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  Partner: UNT Libraries
 Department: Department of Chemistry
 Decade: 2010-2019
 Collection: UNT Theses and Dissertations
Ab Initio and Density Functional Investigation of the Conformer Manifold of Melatonin and a Proposal for a Simple Dft-based Diagnostic for Nondynamical Correlation
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In this work we address two problems in computational chemistry relevant to biomolecular modeling. In the first project, we consider the conformer space of melatonin as a a representative example of “real-life” flexible biomolecules. Geometries for all 52 unique conformers are optimized using spin-component scaled MP2, and then relative energies are obtained at the CCSD (T) level near the complete basis set limit. These are then used to validate a variety of DFT methods with and without empirical dispersion corrections, as well as some lower-level ab initio methods. Basis set convergence is found to be relatively slow due to internal C-H…O and C-H…N contacts. Absent dispersion corrections, many DFT functionals will transpose the two lowest conformers. Dispersion corrections resolve the problem for most functionals. Double hybrids yield particularly good performance, as does MP2.5. In the second project, we propose a simple DFT-based diagnostic for nondynamical correlation effects. Aλ= (1-TAE [ΧλC]/TAE[XC])/λ where TAE is the total atomization energy, XC the “pure” DFT exchange-correlation functional, and ΧλC the corresponding hybrid with 100λ% HF-type exchange. The diagnostic is a good predictor for sensitivity of energetics to the level of theory, unlike most of the wavefunction-based diagnostics. For GGA functionals, Aλ values approaching unity indicate severe non-dynamical correlation. The diagnostic is only weakly sensitive to the basis set (beyond polarized double zeta) and can be applied to problems beyond practical reach of wavefunction ab-initio methods required for other diagnostics. digital.library.unt.edu/ark:/67531/metadc500195/
Acceptor-sensitizers for Nanostructured Oxide Semiconductor in Excitonic Solar Cells
Organic dyes are examined in photoelectrochemical systems wherein they engage in thermal (rather than photoexcited) electron donation into metal oxide semiconductors. These studies are intended to elucidate fundamental parameters of electron transfer in photoelectrochemical cells. Development of novel methods for the structure/property tuning of electroactive dyes and the preparation of nanostructured semiconductors have also been discovered in the course of the presented work. Acceptor sensitized polymer oxide solar cell devices were assembled and the impact of the acceptor dyes were studied. The optoelectronic tuning of boron-chelated azadipyrromethene dyes has been explored by the substitution of carbon substituents in place of fluoride atoms at boron. Stability of singlet exited state and level of reduction potential of these series of aza-BODIPY coumpounds were studied in order to employ them as electron-accepting sensitizers in solid state dye sensitized solar cells. digital.library.unt.edu/ark:/67531/metadc699927/
Accuracy and Efficiency in Computational Chemistry: The Correlation Consistent Composite Approach
One of the central concerns of computational chemistry is that of efficiency (i.e. the development of methodologies which will yield increased accuracy of prediction without requiring additional computational resources – RAM, disk space, computing time). Though the equations of quantum mechanics are known, the solutions to these equations often require a great deal of computing power. This dissertation primarily concerns the theme of improved computational efficiency (i.e. the achievement of greater accuracy with reduced computational cost). Improvements in the efficiency of computational chemistry are explored first in terms of the correlation consistent composite approach (ccCA). The ccCA methodology was modified and this enhanced ccCA methodology was tested against the diverse G3/05 set of 454 energetic properties. As computational efficiency improves, molecules of increasing size may be studied and this dissertation explored the issues (differential correlation and size extensivity effects) associated with obtaining chemically accurate (within 1 kcal mol-1) enthalpies of formation for hydrocarbon molecules of escalating size. Two applied projects are also described; these projects concerned the theoretical prediction of a novel rare gas compound, FKrOH, and the mechanism of human glutathione synthetase’s (hGS) negative cooperativity. The final work examined the prospect for the parameterization of the modified embedded atom method (MEAM) potential using first principles calculations of dimer and trimer energies of nickel and carbon systems. This method of parameterization holds promise for increasing the accuracy of simulations for bulk properties within the field of materials science. digital.library.unt.edu/ark:/67531/metadc84300/
Accurate and Reliable Prediction of Energetic and Spectroscopic Properties Via Electronic Structure Methods
Computational chemistry has led to the greater understanding of the molecular world, from the interaction of molecules, to the composition of molecular species and materials. Of the families of computational chemistry approaches available, the main families of electronic structure methods that are capable of accurate and/or reliable predictions of energetic, structural, and spectroscopic properties are ab initio methods and density functional theory (DFT). The focus of this dissertation is to improve the accuracy of predictions and computational efficiency (with respect to memory, disk space, and computer processing time) of some computational chemistry methods, which, in turn, can extend the size of molecule that can be addressed, and, for other methods, DFT, in particular, gain greater insight into which DFT methods are more reliable than others. Much, though not all, of the focus of this dissertation is upon transition metal species – species for which much less method development has been targeted or insight about method performance has been well established. The ab initio approach that has been targeted in this work is the correlation consistent composite approach (ccCA), which has proven to be a robust, ab initio computational method for main group and first row transition metal-containing molecules yielding, on average, accurate thermodynamic properties, i.e., within 1 kcal/mol of experiment for main group species and within 3 kcal/mol of experiment for first row transition metal molecules. In order to make ccCA applicable to systems containing any element from the periodic table, development of the method for second row transition metals and heavier elements, including lower p-block (5p and 6p) elements was pursued. The resulting method, the relativistic pseudopotential variant of ccCA (rp-ccCA), and its application are detailed for second row transition metals and lower p-block elements. Because of the computational cost of ab initio methods, DFT is a popular choice for the study of transition metals. Despite this, the most reliable density functionals for the prediction of energetic properties (e.g. enthalpy of formation, ionization potential, electron affinity, dissociation energy) of transition metal species, have not been clearly identified. The examination of DFT performance for first and second row transition metal thermochemistry (i.e., enthalpies of formation) was conducted and density functionals for the study of these species were identified. And, finally, to address the accuracy of spectroscopic and energetic properties, improvements for a series of density functionals have been established. In both DFT and ab initio methods, the harmonic approximation is typically employed. This neglect of anharmonic effects, such as those related to vibrational properties (e.g. zero-point vibrational energies, thermal contributions to enthalpy and entropy) of molecules, generally results in computational predictions that are not in agreement with experiment. To correct for the neglect of anharmonicity, scale factors can be applied to these vibrational properties, resulting in better alignment with experimental observations. Scale factors for DFT in conjunction with both the correlation and polarization consistent basis sets have been developed in this work. digital.library.unt.edu/ark:/67531/metadc500071/
Advancements in Instrumentation for Fourier Transform Microwave Spectroscopy
