscillating magnetic field is found to alter the yield of exciplex fluorescence in the photoreaction of anthracene-d10 and 1,3-dicyanobenzene. The effect is interpreted in terms of a change in the efficiency of singlet andleftrightarrow; triplet interconversion in the {anthracene cation - DCB anion} radical pair when the oscillating field is in resonance with hyperfine splittings in the DCB anion radical.
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List, Nanna Holmgaard. "Theoretical Description of Electronic Transitions in Large Molecular Systems in the Optical and X-Ray Regions." Doctoral thesis, Department of Physics, Chemistry and Biology, University of Southern Denmark, Denmark, 2015. http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-201156.
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The size and conformational complexity of proteins and other large systems represent major challenges for today's methods of quantum chemistry.This thesis is centered around the development of new computational tools to gain molecular-level insight into electronic transitions in such systems. To meet this challenge, we focus on the polarizable embedding (PE) model, which takes advantage of the fact that many electronic transitions are localized to a smaller part of the entire system.This motivates a partitioning of the large system into two regions that are treated at different levels of theory:The smaller part directly involved in the electronic process is described using accurate quantum-chemical methods, while the effects of the rest of the system, the environment, are incorporated into the Hamiltonian of the quantum region in an effective manner. This thesis presents extensions of the PE model with theaim of expanding its range of applicability to describe electronic transitions in large molecular systemsin the optical and X-ray regions. The developments cover both improvements with regardto the quantum region as well as the embedding potential representing the environment.Regarding the former, a damped linear response formulation has been implemented to allow for calculations of absorption spectra of large molecular systems acrossthe entire frequency range. A special feature of this development is its abilityto address core excitations that are otherwise not easily accessible.Another important development presented in this thesis is the coupling of the PE model to a multi-configuration self-consistent-field description of the quantum region and its further combination with response theory. In essence, this extends the PE model to the study of electronic transitions in large systems that are prone to static correlation --- a situation that is frequently encountered in biological systems. In addition to the direct environmental effects on the electronic structure of the quantum region, another important component of the description of electronic transitions in large molecular systems is an accurate account of the indirect effects of the environment, i.e., the geometrical distortions in the quantum region imposed by the environment. In thisthesis we have taken the first step toward the inclusion of geometry distortions in the PE frameworkby formulating and implementing molecular gradients for the quantum region. To identify critical points related to the environment description, we perform a theoretical analysis of the PE model starting from a full quantum-mechanicaltreatment of a composite system. Based on this, we present strategies for an accurate yet efficient construction of the embedding potentialcovering both the calculation of ground state and transition properties. The accurate representation of the environment makes it possible to reduce the size of the quantum region without compromising the overall accuracy of the final results. This further enables use of highly accurate quantum-chemical methods despite their unfavorable scaling with the size of the system. Finally, some examples of applications will be presented to demonstrate how the PE model may be applied as a tool to gain insight into and rationalize the factors influencing electronic transitions in large molecular systems of increasing complexity.The dissertation was awarded the best PhD thesis prize 2016 by the Danish Academy of Natural Sciences.
QC 20170209
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Raymand, David. "Surface and Interface Studies of ZnO using Reactive Dynamics Simulation." Doctoral thesis, Uppsala universitet, Strukturkemi, 2010. http://urn.kb.se/resolve?urn=urn:nbn:se:uu:diva-129304.
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About 90% of all chemicals are produced with the help of catalysts, substances with the ability to accelerate reactions without being consumed. Metal oxides play a prominent role in catalysis, since they are able to act reversibly in many chemical processes. Zink oxide (ZnO) is used to catalyse a number of industrially important reactions. For many of these reactions water is present as a reactant, product, or byproduct. The surface structure has a significant impact on the catalytic activity. However, currently, no experimental method simultaneously offers the spatial and temporal resolution to directly follow a catalytic process. This thesis explores surface structure dependent dynamical behavior for ZnO surfaces, nanoparticles, and water interfaces, using the computational chemistry method Molecular Dynamics, which enables detailed studies of structural and dynamical processes. Quantum mechanical (QM) calculations have been performed to obtain the energetics of the materials as a function of structure. This data has been used to parametrize reactive force-fields (ReaxFF), since the catalytic processes require both far larger and longer simulations than the capabilities of QM calculations on current computers. The simulations show that when steps are present on the surface, during crystal growth of ZnO, the creation of energetically favorable structures is accelerated. At the ZnO - water interface, structures that favor hydrogen bonding is promoted. At low, monolayer, coverage water adsorbs both molecularly and dissociatively, whereas at high coverage dissociated adsorption is favored. During evaporation from the monolayers, the ratio of dissociated and molecular water is preserved. Surface steps stabilizes the dissociated state as well as increases the rate of dissociation. The dynamical properties of ZnO nanoparticles were explored using Raman measurements and simulation. In both simulation and experiment certain vibrations were suppressed in the nanoparticles, compared to bulk. The simulations show that a narrow surface region lack the bulk-specific vibrations.
