Matching Items (13)
151723-Thumbnail Image.png
Description
The objective of the present investigations is to experimentally determine the fundamental molecular properties of the transient metal containing pieces. The transient molecules have been generated using laser ablation production technique and detected by using laser induced fluorescence technique. Ultra-high resolution spectra of the diatomic molecules, 87SrF, 135&137BaF, YbF, HfF,

The objective of the present investigations is to experimentally determine the fundamental molecular properties of the transient metal containing pieces. The transient molecules have been generated using laser ablation production technique and detected by using laser induced fluorescence technique. Ultra-high resolution spectra of the diatomic molecules, 87SrF, 135&137BaF, YbF, HfF, and IrSi were recorded at a resolution of approximately 30 Mhz. The fine and hyperfine structure of these molecules were determined for the ground and the excited state. The optical Stark splittings of 180HfF and IrSi were recorded and analyzed to determine the permanent electric dipole moments of the ground and the excited state. An effective Hamiltonian operator, including the rotational, centrifugal distortion, spin-orbit, spin-spin, spin-rotation, Λ-doubling, magnetic hyperfine and quadrupole interactions, and Stark effect, was employed to model and analyze the recorded spectra. The electronic spectra of the triatomic molecules, TiO2 and ZrO2, were recorded using pulsed dye laser, LIF, spectrometer at a resolution of 300MHz. These molecules have C2v symmetry. The harmonic frequencies, lifetime measurements were determined. These spectra of ZrO2 and TiO2 were modeled using a normal coordinate analysis and Franck-Condon factor predictions. High resolution field-free and Stark effect spectra of ZrO2 were recorded and for future investigation.
ContributorsLe, Anh Thun (Author) / Steimle, Timothy C (Thesis advisor) / Richert, Ranko (Committee member) / Chizmeshya, Andrew (Committee member) / Arizona State University (Publisher)
Created2013
151277-Thumbnail Image.png
Description
This thesis describes the studies for two groups of molecules in the gas-phase: (a) copper monofluoride (CuF) and copper hydroxide (CuOH); (b) thorium monoxide (ThO) and tungsten carbide (WC). Copper-containing molecules (Group a) are selected to investigate the ionic bonding in transition metal-containing molecules because they have a relatively simple

This thesis describes the studies for two groups of molecules in the gas-phase: (a) copper monofluoride (CuF) and copper hydroxide (CuOH); (b) thorium monoxide (ThO) and tungsten carbide (WC). Copper-containing molecules (Group a) are selected to investigate the ionic bonding in transition metal-containing molecules because they have a relatively simple electronic state distribution due to the nearly filled 3d-orbital. ThO and WC (Group b) are in support of particle physics for the determination of electron electric dipole moment (eEDM), de, the existence of which indicates new physics beyond the Standard Model. The determination of the tiny eEDM requires large electric fields applied to the electron. The 3(Delta)1 states for heavy polar molecules were proposed [E. R. Meyer, J. L. Bohn, and M. P. Deskevich, Phys. Rev. A 73, 062108 (2006)] to determine de with the following attractive features: (1) large electric dipole moments; (2) large internal electric fields, Eeff, experienced by valence electrons; (3) nearly degenerate omega-doublets; (4) extremely small magnetic dipole moments. The H3(Delta)1 state for ThO and the X3(Delta)1 state for WC are both good candidates. Spectroscopic parameters (i.e. molecular electric and magnetic dipole moments, omega-doubling parameters, etc) are required for the 3(Delta)1 states of ThO and WC. High resolution optical spectra (linewidth ~50 MHz) of CuF, CuOH, ThO and WC were recorded field-free and in the presence of a static electric field (or magnetic field) using laser ablation source/supersonic expansion and laser induced fluorescence (LIF) detection. The spectra were modeled by a zero-field effective Hamiltonian operator and a Stark (or Zeeman) Hamiltonian operator with various molecular parameters. The determined molecular parameters are compared to theoretical predictions. The small omega-doubling parameter was well determined using the pump/probe microwave optical double resonance (PPMODR) technique with a much higher resolution (linewidth ~60 kHz) than optical spectroscopy. In addition to the above mentioned studies of the two groups of molecules, a resonance enhanced multi-photon ionization (REMPI) combined with a time-of-flight mass spectrometer (TOFMS) has been developed to identify the molecules responsible for observed LIF signals. The operation of this spectrometer has been tested by recording the mass spectrum of Ti/O2 and the REMPI spectrum for TiO using a two-color excitation scheme.
ContributorsWang, Fang (Author) / Steimle, Timothy C (Thesis advisor) / Chizmeshya, Andrew (Committee member) / Wolf, George (Committee member) / Arizona State University (Publisher)
Created2012
152677-Thumbnail Image.png
Description
Organic optoelectronic devices have remained a research topic of great interest over the past two decades, particularly in the development of efficient organic photovoltaics (OPV) and organic light emitting diodes (OLED). In order to improve the efficiency, stability, and materials variety for organic optoelectronic devices a number of emitting materials,