The efforts of my research have led to the successful construction of several instruments that have helped expand the field of microwave spectroscopy. The classic Balle-Flygare spectrometer has been modified to include two different sets of antenna to operate in the frequency ranges 6-18 GHz and 18-26 GHz, allowing it to function for a large range without having to break vacuum. This modified FTMW instrument houses two low noise amplifiers in the vacuum chamber to allow for the LNAs to be as close to the antenna as physically possible, improving sensitivity. A new innovative Balle-Flygare type spectrometer, the efficient low frequency FTMW, was conceived and built to operate at frequencies as low as 500 MHz through the use of highly curved mirrors. This is new for FTMW techniques that normally operate at 4 GHz or higher with only a few exceptions around 2 GHz. The chirped pulse FTMW spectrometer uses horn antennas to observe spectra that span 2 GHz versus the standard 1 MHz of a cavity technique. This instrument decreases the amount of time to obtain a large spectral region of relative correct intensity molecular transitions. A Nd:YAG laser ablation apparatus was attached to the classic Balle-Flygare and chirped pulse FTMW spectrometers. This allowed the study of heavy metal containing compounds. The instruments I constructed and the techniques I used have allowed the discovery of further insights into molecular chemistry. I have seen the effects of fluorinating an alkyl halide by determining the geometry of the carbon backbone of trans-1-iodoperfluoropropane and observing a ΔJ = 3 forbidden transition caused by a strong quadrupole coupling constant on this heavy molecule. The quadrupole coupling tensors of butyronitrile, a molecule observed in space, have been improved. The nuclear quadrupole coupling tensor of difluoroiodomethane was added to a list of variably fluorinated methyl halides upholding a trend for the magnitude of χzz. The study of SrS led to the determination of the Born-Oppenheimer breakdown terms and improving the precision of the SrS internuclear distance. I have also conducted the first pure rotational spectroscopic investigation on an actinide containing molecule, ThO. digital.library.unt.edu/ark:/67531/metadc84308/
Affordances of Instrumentation in General Chemistry Laboratories
The purpose of this study is to find out what students in the first chemistry course at the undergraduate level (general chemistry for science majors) know about the affordances of instrumentation used in the general chemistry laboratory and how their knowledge develops over time. Overall, students see the PASCO™ system as a useful and accurate measuring tool for general chemistry labs. They see the probeware as easy to use, portable, and able to interact with computers. Students find that the PASCO™ probeware system is useful in their general chemistry labs, more advanced chemistry labs, and in other science classes, and can be used in a variety of labs done in general chemistry. Students learn the affordances of the probeware through the lab manual, the laboratory teaching assistant, by trial and error, and from each other. The use of probeware systems provides lab instructors the opportunity to focus on the concepts illustrated by experiments and the opportunity to spend time discussing the results. In order to teach effectively, the instructor must know the correct name of the components involved, how to assemble and disassemble it correctly, how to troubleshoot the software, and must be able to replace broken or missing components quickly. The use of podcasts or Web-based videos should increase student understanding of affordances of the probeware. digital.library.unt.edu/ark:/67531/metadc30510/
Boron Nitride by Atomic Layer Deposition: A Template for Graphene Growth
The growth of single and multilayer BN films on several substrates was investigated. A typical atomic layer deposition (ALD) process was demonstrated on Si(111) substrate with a growth rate of 1.1 Å/cycle which showed good agreement with the literature value and a near stoichiometric B/N ratio. Boron nitride films were also deposited by ALD on Cu poly crystal and Cu(111) single crystal substrates for the first time, and a growth rate of ~1ML/ALD cycle was obtained with a B/N ratio of ~2. The realization of a h-BN/Cu heterojunction was the first step towards a graphene/h-BN/Cu structure which has potential application in gateable interconnects. digital.library.unt.edu/ark:/67531/metadc84305/
Carbon Nanostructure Based Donor-acceptor Systems for Solar Energy Harvesting
Carbon nanostructure based functional hybrid molecules hold promise in solarenergy harvesting. Research presented in this dissertation systematically investigates building of various donor-acceptor nanohybrid systems utilizing enriched single walled carbon nanotube and graphene with redox and photoactive molecules such as fullerene, porphyrin, and phthalocyanine. Design, synthesis, and characterization of the donor-acceptor hybrid systems have been carefully performed via supramolecular binding strategies. Various spectroscopic studies have provided ample information in terms of establishment of the formation of donor-acceptor hybrids and their extent of interaction in solution and eventual rate of photoinduced electron and/or energy transfer. Electrochemical studies enabled construction of energy level diagram revealing energetic details of the possible different photochemical events supported by computational studies carried out to establish the HOMO-LUMO levels in the donor acceptor systems. Transient absorption studies confirmed formation of charge separated species in the donor-acceptor systems which have been supported by electron mediation experiments. Based on the photoelectrochemical studies, IPCE of 8% was reported for enriched SWCNT(7,6)-ZnP donor-acceptor systems. In summary, the present investigation on the various nanocarbon sensitized donor-acceptor hybrids substantiates tremendous prospect, that could very well become the next generation of materials in building efficient solar energy harvesting devices andphotocatalyst. digital.library.unt.edu/ark:/67531/metadc407823/
Characterization of Ionic Liquid Solvents Using a Temperature Independent, Ion-specific Abraham Parameter Model
Experimental data for the logarithm of the gas-to-ionic liquid partition coefficient (log K) have been compiled from the published literature for over 40 ionic liquids over a wide temperature range. Temperature independent correlations based on the Gibbs free energy equation utilizing known Abraham solvation model parameters have been derived for the prediction of log K for 12 ionic liquids to within a standard deviation of 0.114 log units over a temperature range of over 60 K. Temperature independent log K correlations have also been derived from correlations of molar enthalpies of solvation and molar entropies of solvation, each within standard deviations of 4.044 kJ mol-1 and 5.338 J mol-1 K-1, respectively. In addition, molar enthalpies of solvation and molar entropies of solvation can be predicted from the Abraham coefficients in the temperature independent log K correlations to within similar standard deviations. Temperature independent, ion specific coefficients have been determined for 26 cations and 15 anions for the prediction of log K over a temperature range of at least 60 K to within a standard deviation of 0.159 log units. digital.library.unt.edu/ark:/67531/metadc699933/
Characterization of Novel Solvents and Absorbents for Chemical Separations
Predictive methods have been employed to characterize chemical separation mediums including solvents and absorbents. These studies included creating Abraham solvation parameter models for room-temperature ionic liquids (RTILs) utilizing novel ion-specific and group contribution methodologies, polydimethyl siloxane (PDMS) utilizing standard methodology, and the micelles cetyltrimethylammonium bromide (CTAB) and sodium dodecylsulfate (SDS) utilizing a combined experimental setup methodology with indicator variables. These predictive models allows for the characterization of both standard and new chemicals for use in chemical separations including gas chromatography (GC), solid phase microextraction (SPME), and micellar electrokinetic chromatography (MEKC). Gas-to-RTIL and water-to-RTIL predictive models were created with a standard deviation of 0.112 and 0.139 log units, respectively, for the ion-specific model and with a standard deviation of 0.155 and 0.177 log units, respectively, for the group contribution fragment method. Enthalpy of solvation for solutes dissolved into ionic liquids predictive models were created with ion-specific coefficients to within standard deviations of 1.7 kJ/mol. These models allow for the characterization of studied ionic liquids as well as prediction of solute-solvent properties of previously unstudied ionic liquids. Predictive models were created for the logarithm of solute's gas-to-fiber sorption and water-to-fiber sorption coefficient for polydimethyl siloxane for wet and dry conditions. These models were created to standard deviations of 0.198 and 0.122 logunits for gas-to-PDMS wet and dry, respectively, as well as 0.164 and 0.134 log units for water-to-PDMS wet and dry, respectively. These models are particularly useful in solid phase microextraction separations. Micelles were studied to create predictive models of the measured micelle-water partition coefficient as well as models of measured MEKC chromatographic retention factors for CTAB and SDS. The resultant predictive models were created with standard deviations of 0.190 log units for the logarithm of the mole fraction concentration of water-to-CTAB, 0.171 log units for the combined logarithms of both the mole fraction concentration of water-to-CTAB and measured MEKC chromatographic retention factors for CTAB, and 0.153 log units for the combined logarithms of both the mole fraction concentration of water-to-SDS and measured MEKC chromatographic retention factors for SDS. digital.library.unt.edu/ark:/67531/metadc67989/