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Qin, Feili. "Metal Oxide Reactions in Complex Environments: High Electric Fields and Pressures above Ultrahigh Vacuum." Thesis, University of North Texas, 2005. https://digital.library.unt.edu/ark:/67531/metadc4843/.
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Metal oxide reactions at metal oxide surfaces or at metal-metal oxide interfaces are of exceptional significance in areas such as catalysis, micro- and nanoelectronics, chemical sensors, and catalysis. Such reactions are frequently complicated by the presence of high electric fields and/or H2O-containing environments. The focus of this research was to understand (1) the iron oxide growth mechanism on Fe(111) at 300 K and 500 K together with the effect of high electric fields on these iron oxide films, and (2) the growth of alumina films on two faces of Ni3Al single crystal and the interaction of the resulting films with water vapor under non-UHV conditions. These studies were conducted with AES, LEED, and STM. XPS was also employed in the second study. Oxidation of Fe(111) at 300 K resulted in the formation of Fe2O3 and Fe3O4. The substrate is uniformly covered with an oxide film with relatively small oxide islands, i.e. 5-15 nm in width. At 500 K, Fe3O4 is the predominant oxide phase formed, and the growth of oxide is not uniform, but occurs as large islands (100 - 300 nm in width) interspersed with patches of uncovered substrate. Under the stress of STM induced high electric fields, dielectric breakdown of the iron oxide films formed at 300 K occurs at a critical bias voltage of 3.8 ± 0.5 V at varying field strengths. No reproducible result was obtained from the high field stress studies of the iron oxide formed at 500 K. Ni3Al(110) and Ni3Al(111) were oxidized at 900 K and 300 K, respectively. Annealing at 1100 K was required to order the alumina films in both cases. The results demonstrate that the structure of the 7 Å alumina films on Ni3Al(110) is k-like, which is in good agreement with the DFT calculations. Al2O3/Ni3Al(111) (γ'-phase) and Al2O3/Ni3Al(110) (κ-phase) films undergo drastic reorganization and reconstruction, and the eventual loss of all long-range order upon exposure to H2O pressure > 10-5 Torr. Al2O3/Ni3Al(110) film is significantly more sensitive to H2O vapor than the Al2O3/Ni3Al(111) film, and this may be due to the incommensurate nature of the oxide/Ni3Al(110) interface. STM measurements indicate that this effect is pressure- rather than exposure- dependent, and that the oxide instability is initiated at the oxide surface, rather than at the oxide/metal interface. The effect is not associated with formation of a surface hydroxide, yet is specific to H2O (similar O2 exposures have no effect).
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Li, Jing. "Applications of optical-cavity-based spectroscopic techniques in the condensed phase." Thesis, University of Oxford, 2014. http://ora.ox.ac.uk/objects/uuid:d6a0c476-e67f-4390-a63a-e3cb9e60bf2c.