Organic optoelectronic devices have remained a research topic of great interest over the past two decades, particularly in the development of efficient organic photovoltaics (OPV) and organic light emitting diodes (OLED). In order to improve the efficiency, stability, and materials variety for organic optoelectronic devices a number of emitting materials, absorbing materials, and charge transport materials were developed and employed in a device setting. Optical, electrical, and photophysical studies of the organic materials and their corresponding devices were thoroughly carried out. Two major approaches were taken to enhance the efficiency of small molecule based OPVs: developing material with higher open circuit voltages or improved device structures which increased short circuit current. To explore the factors affecting the open circuit voltage (VOC) in OPVs, molecular structures were modified to bring VOC closer to the effective bandgap, ∆EDA, which allowed the achievement of 1V VOC for a heterojunction of a select Ir complex with estimated exciton energy of only 1.55eV. Furthermore, the development of anode interfacial layer for exciton blocking and molecular templating provide a general approach for enhancing the short circuit current. Ultimately, a 5.8% PCE was achieved in a single heterojunction of C60 and a ZnPc material prepared in a simple, one step, solvent free, synthesis. OLEDs employing newly developed deep blue emitters based on cyclometalated complexes were demonstrated. Ultimately, a peak EQE of 24.8% and nearly perfect blue emission of (0.148,0.079) was achieved from PtON7dtb, which approaches the maximum attainable performance from a blue OLED. Furthermore, utilizing the excimer formation properties of square-planar Pt complexes, highly efficient and stable white devices employing a single emissive material were demonstrated. A peak EQE of over 20% for pure white color (0.33,0.33) and 80 CRI was achieved with the tridentate Pt complex, Pt-16. Furthermore, the development of a series of tetradentate Pt complexes yielded highly efficient and stable single doped white devices due to their halogen free tetradentate design. In addition to these benchmark achievements, the systematic molecular modification of both emissive and absorbing materials provides valuable structure-property relationship information that should help guide further developments in the field.
ContributorsFleetham, Tyler Blain (Author) / Li, Jian (Thesis advisor) / Alford, Terry (Committee member) / Adams, James (Committee member) / Arizona State University (Publisher)
Created2014
152875-Thumbnail Image.png
Description
Protein-surface interactions, no matter structured or unstructured, are important in both biological and man-made systems. Unstructured interactions are more difficult to study with conventional techniques due to the lack of a specific binding structure. In this dissertation, a novel approach is employed to study the unstructured interactions between proteins and

Protein-surface interactions, no matter structured or unstructured, are important in both biological and man-made systems. Unstructured interactions are more difficult to study with conventional techniques due to the lack of a specific binding structure. In this dissertation, a novel approach is employed to study the unstructured interactions between proteins and heterogonous surfaces, by looking at a large number of different binding partners at surfaces and using the binding information to understand the chemistry of binding. In this regard, surface-bound peptide arrays are used as a model for the study. Specifically, in Chapter 2, the effects of charge, hydrophobicity and length of surface-bound peptides on binding affinity for specific globular proteins (&beta-galactosidase and &alpha1-antitrypsin) and relative binding of different proteins were examined with LC Sciences peptide array platform. While the general charge and hydrophobicity of the peptides are certainly important, more surprising is that &beta-galactosidase affinity for the surface does not simply increase with the length of the peptide. Another interesting observation that leads to the next part of the study is that even very short surface-bound peptides can have both strong and selective interactions with proteins. Hence, in Chapter 3, selected tetrapeptide sequences with known binding characteristics to &beta-galactosidase are used as building blocks to create longer sequences to see if the binding function can be added together. The conclusion is that while adding two component sequences together can either greatly increase or decrease overall binding and specificity, the contribution to the binding affinity and specificity of the individual binding components is strongly dependent on their position in the peptide. Finally, in Chapter 4, another array platform is utilized to overcome the limitations associated with LC Sciences. It is found that effects of peptide sequence properties on IgG binding with HealthTell array are quiet similar to what was observed with &beta-galactosidase on LC Science array surface. In summary, the approach presented in this dissertation can provide binding information for both structured and unstructured interactions taking place at complex surfaces and has the potential to help develop surfaces covered with specific short peptide sequences with relatively specific protein interaction profiles.
ContributorsWang, Wei (Author) / Woodbury, Neal W (Thesis advisor) / Liu, Yan (Committee member) / Chaput, John (Committee member) / Arizona State University (Publisher)
Created2014
156536-Thumbnail Image.png
Description
New forms of carbon are being discovered at a rapid rate and prove to be on the frontier of cutting edge technology. Carbon possesses three energetically competitive forms of orbital hybridization, leading to exceptional blends of properties unseen in other materials. Fascinating properties found among carbon allotropes, such as, fullerenes,