Chirped-Pulse Fourier Transform Microwave Spectroscopy of Fluoroiodoacetonitrile and Chloropentafluoroacetone
This work focuses on finding the complete iodine and nitrogen nuclear electric quadrupole coupling tensors for fluoroiodoacetonitrile using chirped-pulse Fourier transform microwave spectroscopy. Fluoroiodoacetonitrile contains two hyperfine nuclei, iodine (I=5/2) and nitrogen (I=1) and the spectra were observed with great resolution. A total of 499 transitions were observed for this molecule. The a, b and c rotational constants were obtained. A study of chloropentafluoroacetone was also done using chirped-pulse Fourier transform microwave spectroscopy. The two chlorine isotopes for this molecule, Cl-35 and Cl-37 were observed and 326 and 170 transitions were recorded, respectively. digital.library.unt.edu/ark:/67531/metadc84230/
Computational Investigation of Molecular Optoelectronic and Biological Systems
The scope of work in this dissertation has comprised several major investigations on applications and theoretical studies of ab initio quantum mechanics and density functional theory where those techniques were applied to the following: (i) investigation of the performance of density functionals for the computations of molecular properties of 3d transition metal containing systems; (ii) guidance for experimental groups for rational design of macrometallocyclic multinuclear complexes with superior π-acidity and π-basicity that are most suitable for p- and n-type semiconductors of metal-organic molecules and nanomaterials; (iii) investigation of the metallo-aromaticity of multi-nuclear metal complexes; (iv) investigation of the kinetics and thermodynamics of copper-mediated nitrene insertion into C-H and H-H bond; and (v) accurate computations of dissociation energies of hydrogen-bonded DNA duplex moieties utilizing the resolution of identity correlation consistent composite approach (RI-ccCA). digital.library.unt.edu/ark:/67531/metadc84288/
Computational Studies of Inorganic Systems with a Multiscale Modeling Approach: From Atomistic to Continuum Scale
Multiscale modeling is an effective tool for integrating different computational methods, creating a way of modeling diverse chemical and physical phenomena. Presented are studies on a variety of chemical problems at different computational scales and also the combination of different computational methods to study a single phenomenon. The methods used encompass density functional theory (DFT), molecular dynamics (MD) simulations and finite element analysis (FEA). The DFT studies were conducted both on the molecular level and using plane-wave methods. The particular topics studied using DFT are the rational catalyst design of complexes for C—H bond activation, oxidation of nickel surfaces and the calculation of interaction properties of carbon dioxide containing systems directed towards carbon dioxide sequestration studies. Second and third row (typically precious metals) transition metal complexes are known to possess certain electronic features that define their structure and reactivity, and which are usually not observed in their first-row (base metal) congeners. Can these electronic features be conferred onto first-row transition metals with the aid of non-innocent and/or very high-field ligands? Using DFT, the impact of these electronic features upon methane C—H bond activation was modeled using the dipyridylazaallyl (smif) supporting ligand for late, first-row transition metal (M) imide, oxo and carbene complexes (M = Fe, Co, Ni, Cu; E = O, NMe, CMe2). To promote a greater understanding of the process and nature of metal passivation, first-principles analysis of partially oxidized Ni(111) and Ni(311) surface and ultra-thin film NiO layers on Ni(111) was performed. A bimodal theoretical strategy that considers the oxidation process using either a fixed GGA functional for the description of all atoms in the system, or a perturbation approach, that perturbs the electronic structure of various Ni atoms in contact with oxygen by application of the GGA+U technique was applied. Binding energy of oxygen to the nickel surfaces, charge states of nickel and oxygen, and the preferred binding mode of oxygen to nickel were studied to gain a better understanding of the formation of oxide layers. Using density functional theory, the thermodynamic properties for developing interaction potentials for molecular dynamics simulations of carbon dioxide systems were calculated. The interactions considered are Ni + H2O, Ni + Ni, Ni + CO2, CO2 + CO2, CO2 + H2O and H2O + H2O. These systems were chosen as the possible interactions that can occur when carbon dioxide is stored in the ocean. Molecular dynamics simulations using the results from the DFT studies were also conducted. Finally, thermal conduction analysis was performed on layered functionally graded materials (FGM) subjected to thermal shock by sudden cooling of the material in order to investigate the results obtained from three different mixing laws: linear, quadratic, and half-order. The functionally graded material considered was a composite of nickel and carbon nanotubes at different compositions varying from two to five layers. The middle layers for the three to five layers are composed of graded (i.e., gradually changing) percentages of nickel and carbon nanotube. The thermal conductivity, specific heat and density for the composites were calculated depending on the percentages of materials in each layer, and assuming different rules of mixture. digital.library.unt.edu/ark:/67531/metadc283802/
Computational Study of Small Molecule Activation via Low-Coordinate Late First-Row Transition Metal Complexes
Methane and dinitrogen are abundant precursors to numerous valuable chemicals such as methanol and ammonia, respectively. However, given the robustness of these substrates, catalytically circumventing the high temperatures and pressures required for such transformations has been a challenging task for chemists. In this work, computational studies of various transition metal catalysts for methane C-H activation and N2 activation have been carried out. For methane C-H activation, catalysts of the form LnM=E are studied, where Ln is the supporting ligand (dihydrophosphinoethane or β-diketiminate), E the activating ligand (O, NCH3, NCF3) at which C-H activation takes place, and M the late transition metal (Fe,Co,Ni,Cu). A hydrogen atom abstraction (HAA) / radical rebound (RR) mechanism is assumed for methane functionalization (CH4 à CH3EH). Since the best energetics are found for (β-diket)Ni=O and (β-diket)Cu=O catalysts, with or without CF3 substituents around the supporting ligand periphery, complete methane-to-methanol cycles were studied for such systems, for which N2O was used as oxygen atom transfer (OAT) reagent. Both monometallic and bimetallic OAT pathways are addressed. Monometallic Fe-N2 complexes of various supporting ligands (LnFe-N2) are studied at the beginning of the N2 activation chapter, where the effect of ligand on N2 activation in end-on vs. side-on N2 isomers is discussed. For (β-diket)Fe-N2 complexes, the additional influence of diketiminate donor atom (N(H) vs. S) is briefly addressed. The remainder of the chapter expands upon the treatment of β-diketiminate complexes. First, the activation and relative stabilities of side-bound and end-bound N2 isomers in monometallic ((β-diket)M-N2) and bimetallic ((β-diket)M-N2-M(β-diket)) first row transition metal complexes are addressed. Second, the thermodynamics of H/H+/H- addition to (β-diket)Fe-bound N2, followed by subsequent H additions up to release of ammonia, is discussed, for which two mechanisms (distal and alternating) are considered. Finally, the chapter concludes with partial distal and alternating mechanisms for H addition to N2 in bimetallic (β-diket)Fe-N2-Fe(β-diket) and (β-diket)M-N2-M(β-diket) (M = Ti,V,Fe), respectively. digital.library.unt.edu/ark:/67531/metadc28462/
Cu Electrodeposition on Ru-Ta and Corrosion of Plasma Treated Cu in Post Etch Cleaning Solution
In this work, the possibility of Cu electrodeposition on Ru-Ta alloy thin films is explored. Ru and Ta were sputter deposited on Si substrate with different composition verified by RBS. Four point probe, XRD, TEM and AFM were used to study the properties of Ru-Ta thin films such as sheet resistance, crystallinity, grain size, etc. Cyclic voltammetry is used to study the Cu electrodeposition characteristics on Ru-Ta after various surface pretreatments. The results provide insights on the removal of Ta oxide such that it enables better Cu nucleation and adhesion. Bimetallic corrosion of Cu on modified Ru-Ta surface was studied in CMP related chemicals. In Cu interconnect fabrication process, the making of trenches and vias on low-k dielectric films involves the application of fluorocarbon plasma etch gases. Cu microdots deposited on Ru and Ta substrate were treated by fluorocarbon plasma etch gases such as CF4, CF4+O2, CH2F2, C4F8 and SF6 and investigated by using x-ray photoelectron spectroscopy, contact angle measurement and electrochemical techniques. Micropattern corrosion screening technique was used to measure the corrosion rate of plasma treated Cu. XPS results revealed different surface chemistry on Cu after treating with plasma etching. The fluorine/carbon ratio of the etching gases results in different extent of fluorocarbon polymer residues and affects the cleaning efficiency and Cu corrosion trends. digital.library.unt.edu/ark:/67531/metadc84286/