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Cavity ring-down spectroscopy (CRDS) and cavity enhanced absorption spectroscopy (CEAS) are two well-established absorption spectroscopic techniques originally developed for gas-phase samples. Condensed-phase applications of these techniques still remain rare, complicated as they are by additional background losses induced by condensed-phase samples as well as the intracavity components in which the sample is constrained. This thesis is concerned with the development and application of optical-cavity-based techniques in the condensed phase. Polarization-dependent evanescent wave CRDS (EW-CRDS) has been used to study the molecular orientation at the solid/air and solid/liquid interfaces. An increase in average orientation angle with respect to the surface normal has been observed for both methylene blue and coumarin molecules as a function of coverage at the fused silica/air interface. An orientation-angle-dependent photobleaching of pyridin molecules at the fused silica/methanol interface have also been observed. EW-CRDS has also been used to monitor slow in situ photobleaching of thin dye films deposited on the prism surface. The photobleaching dynamics is interpreted as a combination of first- and second-order processes. A significant fraction of this thesis has been devoted to studying magnetic field effects (MFEs) on the kinetics of the radical pair (RP) reactions in solution, in an effort to understand the ability of animals to sense the geomagnetic field. Two novel optical-cavity-based techniques – broadband CEAS (BBCEAS) and CRDS have been developed for this purpose. BBCEAS uses a supercontinuum (SC) source as the cavity light source and a CCD camera as photodetector, enabling simultaneous acquisition of absorption spectrum across the whole visible region (400 – 800 nm). In CRDS, a tunable optical parametric oscillator has been used as the cavity light source. Combined with the switching of external magnetic field (SEMF) method, this technique allows the decay kinetics of the geminate RPs to be monitored, with nanosecond resolution. Both BBCEAS and CRDS provide sensitivity superior to single-pass transient absorption (TA), a technique traditionally used in the MFE studies. A series of photochemical systems have been studied by BBCEAS and CRDS, respectively, among which, the MFEs of drosophila melanogaster cryptochrome has been observed. Importantly, this is the first time an MFE has been observed in an animal cryptochrome, and provides key supporting evidence for the cryptochrome hypothesis of magnetoreception in animals. Besides the optical-cavity-based techniques, a novel fluorescence detection method of MFEs has also been demonstrated. This technique proved ultrahigh sensitivity when applicable.
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Neil, Simon R. T. "Condensed-phase applications of cavity-based spectroscopic techniques." Thesis, University of Oxford, 2012. http://ora.ox.ac.uk/objects/uuid:4431e46e-1226-4950-aa5d-ce22e0309ba9.
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This thesis describes the development and application of condensed-phase cavity-based spectroscopic techniques - namely cavity ring-down spectroscopy (CRDS); cavity enhanced absorption spectroscopy (CEAS); broadband cavity enhanced absorption spectroscopy (BBCEAS) and evanescent wave (EW) variants of all three. The recently-developed cavity technique of EW-broadband cavity enhanced absorption spectroscopy (EW-BBCEAS) has been used—in combination with a supercontinuum source (SC) and a sensitive, fast readout CCD detector—to record of the full visible spectrum (400–700 nm) of a silica-liquid interfacial layer (with an effective thickness ca. 1 µm), at rapid acquisition rates (> 600 Hz) that are sufficient to follow fast kinetics in the condensed phase, in real time. The sensitivity achieved (Amin= 3.9 x 10-5) is comparable with previous EW-CRDS and EW-CEAS studies, but the spectral region accessed in this broadband variant is much larger. The study of liquid|air interfaces using EW cavity-based techniques is also illustrated for the first time. The first application of BBCEAS to the analysis of microfluidic samples, flowing through a microfluidic chip, is illustrated. Proof-of-principle experiments are presented, demonstrating the technique’s ability to provide full visible broadband spectral measurements of flowing microfluidic droplets, with both high detection sensitivity (αmin < 10-2 cm-1) and excellent spatial and temporal resolution: an SC light source and sensitive, fast readout CCD allowed measurement repetition rates of 273 Hz, whilst probing a very small sample volume (ca. 90 nL). A significant portion of this thesis is devoted to demonstrating the powerful capabilities of CEAS, CRDS and BBCEAS in monitoring radical recombination reactions and associated magnetic field effects (MFEs) in solution. The efficacy of CEAS as a high-sensitivity MFE detection method has been established in a proof-of-principle study, using narrow band CEAS in combination with phase-sensitive detection: MFE-induced absorbance changes of ca. 10-6 could be detected using the modulated CEAS technique and the data are shown to be superior to those obtained using conventional transient absorption (TA) methods typically employed for MFE measurements. The powerful capabilities of CRDS in monitoring radical recombination reactions and associated MFEs are also demonstrated. In particular, a pump-probe CRDS variant allows not only high sensitivity (Amin on the order 10-6), but also sub-microsecond time-resolution. Combined, these features represent significant advantages over TA. Finally, SC-BBCEAS is used to measure full visible spectra of photoinduced reactions and their MFEs. The applicability of this approach to in vitro MFE studies of Drosophila cryptochrome is demonstrated—the results mark the first in vitro observation of a magnetic field response in an animal cryptochrome, a key result supporting the hypothesis that cryptochromes are involved in the magnetic sense in animals.