New forms of carbon are being discovered at a rapid rate and prove to be on the frontier of cutting edge technology. Carbon possesses three energetically competitive forms of orbital hybridization, leading to exceptional blends of properties unseen in other materials. Fascinating properties found among carbon allotropes, such as, fullerenes, carbon nanotubes, and graphene have led to new and exciting advancement, with recent applications in defense, energy storage, construction, and electronics. Various combinations of extreme strength, high electrical and thermal conductivity, flexibility, and light weight have led to new durable and flexible display screens, optoelectronics, quantum computing, and strength enhancer coating. The quest for new carbon allotropes and future application persists.

Despite the advances in carbon-based technology, researchers have been limited to sp3 and sp2 hybridizations. While sp3 and sp2 hybridizations of carbon are well established and understood, the simplest sp1 hybridized carbon allotrope, carbyne, has been impossible to synthesize and remains elusive. This dissertation presents recent results in characterizing a new sp1 carbon material produced from using pulsed laser ablation in liquid (PLAL) to ablate a gold surface that is immersed in a carbon rich liquid. The PLAL technique provides access to extremely non-thermal environmental conditions where unexplored chemical reactions occur and can be explored to access the production of new materials. A combination of experimental and theoretical results suggests gold clusters can act as stabilizing agents as they react and adsorb onto the surface of one dimensional carbon chains to form a new class of materials termed “pseudocarbynes”. Data from several characterization techniques, including Raman spectroscopy, UV/VIS spectroscopy, and transmission electron microscopy (TEM), provide evidence for the existence of pseudocarbyne. This completely new material may possess outstanding properties, a trend seen among carbon allotropes, that can further scientific advancements.
ContributorsFujikado, Nancy (Author) / Sayres, Scott G (Thesis advisor) / Rege, Kaushal (Thesis advisor) / Green, Matthew D (Committee member) / Arizona State University (Publisher)
Created2018
154699-Thumbnail Image.png
Description
Unmanned aerial vehicles have received increased attention in the last decade due to their versatility, as well as the availability of inexpensive sensors (e.g. GPS, IMU) for their navigation and control. Multirotor vehicles, specifically quadrotors, have formed a fast growing field in robotics, with the range of applications spanning from

Unmanned aerial vehicles have received increased attention in the last decade due to their versatility, as well as the availability of inexpensive sensors (e.g. GPS, IMU) for their navigation and control. Multirotor vehicles, specifically quadrotors, have formed a fast growing field in robotics, with the range of applications spanning from surveil- lance and reconnaissance to agriculture and large area mapping. Although in most applications single quadrotors are used, there is an increasing interest in architectures controlling multiple quadrotors executing a collaborative task. This thesis introduces a new concept of control involving more than one quadrotors, according to which two quadrotors can be physically coupled in mid-flight. This concept equips the quadro- tors with new capabilities, e.g. increased payload or pursuit and capturing of other quadrotors. A comprehensive simulation of the approach is built to simulate coupled quadrotors. The dynamics and modeling of the coupled system is presented together with a discussion regarding the coupling mechanism, impact modeling and additional considerations that have been investigated. Simulation results are presented for cases of static coupling as well as enemy quadrotor pursuit and capture, together with an analysis of control methodology and gain tuning. Practical implementations are introduced as results show the feasibility of this design.
ContributorsLarsson, Daniel (Author) / Artemiadis, Panagiotis (Thesis advisor) / Marvi, Hamidreza (Committee member) / Berman, Spring (Committee member) / Arizona State University (Publisher)
Created2016
168483-Thumbnail Image.png
Description
All known life requires three main metabolic components to grow: an energy source, an electron source, and a carbon source. For energy, an organism can use light or chemical reactions. For electrons, an organism can use metals or organic molecules. For carbon, an organism can use organic or inorganic carbon.