Design and Development of Soft Landing Ion Mobility: A Novel Instrument for Preparative Material Development
The design and fabrication of a novel soft landing instrument Soft Landing Ion Mobility (SLIM) is described here. Topics covered include history of soft landing, gas phase mobility theory, the design and fabrication of SLIM, as well as applications pertaining to soft landing. Principle applications devised for this instrument involved the gas phase separation and selection of an ionized component from a multicomponent gas phase mixture as combing technique to optimize coatings, catalyst, and a variety of alternative application in the sciences. digital.library.unt.edu/ark:/67531/metadc84197/
Design, Synthesis and Screening of Homoleptic and Heteroleptic Platinum(ii) Pyridylazolate Complexes for N-type Semiconducting and Light-emitting Devices
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A series of heteroleptic and homoleptic platinum(II) complexes has been synthesized and characterized towards their use in thin film devices such as organic light-emitting diodes (OLEDs) and organic thin film transistors (OTFTs). Pyridylpyrazolate- and pyridyltetrazolate-containing ligands were selected due to their structural rigidity and ease of functionalization. Single-crystal x-ray diffraction studies of two selected heteroleptic complexes show strong aggregation with preferential stacking into vertical columns with a varying degree of overlap of the neighboring square planar molecular units. It is shown that the close proximity of the molecules to one another in the stack increases semiconducting character, phosphorescence quantum yields, and shorter radiative lifetimes. The potential for these materials towards incorporation into high-efficiency doping free white OLEDs (DFW-OLEDs) for solid-state lighting and display applications has been realized and will be expanded upon by present and future embodiments of materials in this thesis. digital.library.unt.edu/ark:/67531/metadc283853/
Determination of Molecular Descriptors for Illegal Drugs by Gc-fid Using Abraham Solvation Model
The Abraham solvation parameter model is a good approach for analyzing and predicting biological activities and partitioning coefficients. The general solvation equation has been used to predict the solute property (SP) behavior of drug compounds between biological barriers. Gas chromatography (GC) retention time can be used to predict molecular descriptors, such as E, S, A, B & L for existing and newly developed drug compounds. In this research, six columns of different stationary phases were used to predict the Abraham molecular descriptors more accurately. The six stationary phases used were 5% phenylmethyl polysiloxane, 6% cyanopropylphenyl 94% dimethylpolysiloxane, 5% diphenyl 95% dimethylpolysiloxane, 100% dimethylpolysiloxane, polyethylene glycol and 35% diphenyl 65% dimethylpolysiloxane. Retention times (RT) of 75 compounds have been measured and logarithm of experimental average retention time Ln(RTexp) are calculated. The Abraham solvation model is then applied to predict the process coefficients of these compounds using the literature values of the molecular descriptors (Acree Compilation descriptors). Six correlation equations are built up as a training set for each of the six columns. The six equations are then used to predict the molecular descriptors of the illegal drugs as a test set. This work shows the ability to extract molecular information from a new compound by utilizing commonly used GC columns available with the desired stationary phases. One can simply run the new compound in GC using these columns to get the retention time. Plugging in the retention time into the developed equations for each of the column will predict the molecular descriptors for the test compound and will give some information about the properties of the compound. digital.library.unt.edu/ark:/67531/metadc407830/
Development of a Laponite Pluronic Composite for Foaming Applications
The focus of the following research was to provide an optimized particle stabilized foam of Laponite and Pluronic L62 in water by understanding (1) the Laponite-Pluronic interactions and properties for improved performance in a particle stabilized foam and (2) the interfacial properties between air and the Laponite-Pluronic complex. These studies were conducted using both bulk and interfacial rheology, XRD, sessile droplet, TGA and UV-vis. Two novel and simple techniques, lamella break point and capillary breakup extensional rheometry, were used to both understand the Laponite Pluronic L62 interaction and determine a different mechanism for foaming properties. Bulk rheological properties identified an optimal Laponite concentration of 2% with Pluronic L62 ranging from 2.5% and 6.5%, due to the ease of flow for the dispersion. The Pluronic L62 was observed to enhance the Laponite bulk rheological properties in solution. Additionally TGA showed a similar trend in thermal resistance to water with both addition of Laponite and Pluronic L62. XRD demonstrated that 0.25% Pluronic intercalated into Laponite from dried 2% Laponite films. XRD demonstrated that the Laponite matrix was saturated at 1% Pluronic L62. UV-vis demonstrated that a monolayer of Pluronic L62 is observed up to 0.65% Pluronic L62 onto Laponite. Interfacial rheology showed that Laponite enhances Pluronic L62 at the air-liquid interface by improving the storage modulus as low at 0.65% Pluronic L62 with 2% Laponite. The lamella breakpoint of Laponite with Pluronic films indicate strong film interaction due to higher increases in mass. Extensional rheology indicates that 2.5% to 6.5% Pluronic with 2% Laponite show the most filament resistance to stretching. digital.library.unt.edu/ark:/67531/metadc271798/
The Development of an Analytical Microwave Electromagnetic Pulse Transmission Probe and Preliminary Test Results
Within this educational endeavor instrumental development was explored through the investigation of microwave induce stable electromagnetic waves within a non-linear yttrium iron garnet ferromagnetic waveguide. The resulting magnetostatic surface waves were investigated as a possible method of rapid analytical evaluation of material composition. Initial analytical results indicate that the interaction seen between wave and material electric and magnetic fields will allow phase coherence recovery andanalysis leading to enhancement of analytical value. The ferromagnetic waveguide selected for this research was a high quality monocrystalline YIG (yttrium iron garnet) film. Magnetostatic spin waves (MSW) were produced within the YIG thin waveguide. Spin waves with desired character were used to analytically scan materials within the liquid and solid phase. digital.library.unt.edu/ark:/67531/metadc67987/
Development of Novel Semi-conducting Ortho-carborane Based Polymer Films: Enhanced Electronic and Chemical Properties
A novel class of semi-conducting ortho-carborane (B10C2H12) based polymer films with enhanced electronic and chemical properties has been developed. The novel films are formed from electron-beam cross-linking of condensed B10C2H12 and B10C2H12 co-condensed with aromatic linking units (Y) (Y=1,4-diaminobenzene (DAB), benzene (BNZ) and pyridine (PY)) at 110 K. The bonding and electronic properties of the novel films were investigated using X-ray photoelectron spectroscopy (XPS), UV photoelectron spectroscopy (UPS) and Mulliken charge analysis using density functional theory (DFT). These films exhibit site-specific cross-linking with bonding, in the pure B10C2HX films, occurring at B sites non-adjacent to C in the B10C2H12 icosahedra. The B10C2H12:Y films exhibit the same phenomena, with cross-linking that creates bonds primarily between B sites non-adjacent to C in the B10C2H12 icosahedra to C sites in the Y linking units. These novel B10C2HX: Y linked films exhibit significantly different electron structure when compared to pure B10C2HX films as seen in the UPS spectra. The valence band maxima (VBM) shift from - 4.3 eV below the Fermi level for pure B10C2HX to -2.6, -2.2, and -1.7 for B10C2HX:BNZ, B10C2HX:PY, and B10C2HX:DAB, respectively. The top of the valence band is composed of states derived primarily from the Y linking units, suggesting that the bottom of the conduction band is composed of states primarily from B10C2H12. Consequently these B10C2HX:Y films may exhibit longer electron-hole separation lifetimes as compared to pure B10C2HX films. This research should lead to an enhancement of boron carbide based neutron detectors, and is of potential significance for microelectronics, spintronics and photo-catalysis. digital.library.unt.edu/ark:/67531/metadc283826/
Diimine(dithiolate)platinum(ii) Chromophores: Synthesis, Spectroscopy, and Material Applications