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Deeth, R. J. "Redirected ligand-field analysis : applications of the cellular ligand-field model." Thesis, University of Cambridge, 1985. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.355257.
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Bertram, Janet. "Effects of cow urine and its constituents on soil microbial populations and nitrous oxide emissions." Diss., Lincoln University, 2009. http://hdl.handle.net/10182/1334.
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New Zealand’s 5.3 million strong dairy herd returns approximately 106 million litres of urine to pasture soils daily. The urea in that urine is rapidly hydrolysed to ammonium (NH₄⁺), which is then nitrified, with denitrification of nitrate (NO₃⁻) ensuing. Nitrous oxide (N₂O), a potent greenhouse gas (GHG), is produced via nitrification and denitrification, which are enzyme-catalysed processes mediated by soil microbes. Thus microbes are linked intrinsically to urine patch chemistry. However, few previous studies have investigated microbial dynamics in urine patches. Therefore the objective of these four experiments was to investigate the effects on soil microbial communities of cow urine deposition. Methods used included phospholipid fatty acid (PLFA) analyses of microbial community structure and microbial stress, dehydrogenase activity (DHA) assays measuring microbial activity, and headspace gas sampling of N₂O, ammonia (NH₃) and carbon dioxide (CO₂) fluxes. Experiment 1, a laboratory study, examined the influence of soil moisture and urinary salt content on the microbial community. Both urine application and high soil moisture increased microbial stress, as evidenced by significant changes in PLFA trans/cis and iso/anteiso ratios. Total PLFAs and DHA showed a short-term (< 1 week) stimulatory effect on microbes after urine application. Mean cumulative N₂O-N fluxes were 2.75% and 0.05% of the nitrogen (N) applied, from the wet (70% WFPS) and dry (35% WFPS) soils, respectively. Experiment 2, a field trial, investigated nutrient dynamics and microbial stress with plants present. Concentrations of the micronutrients, copper, iron and molybdenum, increased up to 20-fold after urine application, while soil phosphorus (P) concentrations decreased from 0.87 mg kg ⁻¹ to 0.48 mg kg⁻¹. Plant P was also lower in urine patches, but total PLFAs were higher, suggesting that microbes had utilised the available nutrients. Microbial stress again resulted from urine application but, in contrast to experiment 1, the fungal biomass recovered after its initial inhibition. Studies published during the course of this thesis reported that hippuric acid (HA) and its hydrolysis product benzoic acid (BA) significantly reduced N₂O-N emissions from synthetic cow urine, thus experiment 3 investigated this effect using real cow urine. Cumulative N₂O-N fluxes were 16.8, 5.9 and 4.7% of N applied for urine (U) alone, U+HA and U+BA, respectively. Since NH₃-N volatilisation remained unchanged, net gaseous N emissions were reduced. Trends in total PLFAs and microbial stress were comparable to experiment 1 results. Experiment 4 studied HA effects at different temperatures and found no inhibition of N₂O-N fluxes from HA-amended urine. However, mean cumulative N₂O-N fluxes were reduced from 7.6% of N applied at 15–20°C to 0.2% at 5–10°C. Total cumulative N emissions (N₂O-N + NH₃-N) were highest at 20°C (17.5% of N applied) and lowest at 10°C (9.8% of N applied). Microbial activity, measured as potential DHA, increased with increasing temperature. This work has clearly shown that the stimulation and inhibition of the soil microbial community by urine application are closely linked to soil chemistry and have significant impacts not only on soil nutrient dynamics but also on N₂O-N emissions and their possible mitigation.
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Mark, Lewis Paul. "Carbon nanotubes and other highly curved surfaces for field emission and field-promoted ionisation." Thesis, University of Warwick, 2009. http://wrap.warwick.ac.uk/3170/.