All known life requires three main metabolic components to grow: an energy source, an electron source, and a carbon source. For energy, an organism can use light or chemical reactions. For electrons, an organism can use metals or organic molecules. For carbon, an organism can use organic or inorganic carbon. Life has adapted to use any mixture of the endpoints for each of the three metabolic components. Understanding how these components are incorporated in a living bacterium on Earth in modern times is relatively straight forward. This becomes much more complicated when trying to determine what metabolisms may have been used in ancient times on Earth or potential novel metabolisms that exist on other planets. One way to examine these possibilities is by creating genetically modified mutant bacteria that have novel metabolisms or proposed ancient metabolisms to study. This thesis is the beginning of a broader study to understand novel metabolisms using Heliobacteria modesticaldum. H. modesticaldum was grown under different environmental conditions to isolate the impacts of energy, electron, and carbon sources on carbon and nitrogen isotope fractionation. Additionally, the wild type and a novel mutant H. modesticaldum were compared to measure the effects of specific enzymes on carbon and nitrogen isotope fractionation. By forcing the bacterium to adapt to different conditions, variation in carbon and nitrogen content and isotopic signature are detected. Specifically, by forcing the bacterium to fix nitrogen as opposed to nitrogen incorporation, the isotopic signature of the bacterium had a noticeable change. Themutant H. modesticaldum also had a different isotopic signature than the wild type. Without the enzyme citrate synthase, H. modesticaldum had to adapt its carbon metabolic cycle, creating a measurable carbon isotope fractionation. The results described here offer new insight into the effects of metabolism on carbon and nitrogen fractionation of ancient or novel organisms.
ContributorsElms, Nicholas (Author) / Hartnett, Hilairy E (Thesis advisor) / Redding, Kevin (Committee member) / Trembath-Reichert, Elizabeth (Committee member) / Anbar, Ariel D (Committee member) / Arizona State University (Publisher)
Created2021
168519-Thumbnail Image.png
Description
This research seeks to answer the question if there is a singular relationship between stishovite nucleation and the atomistic structure of the preshocked amorphous SiO$_2$. To do this a stishovite manufacturing method is developed in which 1,152 samples were produced. The majority of these samples did crystallize. The method was

This research seeks to answer the question if there is a singular relationship between stishovite nucleation and the atomistic structure of the preshocked amorphous SiO$_2$. To do this a stishovite manufacturing method is developed in which 1,152 samples were produced. The majority of these samples did crystallize. The method was produced through two rounds of experiments and fine-tuning with the pressure damp, temperature damp, shock pressure using an NPHug fix, and sample origin. A new random atomic insertion method was used to generate a new and different SiO$_2$ amorphous structure not before seen within the research literature. The optimal values for shock were found to be 60~GPa for randomly atom insertion samples and 55~GPa for quartz origin samples. Temperature damp appeared to have a slight effect optimizing at 0.05~ps and the pressure damp had no visible effect, testing was done with temperature damp from 0.05 to 0.5~ps and pressure damp from 0.1 to 10.0~ps. There appeared to be significant randomness in crystallization behavior. The preshocked and postnucleated samples were transformed into Gaussian fields of crystal, mass, and charge. These fields were divided and classified using a cut-off method taking the number of crystals produced in portions of each simulation and classifying each potion as nucleated or non-nucleated. Data in which some nucleation but not a critical amount was present was removed constituting 2.6\% to 20.3\% of data in all tests. A max method was also used which takes only the maximum portions of each simulation to classify as nucleating. There are three other variables tested within this work, a sample size of 18,000 or 72,728~atoms, Gaussian variance of 1 or 4~\AA, and Convolutional neural network (CNN) architecture of a garden verity or all convolution along with the portioning classification method, sample origination, and Gaussian field type. In total 64 tests were performed to try every combination of variable. No significant classifications were made by the CNNs to nucleation or non-nucleation portions. The results clearly confirmed that the data was not abstracting to atomistic structure and was random by all classifications of the CNNs. The all convolution CNN testing did show smoother outcomes in training with less fluctuations. 59\% of all validation accuracy was held at 0.5 for a random state and 84\% was within $\pm0.02$ of 0.5. It is conclusive that prenucleation structure is not the sole predictor of nucleation behavior. It is not conclusive if prenucleation structure is a partial or non-factor within nucleation of stishovite from amorphous SiO$_2$.
ContributorsChristen, Jonathan Scorr (Author) / Oswald, Jay (Thesis advisor) / Muhich, Christopher (Committee member) / Zhuang, Houlong (Committee member) / Arizona State University (Publisher)
Created2021
154026-Thumbnail Image.png
Description
There has been a vast increase in applications of Unmanned Aerial Vehicles (UAVs) in civilian domains. To operate in the civilian airspace, a UAV must be able to sense and avoid both static and moving obstacles for flight safety. While indoor and low-altitude environments are mainly occupied by static obstacles,