A series of 28 square-planar dithiol(diimine)platinum(II) chromophoric complexes have been synthesized, characterized, and evaluated for potential efficacy in sensitization of solid state photovoltaic devices to the near-infrared regions of the electromagnetic spectrum. The effect of molecular stacking in the solid state and self-association in solution are shown to influence spectral, electronic, and magnetic properties of the chromophores. Such properties are investigated in the pure form and as partners in donor-acceptor charge transfer adducts. Finally, selected chromophores have been incorporated into single layer schottky diodes as neat films and as dopants in multi-layer organic photovoltaic devices. Evaluation of the devices internal quantum efficiency and voltage-current was measured as proof of concept. digital.library.unt.edu/ark:/67531/metadc699877/
Effect of Fluorine and Hydrogen Radical Species on Modified Oxidized Ni(pt)si
NiSi is an attractive material in the production of CMOS devices. The problem with the utilization of NiSi, is that there is no proper method of cleaning the oxide on the surface. Sputtering is the most common method used for the cleaning, but it has its own complications. Dry cleaning methods include the reactions with radicals and these processes are not well understood and are the focus of the project. Dissociated NF3 and NH3 were used as an alternative and XPS is the technique to analyze the reactions of atomic fluorine and nitrogen with the oxide on the surface. A thermal cracker was used to dissociate the NF3 and NH3 into NFx+F and NHx+H. There was a formation of a NiF2 layer on top of the oxide and there was no evidence of nitrogen on the surface indicating that the fluorine and hydrogen are the reacting species. XPS spectra, however, indicate that the substrate SiO2 layer is not removed by the dissociated NF3 and NiF2 growth process. The NiF2 over layer can be reduced to metallic Ni by reacting with dissociated NH3 at room temperature. The atomic hydrogen from dissociated ammonia reduces the NiF2 but it was determined that the atomic hydrogen from the ammonia does not react with SiO2. digital.library.unt.edu/ark:/67531/metadc28421/
The Effect of Plasma on Silicon Nitride, Oxynitride and Other Metals for Enhanced Epoxy Adhesion for Packaging Applications
The effects of direct plasma chemistries on carbon removal from silicon nitride (SiNx) and oxynitride (SiOxNy ) surfaces and Cu have been studied by x-photoelectron spectroscopy (XPS) and ex-situ contact angle measurements. The data indicate that O2,NH3 and He capacitively coupled plasmas are effective at removing adventitious carbon from silicon nitride (SiNx) and Silicon oxynitride (SiOxNy ) surfaces. O2plasma and He plasma treatment results in the formation of silica overlayer. In contrast, the exposure to NH3 plasma results in negligible additional oxidation of the SiNx and SiOxNy surface. Ex-situ contact angle measurements show that SiNx and SiOxNy surfaces when exposed to oxygen plasma are initially more hydrophilic than surfaces exposed to NH3 plasma and He plasma, indicating that the O2 plasma-induced SiO2 overlayer is highly reactive towards ambient corresponding to increased roughness measured by AFM. At longer ambient exposures (>~10 hours), however surfaces treated by either O2, He or NH3 plasma exhibit similar steady state contact angles, correlated with rapid uptake of adventitious carbon, as determined by XPS. Surface passivation by exposure to molecular hydrogen prior to ambient exposure significantly retards the increase in the contact angle upon the exposure to ambient. The results suggest a practical route to enhancing the time available for effective bonding to surfaces in microelectronics packaging applications. digital.library.unt.edu/ark:/67531/metadc700040/
Effects of Using Logic and Spatial Cybergames to Improve Student Success Rates in Lower-Division Chemistry Courses
A study was conducted to investigate the relationships between cybergaming treatment groups and the control group (N = 99: ncontrol = 8; nlogic = 29; nspatial = 30; ncombination = 32) with success in the organic chemistry I course as measured by achievement over a 10-week period. The treatment groups included logic training, spatial training, and combination logic-spatial training. Students' ability was measured by pre/post exams using the Group Assessment of Logical Thinking (GALT) to measure logic ability, Purdue Visualizations of Rotations (ROT) test to measure spatial skills, and the General-Organic-Biochemistry (GOB) Exam to measure content attainment. Finally, students' responses about participation in this experience were evaluated using open- and closed-ended questions on a self-developed survey. A second study was conducted to evaluate the relationship between the cybergaming treatment and control groups (N = 88: nexperimental = 27; ncontrol = 61) with success in the general chemistry I course as measured by achievement and final course averages and grades. The cybergaming treatment group underwent intensive combination logic-spatial training for 10 weeks. Students' progress was measured using three pre/post instruments: Group Assessment of Logical Thinking (GALT) measured logic ability, Purdue Visualizations of Rotations (ROT) Test measured spatial skills, and the California Chemistry Diagnostic Exam measured content attainment. Finally, students' responses about their participation in this experience were evaluated using open- and closed-ended questions on a self-developed survey. Analyses of the data were performed to determine the relationships between cybergaming treatments and control groups in organic chemistry I and general chemistry I courses. In organic chemistry I results showed no statistical or practical significance as to students' success. In general chemistry I results indicated statistical significance and medium practicality for students with an average grade of C and for females over males as to improvement of spatial skills. digital.library.unt.edu/ark:/67531/metadc68010/
Electrochemical Depostion of Bismuth on Ruthenium and Ruthenium Oxide Surfaces
Cyclic voltammetry experiments were performed to compare the electrodeposition characteristics of bismuth on ruthenium. Two types of electrodes were used for comparison: a Ru shot electrode (polycrystalline) and a thin film of radio-frequency sputtered Ru on a Ti/Si(100) support. Experiments were performed in 1mM Bi(NO3)3/0.5M H2SO4 with switching potentials between -0.25 and 0.55V (vs. KCl sat. Ag/AgCl) and a 20mV/s scan rate. Grazing incidence x-ray diffraction (GIXRD) determined the freshly prepared thin film electrode was hexagonally close-packed. After thermally oxidizing at 600°C for 20 minutes, the thin film adopts the tetragonal structure consistent with RuO2. a hydrated oxide film (RuOx?(H2O)y) was made by holding 1.3V on the surface of the film in H2SO4 for 60 seconds and was determined to be amorphous. Underpotential deposition of Bi was observed on the metallic surfaces and the electrochemically oxidized surface; it was not observed on the thermal oxide. digital.library.unt.edu/ark:/67531/metadc115169/
Electrochemical Quartz Crystal Microbalance Study Of Bismuth Underpotential Deposition On Ruthenium And On Electrochemically Formed Ruthenium Oxide
Kinetics and thermodynamics of bismuth (Bi) underpotential deposition (UPD) on ruthenium (Ru) and on electrochemically formed Ru oxide are studied using electrochemical quartz crystal microbalance technique. The Bi UPD and Bi bulk deposition are observed both on Ru and on electrochemically formed Ru oxide electrodes. The anodic peak potential of Bi UPD shifts slightly to positive potential as the scan rate increases. The peak current ratio (IAnode/ICathode) of Bi UPD and Bi bulk increases as the scan rate increases. Bi monolayer coverage calculated from mass (MLMass) and from charge (MLCharge) with scan rates dependent are compared both in Bi UPD region and in Bi bulk region. Stability and oxidation time effects are also investigated. Bi UPD on Ru and on electrochemically formed Ru oxide are quasi-reversible, scan rate independent, oxidation time dependent, and have higher plating efficiency on Ru. However, Bi bulk deposition on Ru and on electrochemically formed Ru oxide are quasi-reversible, scan rate dependent, oxidation time independent, and have higher plating efficiency on electrochemically formed Ru oxide. Both Bi UPD adatoms and Bi bulk are unstable in 0.5M H2SO4. digital.library.unt.edu/ark:/67531/metadc103354/
Electrochemically Deposited Metal Alloy-silicate Nanocomposite Corrosion Resistant Materials