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The thesis describes the development of various novel emitters for the production of gaseous ions from solutions of non-volatile, thermally labile samples for the purposes of mass spectrometry. Nano-electrospray emitters each containing two separated channels running throughout the length of the emitter were fabricated and evaluated. These emitters were made from “theta-shaped” borosilicate capillaries, employing a number of different coating procedures. Loading of different solutions into the channels demonstrated the possibility of studying solute interactions on ultrashort timescales. It is proposed that interactions took place in a shared Taylor cone. The formation of specific adducts from vancomycin and diacetyl-l-lysyld- alanyl-d-alanine was observed by mass spectrometry. From consideration of the extent of H/D exchange between vancomycin and deuterated vancomycin, it was concluded that the interaction times were of the order of 10-5 s. Underlying theoretical considerations, design and fabrication from carbon nanotubes (CNTs) of emitters for field desorption and field ionization ion sources are described and discussed. The emitters fabricated made use of arrays of vertically aligned multi-walled CNTs with in most cases an average length and radius of 15 μm and 35 nm respectively. Emitters using dense coverings of nanotubes and emitters with nanotubes selectively grown so that the height of each nanotube was twice its separation from its nearest neighbour were investigated. Characterisation of the CNTs by field electron-emission confirmed their effectiveness as field emitters. Fowler-Nordhein plots indicated fields of 6.14x109 +/- 0.72x109 V/m at a potential of 700 V. Field ionization of He, Ar, Xe, methane and acetone was achieved with these same CNTs; neither the inert gases nor methane have been field ionised with conventional activated-wire emitters. The fields generally accepted to be required for field ionisation of He and Ar are of the order of several 1010 V/m. To create emitters which would not need to be removed from vacuum between experiments, a means of injecting both liquids and gaseous samples directly to the bottom of the CNTs was devised. This involved drilling 20 μm diameter holes through the silicon substrate between intended sites of nanotube growth, but before actually growing the CNTs. It was discovered that the presence of the holes led to surface migration of the nickel catalysts initiating CNT growth. Experiments undertaken to achieve mass spectrometric measurements with the arrays of CNTs as emitters are described and discussed.
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Khanal, Kiran. "Liquid-Crystalline Ordering in Semiflexible Polymer Melts and Blends: A Monte Carlo Simulation Study." University of Akron / OhioLINK, 2013. http://rave.ohiolink.edu/etdc/view?acc_num=akron1373901748.
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Bridgeman, Adam J. "Vibronic intensity in ligand-field analysis." Thesis, University of Cambridge, 1995. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.338139.
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Qi, Yabing. "Field-induced phenomena in colloidal suspensions /." View Abstract or Full-Text, 2002. http://library.ust.hk/cgi/db/thesis.pl?PHYS%202002%20QI.
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Thesis (M. Phil.)--Hong Kong University of Science and Technology, 2002.Includes bibliographical references (leaves 57-60). Also available in electronic version. Access restricted to campus users.
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Maguire, Steven. "Magnetic field control of silver nanoparticle formation." Thesis, University of Ottawa (Canada), 2006. http://hdl.handle.net/10393/27390.
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Silver nanoparticles can be readily generated in micellar environments by ketyl radicals formed from the photoreduction of benzophenone in the presence of a suitable hydrogen donor. The yield of these ketyl radicals can be increased by extending the lifetime of the triplet radical pair through Zeeman splitting of the triplet sublevels in an externally applied magnetic field. This provides control over the rate of photogeneration of nanoparticles under very mild conditions. The rate of photogeneration can be monitored by the distinctive surface plasmon resonance absorption around 420 nm. In this work, micelles of sodium dodecyl sulphate (SDS) were employed, and 1,4-cyclohexadiene (1,4-CHD), an excellent hydrogen donor, was used to promote the generation of ketyl radicals. When benzophenone and a silver salt are added to this system and it is irradiated in the presence of a magnetic field, the rate of appearance of the plasmon band is enhanced. In addition to serving as a hydrogen donor, 1,4-CHD also has a stabilising influence on the nanoparticles, adsorbing onto the surface and preventing aggregation. 1,4-CHD added to a solution of nanoparticles synthesised without the diene present will even break up existing aggregates.
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Robinson, Alexander Joseph. "Magnetic field effects on biological systems." Thesis, University of Oxford, 2010. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.543006.
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吳潔貞 and Kit-ching Betty Ng. "Correlation effects in crystal field splitting." Thesis, The University of Hong Kong (Pokfulam, Hong Kong), 1986. http://hub.hku.hk/bib/B31230714.
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Carey, John Joseph. "Near field effects of terahertz pulses." Thesis, University of Strathclyde, 2003. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.273433.
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Ng, Kit-ching Betty. "Correlation effects in crystal field splitting /." [Hong Kong : University of Hong Kong], 1986. http://sunzi.lib.hku.hk/hkuto/record.jsp?B12323342.
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Fedele, Giorgio. "Electromagnetic field effects in Drosophila melanogaster." Thesis, University of Leicester, 2015. http://hdl.handle.net/2381/39852.