There has been a vast increase in applications of Unmanned Aerial Vehicles (UAVs) in civilian domains. To operate in the civilian airspace, a UAV must be able to sense and avoid both static and moving obstacles for flight safety. While indoor and low-altitude environments are mainly occupied by static obstacles, risks in space of higher altitude primarily come from moving obstacles such as other aircraft or flying vehicles in the airspace. Therefore, the ability to avoid moving obstacles becomes a necessity

for Unmanned Aerial Vehicles.

Towards enabling a UAV to autonomously sense and avoid moving obstacles, this thesis makes the following contributions. Initially, an image-based reactive motion planner is developed for a quadrotor to avoid a fast approaching obstacle. Furthermore, A Dubin’s curve based geometry method is developed as a global path planner for a fixed-wing UAV to avoid collisions with aircraft. The image-based method is unable to produce an optimal path and the geometry method uses a simplified UAV model. To compensate

these two disadvantages, a series of algorithms built upon the Closed-Loop Rapid Exploratory Random Tree are developed as global path planners to generate collision avoidance paths in real time. The algorithms are validated in Software-In-the-Loop (SITL) and Hardware-In-the-Loop (HIL) simulations using a fixed-wing UAV model and in real flight experiments using quadrotors. It is observed that the algorithm enables a UAV to avoid moving obstacles approaching to it with different directions and speeds.
ContributorsLin, Yucong (Author) / Saripalli, Srikanth (Thesis advisor) / Scowen, Paul (Committee member) / Fainekos, Georgios (Committee member) / Thangavelautham, Jekanthan (Committee member) / Youngbull, Cody (Committee member) / Arizona State University (Publisher)
Created2015
Description
This study aims to address the deficiencies of the Marcus model of electron transfer

(ET) and then provide modifications to the model. A confirmation of the inverted energy

gap law, which is the cleanest verification so far, is presented for donor-acceptor complexes.

In addition to the macroscopic properties of the solvent, the physical

This study aims to address the deficiencies of the Marcus model of electron transfer

(ET) and then provide modifications to the model. A confirmation of the inverted energy

gap law, which is the cleanest verification so far, is presented for donor-acceptor complexes.

In addition to the macroscopic properties of the solvent, the physical properties of the solvent

are incorporated in the model via the microscopic solvation model. For the molecules

studied in this dissertation, the rate constant first increases with cooling, in contrast to the

prediction of the Arrhenius law, and then decreases at lower temperatures. Additionally,

the polarizability of solute, which was not considered in the original Marcus theory, is included

by the Q-model of ET. Through accounting for the polarizability of the reactants, the

Q-model offers an important design principle for achieving high performance solar energy

conversion materials. By means of the analytical Q-model of ET, it is shown that including

molecular polarizability of C60 affects the reorganization energy and the activation barrier

of ET reaction.

The theory and Electrochemistry of Ferredoxin and Cytochrome c are also investigated.

By providing a new formulation for reaction reorganization energy, a long-standing disconnect

between the results of atomistic simulations and cyclic voltametery experiments is

resolved. The significant role of polarizability of enzymes in reducing the activation energy

of ET is discussed. The binding/unbinding of waters to the active site of Ferredoxin leads

to non-Gaussian statistics of energy gap and result in a smaller activation energy of ET.

Furthermore, the dielectric constant of water at the interface of neutral and charged

C60 is studied. The dielectric constant is found to be in the range of 10 to 22 which is

remarkably smaller compared to bulk water( 80). Moreover, the interfacial structural

crossover and hydration thermodynamic of charged C60 in water is studied. Increasing the

charge of the C60 molecule result in a dramatic structural transition in the hydration shell,

which lead to increase in the population of dangling O-H bonds at the interface.
ContributorsWaskasi, Morteza M (Author) / Matyushov, Dmitry (Thesis advisor) / Richert, Ranko (Committee member) / Heyden, Matthias (Committee member) / Beckstein, Oliver (Committee member) / Arizona State University (Publisher)
Created2019