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Zinc-nickel ?-phase silicate and copper-nickel silicate corrosion resistant coatings have been prepared via electrochemical methods to improve currently available corrosion resistant materials in the oil and gas industry. A layered silicate, montmorillonite, has been incorporated into the coatings for increased corrosion protection. For the zinc nickel silicate coatings, optimal plating conditions were determined to be a working pH range of 9.3 -9.5 with a borate based electrolyte solution, resulting in more uniform deposits and better corrosion protection of the basis metal as compared to acidic conditions. Quality, strongly adhering deposits were obtained quickly with strong, even overall coverage of the metal substrate. The corrosion current of the zinc-nickel-silicate coating is Icorr = 3.33E-6 for a borate based bath as compared to a zinc-nickel bath without silicate incorporation (Icorr = 3.52E-5). Step potential and direct potential methods were examined, showing a morphological advantage to step potential deposition. The effect of borate addition was examined in relation to zinc, nickel and zinc-nickel alloy deposition. Borate was found to affect the onset of hydrogen evolution and was examined for absorption onto the electrode surface. For copper-nickel silicate coatings, optimal conditions were determined to be a citrate based electrolytic bath, with pH = 6. The solutions were stable over time and strong adhering, compact particle deposits were obtained. The corrosion current of the copper-nickel-silicate coatings is Icorr = 3.86E-6 (copper-nickel coatings without silicate, Icorr = 1.78E-4). The large decrease in the corrosion current as the silicate is incorporated into the coating demonstrates the increase in corrosion resistance of the coatings with the incorporation of silicates. digital.library.unt.edu/ark:/67531/metadc271794/
Electrodeposition of Nickel and Nickel Alloy Coatings with Layered Silicates for Enhanced Corrosion Resistance and Mechanical Properties
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The new nickel/layered silicate nanocomposites were electrodeposited from different pHs to study the influence on the metal ions/layered silicate plating solution and on the properties of the deposited films. Nickel/layered silicate nanocomposites were fabricated from citrate bath atacidic pHs (1.6−3.0), from Watts’ type solution (pH ~4-5), and from citrate bath at basic pH (~9). Additionally, the new nickel/molybdenum/layered silicate nanocomposites were electrodeposited from citrate bath at pH 9.5. The silicate, montmorillonite (MMT), was exfoliated by stirring in aqueous solution over 24 hours. The plating solutions were analyzed for zeta potential, particle size, viscosity, and conductivity to investigate the effects of the composition at various pHs. The preferred crystalline orientation and the crystalline size of nickel, nickel/layered silicate, nickel/molybdenum, and nickel/molybdenum/layered silicate films were examined by X-ray diffraction. The microstructure of the coatings and the surface roughness was investigated by scanning electron microscopy and atomic force microscopy. Nickel/molybdenum/layered silicate nanocomposites containing low content of layered silicate (1.0 g/L) had increase 32 % hardness and 22 % Young’s modulus values over the pure nickel/molybdenum alloy films. The potentiodynamic polarization and electrochemical impedance measurements showed that the nickel/molybdenum/layered silicate nanocomposite layers have higher corrosion resistance in 3.5% NaCl compared to the pure alloy films. The corrosion current density of the nickel/molybdenum/layered silicate nanocomposite composed of 0.5 g/L MMT is 0.63 µA·cm-2 as compare to a nickel/molybdenum alloy which is 2.00 µA·cm-2. digital.library.unt.edu/ark:/67531/metadc699999/
Examination and Development of the Correlation Consistent Composite Approach
The primary focus of this dissertation is the advancement of the correlation consistent composite approach (ccCA) methodology from its original formulation to the current implementation. Although for large main group test sets which contained both first- (Li-Ne) and second-row (Na-Ar) species ccCA produced chemical accuracy (generally estimated as a deviation of ~1 kcal mol-1 from reliable experiment), the second-row species were smaller in molecular size in comparison to their corresponding first-row species. Previous theoretical work has shown that the accuracy for theoretical calculations involving second-row species (specifically sulfur-containing species) are more basis set dependent than first-row species. Therefore, an analysis of the accuracy of ccCA for sulfur-containing species is warranted. The ccCA methodology is used to evaluate both enthalpies of formation and bond dissociation energies of sulfur-containing species as well as examine isomerization energies for three sets of sulfur-containing isomers. During the testing of ccCA for sulfur-containing species two observations were made which led to further investigations. First, there is no agreement between different theoretical methodologies on the lowest energetic isomer between SNO and NSO. In fact, G3 and G3B3 which differ only by the geometry of the single-point calculations do not agree on the lowest isomer. For this reason, larger, more complete theoretical treatments of SNO and NSO are investigated. Second, for open-shell sulfur-containing systems the accuracy of the ccCA methodology begins to degrade when spin-contamination becomes non-negligible. Therefore, we investigate the accuracy of the ccCA methodology when spin-contamination is removed from the wavefunction. Finally, the ccCA methodology is utilized in a multilayer ONIOM approach as the high level of theory in conjunction with density functional theory as the low level for the C-H bond dissociation energies of anthracene and fluorene analogues. digital.library.unt.edu/ark:/67531/metadc33213/
Examining and Characterizing Changes in First Year High School Chemistry Curricula
Many students currently entering college are able to solve mathematical problems but often do not understand the chemistry concepts underlying their calculations. High school chemistry teachers from Texas and the United States (US) were surveyed as to what topics they teach in their chemistry classes. A subset of Texas teachers was also interviewed about their instruction. The survey indicated that less-experienced Texas teachers are omitting a number of topics from their chemistry instruction, as compared to more experienced teachers. No differences were seen for those topics among US teachers. Chemistry textbooks from 1930 to the current 2002 Texas state adoptions were analyzed for inclusion of these topics. The only textbooks that were missing topics were from the 1930s. All others contained the topics. In general, textbooks have been increasing numbers of questions and problems for each topic, with the number of quantitative problems increasing at a greater rate than qualitative problems. Analysis of interview transcripts revealed that the main reason for omission of topics by less-experienced Texas chemistry teachers is that these topics are not assessed on the Texas Assessment of Knowledge and Skills science exam. Omitted topics were both qualitative and quantitative; the common factor is that they are not tested. School administrators reportedly reinforce this practice. Archival data regarding textbook usage by general chemistry students showed that students' course grades are not correlated to the amount of time they spend using their textbook. With topics included in textbooks, and no relationship between textbook usage and student grades, observed changes in chemistry courses must be due to changes in classroom instruction. With new course standards adopted by Texas for chemistry and the development of end-of-course exams, these changes should produce graduates who understand chemistry concepts as well as they solve mathematical chemistry problems. Repeating this study in 5 years may show that increasing the amount of chemistry tested will produce students entering college with a better conceptual background in chemistry. digital.library.unt.edu/ark:/67531/metadc30468/
Experimental Determination of L, Ostwald Solubility Solute Descriptor for Illegal Drugs By Gas Chromatography and Analysis By the Abraham Model
The experiment successfully established the mathematical correlations between the logarithm of retention time of illegal drugs with GC system and the solute descriptor L from the Abraham model. the experiment used the method of Gas Chromatography to analyze the samples of illegal drugs and obtain the retention time of each one. Using the Abraham model to calculate and analyze the sorption coefficient of illegal drugs is an effective way to estimate the drugs. Comparison of the experimental data and calculated data shows that the Abraham linear free energy relationship (LFER) model predicts retention behavior reasonably well for most compounds. It can calculate the solute descriptors of illegal drugs from the retention time of GC system. However, the illegal drugs chosen for this experiment were not all ideal for GC analysis. HPLC is the optimal instrument and will be used for future work. HPLC analysis of the illegal drug compounds will allow for the determination of all the solute descriptors allowing one to predict the illegal drugs behavior in various Abraham biological and medical equations. the results can be applied to predict the properties in biological and medical research which the data is difficult to measure. the Abraham model will predict more accurate results by increasing the samples with effective functional groups. digital.library.unt.edu/ark:/67531/metadc115179/
First-Semester General Chemistry Curriculum Comparison of Student Success on ACS Examination Questions Grouped by Topic Following an Atoms First or Traditional Instructional Approach.