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Many higher animals have evolved the ability to use the Earth’s magnetic field, particularly for orientation. However, the biophysical mechanism by which magnetoreception is achieved remains elusive. One theoretical model (the radical pair mechanism - RPM) proposes that the geomagnetic field is perceived by chemical reactions involving the blue-light photoreceptor Cryptochrome (CRY). Recent evidence supports the RPM in Drosophila melanogaster and reveals a mechanistic link with the circadian clock. Here I have confirmed, albeit with rather different results, that a low frequency electromagnetic field (AC-EMF) along with a Static Field (SF) exposure does affect circadian and activity behaviour in the fruit fly. Furthermore, I have developed two new assays to investigate the effects of EMF in Drosophila melanogaster, negative geotaxis and an additional light wavelength preference assay, revealing a net CRY-dependent response. My data support the idea of CRY mediated magnetoreception, thereby indirectly supporting the RPM. Furthermore, I provide some striking new results that challenge our view that only the canonical clock neurons contribute to behavioural rhythms in Drosophila melanogaster.
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Hassan, Sultan. "Collective effects in multi-field inflation." Master's thesis, University of Cape Town, 2013. http://hdl.handle.net/11427/6618.
Full textAbstract:
We present a new model of multi-field inflation in the limit when, N, the number of fields is very large. To implement this limit, we reformulate the problem in terms of a colourless bilocal field [(x; y) which encodes the collective degrees of freedom of the N scalar fields. As a concrete example, we apply the collective field theory formalism to the bosonic O(N) vector model with quartic self interaction minimally coupled to gravity and show how this may be used to model the quantum to classical transition out of inflation.
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Li, Xian Ph D. Massachusetts Institute of Technology. "Terahertz-field-induced nonlinearity in phonons, electrons and spins." Thesis, Massachusetts Institute of Technology, 2019. https://hdl.handle.net/1721.1/122713.
Full textAbstract:
Thesis: Ph. D., Massachusetts Institute of Technology, Department of Chemistry, 2019Cataloged from PDF version of thesis.
Includes bibliographical references (pages 189-210).
In this thesis, I describe work aimed at understanding nonlinear material responses initiated by strong terahertz (THz) field excitation. I discuss two aspects of nonlinear THz spectroscopy in condensed-matter materials: developments of experimental THz capabilities and spectroscopy methods and their applications in investigating ultrafast nonlinear dynamics in different classes of materials. I first describe the THz generation, detection and spectroscopy methods, which are the basis of all of our studies. We have generated strong single- and multi-cycle THz pulses covering several spectral ranges using inorganic and organic crystals and developed linear and nonlinear THz spectroscopy techniques to interrogate light-matter interactions based on different observables and/or symmetry criteria.
We have demonstrated a new method for studying time-domain electron paramagnetic resonance that allows us to measure THz-frequency fine structures of spin energy levels on a tabletop and have developed nonlinear two-dimensional (2D) magnetic resonance spectroscopy to distinguish nonlinear THz-spin interaction pathways. We also show that THz-pump, optical-probe spectroscopy, including THz field-induced second-harmonic generation spectroscopy and THz Kerr effect spectroscopy, can be extended to study phase transitions in quantum paraelectric and topological materials. We have employed the THz methods to drive and detect nonlinear responses from several degrees of freedom in the materials. We have demonstrated collective coherent control over material structure by inducing a quantum paraelectric to ferroelectric phase transition using intense THz electric fields in strontium titanate.
We show that a single-cycle THz field is able to drive ions along the microscopic pathway leading directly to their locations in a new crystalline phase on an ultrafast timescale. We have driven highly nonlinear lattice and electronic responses in a topological crystalline insulator by dynamically perturbing the protecting crystalline symmetry through THz phonon excitation. We have observed oscillations in optical reflectivity that may be associated with electronic gap opening and modulation in the topological surface states. Finally, we have demonstrated nonlinear manipulation of collective spin waves in a canted antiferromagnet using strong THz magnetic fields and we have observed full sets of the second- and third-order nonlinear responses in 2D THz magnetic resonance spectra, which are accurately reproduced in our numerical simulations.
by Xian Li.
Ph. D.
Ph.D. Massachusetts Institute of Technology, Department of Chemistry
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McKeating, Paul D. "Magnetic field effects on radical pair reactions." Thesis, University of Oxford, 2004. http://ethos.bl.uk/OrderDetails.do?uin=uk.bl.ethos.400216.
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