This study uses the ACS first-term general chemistry exam to determine if one curriculum approach is more effective in increasing student success than the other based on their performance on the ACS exam. Two chemistry curriculum approaches were evaluated in this study; the traditional curriculum (TC) and the Atoms First (AF) approach. The sample population was first-semester general chemistry students at Collin College in Frisco, TX. An independent sample t-test was used to determine if there were differences in overall performance between the two curriculum approaches on two different versions of the ACS exam. The results from this study show that AF approach may be a better alternative to the TC approach as they performed statistically significantly better on the 2005 exam version. Factor analysis was used to determine if there were differences between the two curriculum approaches by topic on the ACS exam. Eight different topics were chosen based on topics listed on the ACS Examinations Institute Website. The AF students performed better at a statistically significant level than the TC students on the topics of descriptive chemistry and periodicity, molecular structure, and stoichiometry. Item response theory was used to determine the chemistry content misconceptions held by the students taught under both curriculum approaches. It was determined that for both curriculum groups the same misconceptions as determined by the Zcrit values persisted. digital.library.unt.edu/ark:/67531/metadc799539/
Forensic Science Applications Utilizing Nanomanipulation-Coupled to Nanospray Ionization-Mass Spectrometry for the Analysis of Ultra-Trace Illicit Drugs
Presented in this thesis are two methods that are coupled to the instrumentation for the recovery and analysis of ultra-trace illicit drug residues. The electrostatic dust lifting process is coupled with nanomanipulation-nanospray ionization to retrieve drug particles off of hard surfaces for analysis. For the second method, drug residues from fingerprint impressions are extracted followed by analysis. The methodology of these hyphenated techniques toward forensic science applications is applied as to explore limits of detection, sensitivity, and selectivity of analytes as well as immediacy and efficiency of analysis. The application of nanomanipulation-coupled to nanospray ionization-mass spectrometry toward forensic science based applications is considered as future improvements to trace and ultra-trace analysis. digital.library.unt.edu/ark:/67531/metadc33209/
Free Radical Chemistries at the Surface of Electronic Materials
The focus of the following research was to (1) understand the chemistry involved in nitriding an organosilicate glass substrate prior to tantalum deposition, as well as the effect nitrogen incorporation plays on subsequent tantalum deposition and (2) the reduction of a native oxide, the removal of surface contaminants, and the etching of a HgCdTe surface utilizing atomic hydrogen. These studies were investigated utilizing XPS, TEM and AFM. XPS data show that bombardment of an OSG substrate with NH3 and Ar ions results in the removal of carbon species and the incorporation of nitrogen into the surface. Tantalum deposition onto a nitrided OSG surface results in the initial formation of tantalum nitride with continued deposition resulting in the formation of tantalum. This process is a direct method for forming a thin TaN/Ta bilayer for use in micro- and nanoelectronic devices. Exposure to atomic hydrogen is shown to increase the surface roughness of both air exposed and etched samples. XPS results indicate that atomic hydrogen reduces tellurium oxide observed on air exposed samples via first-order kinetics. The removal of surface contaminants is an important step prior to continued device fabrication for optimum device performance. It is shown here that atomic hydrogen effectively removes adsorbed chlorine from the HgCdTe surface. digital.library.unt.edu/ark:/67531/metadc31552/
Free Radical Induced Oxidation, Reduction and Metallization of NiSi and Ni(Pt)Si Surfaces
NiSi and Ni(Pt)Si, and of the effects of dissociated ammonia on oxide reduction was carried out under controlled ultrahigh vacuum (UHV) conditions. X-ray photoelectron spectroscopy (XPS) has been used to characterize the evolution of surface composition. Vicinal surfaces on NiSi and Ni(Pt)Si were formed in UHV by a combination of Ar+ sputtering and thermal annealing. Oxidation of these surfaces in the presence of either O+O2 or pure O2 at room temperature results in the initial formation of a SiO2 layer ~ 7 Å thick. Subsequent exposure to O2 yields no further oxidation. Continued exposure to O+O2, however, results in rapid silicon consumption and, at higher exposures, the kinetically-driven oxidation of the transition metal(s), with oxides >35Ǻ thick formed on all samples, without passivation. The addition of Pt retards but does not eliminate oxide growth or Ni oxidation. At higher exposures, in Ni(Pt)Si surface the kinetically-limited oxidation of Pt results in Pt silicate formation. Substrate dopant type has almost no effect on oxidation rate. Reduction of the silicon oxide/metal silicate is carried out by reacting with dissociated NH3 at room temperature. The reduction from dissociated ammonia (NHx+H) on silicon oxide/ metal silicate layer shows selective reduction of the metal oxide/silicate layer, but does not react with SiO2 at ambient temperature. digital.library.unt.edu/ark:/67531/metadc31542/
From Development of Semi-empirical Atomistic Potentials to Applications of Correlation Consistent Basis Sets
The development of the semi-empirical atomistic potential called the embedded atom method (EAM) has allowed for the efficient modeling of solid-state environments, at a lower computational cost than afforded by density functional theory (DFT). This offers the capability of EAM to model the energetics of solid-state phases of varying coordination, including defects, such as vacancies and self-interstitials. This dissertation highlights the development and application of two EAMs: a Ti potential constructed with the multi-state modified embedded atom method (MS-MEAM), and a Ni potential constructed with the fragment Hamiltonian (FH) method. Both potentials exhibit flexibility in the description of different solid-states phases and applications. This dissertation also outlines two applications of DFT. First, a study of structure and stability for solid-state forms of NixCy (in which x and y are integers) is investigated using plane-wave DFT. A ground state phase for Ni2C is elucidated and compared to known and hypothesized forms of NixCy. Also, a set of correlation consistent basis sets, previously constructed using the B3LYP and BLYP density functionals, are studied. They are compared to the well-known to the correlation consistent basis sets that were constructed with higher-level ab initio methodologies through computations of enthalpies of formation and combustion enthalpies. The computational accuracy with regard to experiment is reported. digital.library.unt.edu/ark:/67531/metadc500219/
Fundamental Studies of Copper Bimetallic Corrosion in Ultra Large Scale Interconnect Fabrication Process
In this work, copper bimetallic corrosion and inhibition in ultra large scale interconnect fabrication process is explored. Corrosion behavior of physical vapor deposited (PVD) copper on ruthenium on acidic and alkaline solutions was investigated with and without organic inhibitors. Bimetallic corrosion screening experiments were carried out to determine the corrosion rate. Potentiodynamic polarization experiments yielded information on the galvanic couples and also corrosion rates. XPS and FTIR surface analysis gave important information pertaining inhibition mechanism of organic inhibitors. Interestingly copper in contact with ruthenium in cleaning solution led to increased corrosion rate compared to copper in contact with tantalum. On the other hand when cobalt was in contact with copper, cobalt corroded and copper did not. We ascribe this phenomenon to the difference in the standard reduction potentials of the two metals in contact and in such a case a less noble metal will be corroded. The effects of plasma etch gases such as CF4, CF4+O2, C4F8, CH2F2 and SF6 on copper bimetallic corrosion was investigated too in alkaline solution. It was revealed that the type of etching gas plasma chemistry used in Cu interconnect manufacturing process creates copper surface modification which affects corrosion behavior in alkaline solution. The learning from copper bimetallic corrosion studies will be useful in the development of etch and clean formulations that will results in minimum defects and therefore increase the yield and reliability of copper interconnects. digital.library.unt.edu/ark:/67531/metadc499992/
Group 10 Catalyzed Olefin Hydroarylation
Alkyl-arenes are important industry feedstock chemicals that are used as solvents, pharmaceutical precursors, and polymer monomer units. One alkyl-arene, ethylbenzene, is the main focus of this dissertation, and is produced in the million ton a year scale. As alkyl-arenes are important commodity chemicals, catalytic olefin hydroarylation is a lucrative alternative for their production rather than Friedel-Crafts alkylation or various coupling reactions that have lower atom economy, require strong acids, or are energetically demanding. Currently catalytic olefin hydroarylation still suffers from decomposition pathways of the active catalytic complexes, side reactions that lead to waste products, and unfavorable activation barriers, which represent high temperature and pressure. Modifications to the catalytically active system bipyridine platinum(II) (bpyPtII), through computational methods, are explored herein. The work presented here investigates catalytic olefin hydroarylation in order to mitigate the aforementioned difficulties. Included in this study are changes to the electronic profile of the supporting ligand, bpy, through the addition of electron withdrawing or electron donating R groups (methoxy, nitro), definite ligand replacements such as bpy to hydridotris(pyrazolyl)borate (Tp), changes in metal oxidation (II to IV), and replacing the metal center from Pt to Ni. Nickel was selected as a possible alternative to platinum as it is more Earth abundant reducing the monetary requirement for the catalyst. In addition to having a different catalytic energetic profile from platinum. Ni as expected could only facilitate single step hydrogen atom transfers due to its inability to access higher oxidations states. digital.library.unt.edu/ark:/67531/metadc177201/
Homework versus daily quizzes: The effects on academic performance within high school pre-AP chemistry.
This research proposed to evaluate whether homework or daily quizzes were better for academic success within high-school pre-AP chemistry or if differences in the two methods were detectable. The study involved two years of data where homework was assigned and graded and one year of data where homework was suggested but daily quizzes provided the assessment. The mean of each of the unit tests were evaluated and t-tests were calculated. The results showed that over two-thirds of the units had statistically significant data when daily quizzes were utilized. digital.library.unt.edu/ark:/67531/metadc67936/
Impact of Texas High School Science Teacher Credentials on Student Performance in High School Science
A study was conducted to determine the relationship between the credentials held by science teachers who taught at a school that administered the Science Texas Assessment on Knowledge and Skills (Science TAKS), the state standardized exam in science, at grade 11 and student performance on a state standardized exam in science administered in grade 11. Years of teaching experience, teacher certification type(s), highest degree level held, teacher and school demographic information, and the percentage of students who met the passing standard on the Science TAKS were obtained through a public records request to the Texas Education Agency (TEA) and the State Board for Educator Certification (SBEC). Analysis was performed through the use of canonical correlation analysis and multiple linear regression analysis. The results of the multiple linear regression analysis indicate that a larger percentage of students met the passing standard on the Science TAKS state attended schools in which a large portion of the high school science teachers held post baccalaureate degrees, elementary and physical science certifications, and had 11-20 years of teaching experience. digital.library.unt.edu/ark:/67531/metadc149592/
Incorporating Electrochemistry and X-ray Diffraction Experiments Into an Undergraduate Instrumental Analysis Course
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Experiments were designed for an undergraduate instrumental analysis laboratory course, two in X-ray diffraction and two in electrochemistry. Those techniques were chosen due their underrepresentation in the Journal of Chemical Education. Paint samples (experiment 1) and pennies (experiment 2) were characterized using x-ray diffraction to teach students how to identify different metals and compounds in a sample. in the third experiment, copper from a penny was used to perform stripping analyses at different deposition times. As the deposition time increases, the current of the stripping peak also increases. the area under the stripping peak gives the number of coulombs passed, which allows students to calculate the mass of copper deposited on the electrode surface. the fourth experiment was on the effects of variable scan rates on a chemical system. This type of experiment gives valuable mechanistic information about the chemical system being studied. digital.library.unt.edu/ark:/67531/metadc115123/
Interfacial Characterization of Chemical Vapor Deposition (Cvd) Grown Graphene and Electrodeposited Bismuth on Ruthenium Surface
Graphene receives enormous attention owing to its distinctive physical and chemical prosperities. Growing and transferring graphene to different substrates have been investigated. The graphene growing on the copper substrate has an advantage of low solubility of carbon on the copper which allow us to grow mostly monolayer graphene. Graphene sheet of few centimeters can be transferred to 300nm silicon oxide and quartz crystal pre-deposited with metal like Cu and Ru. Characterization of the graphene has been done with Raman and contact angle measurement and recently quartz crystal microbalance (QCM) has been employed. The underpotential deposition (UPD) process of Bi on Ru metal surface is studied using electrochemical quartz crystal microbalance (EQCM) and XPS techniques. Both Bi UPD and Bi bulk deposition are clearly observed on Ru in 1mM Bi (NO3)3/0.5M H2SO4. Bi monolayer coverage calculated from mass (MLMass) and from charge (MLCharge) were compared with respect to the potential scanning rates, anions and ambient controls. EQCM results indicate that Bi UPD on Ru is mostly scan rate independent but exhibits interesting difference at the slower scan. Bi UPD monolayer coverage calculated from cathodic frequency change (ΔfCathodic) is significantly smaller than the monolayer coverage derived from integrated charge under the cathodic Bi UPD peak when scan rate is at least 5 mV/s. XPS is utilized to explore the detailed chemical composition of the observed interfacial process of Bi UPD on Ru. digital.library.unt.edu/ark:/67531/metadc500095/
Interfacial Electrochemistry of Copper and Spectro-Electrochemical Characterization of Oxygen Reduction Reaction
The first part of this dissertation highlights the contents of the electrochemical characterization of Cu and its electroplating on Ru-based substrates. The growth of Ru native oxide does diminish the efficiency of Cu plating on Ru surface. However, the electrochemical formed irreversible Ru hydrate dioxide (RuOxHy) shows better coverage of Cu UPD. The conductive Ru oxides are directly plateable liner materials as potential diffusion barriers for the IC fabrication. The part II of this dissertation demonstrates the development of a new rapid corrosion screening methodology for effective characterization Cu bimetallic corrosion in CMP and post-CMP environments. The corrosion inhibitors and antioxidants were studied in this dissertation. In part III, a new SEC methodology was developed to study the ORR catalysts. This novel SEC cell can offer cheap, rapid optical screening results, which helps the efficient development of a better ORR catalyst. Also, the SEC method is capable for identifying the poisoning of electrocatalysts. Our data show that the RuOxHy processes several outstanding properties of ORR such as high tolerance of sulfation, high kinetic current limitation and low percentage of hydrogen peroxide. digital.library.unt.edu/ark:/67531/metadc103416/
Investigating Molecular Structures: Rapidly Examining Molecular Fingerprints Through Fast Passage Broadband Fourier Transform Microwave Spectroscopy
Microwave spectroscopy is a gas phase technique typically geared toward measuring the rotational transitions of Molecules. The information contained in this type of spectroscopy pertains to a molecules structure, both geometric and electronic, which give insight into a molecule's chemistry. Typically this type of spectroscopy is high resolution, but narrowband ≤1 MHz in frequency. This is achieved by tuning a cavity, exciting a molecule with electromagnetic radiation in the microwave region, turning the electromagnetic radiation o, and measuring a signal from the molecular relaxation in the form of a free induction decay (FID). The FID is then Fourier transformed to give a frequency of the transition. "Fast passage" is defined as a sweeping of frequencies through a transition at a time much shorter (≤10 s) than the molecular relaxation (≈100 s). Recent advancements in technology have allowed for the creation of these fast frequency sweeps, known as "chirps", which allow for broadband capabilities. This work presents the design, construction, and implementation of one such novel, high-resolution microwave spectrometer with broadband capabilities. The manuscript also provides the theory, technique, and motivations behind building of such an instrument. In this manuscript it is demonstrated that, although a gas phase technique, solids, liquids, and transient species may be studied with the spectrometer with high sensitivity, making it a viable option for many molecules wanting to be rotationally studied. The spectrometer has a relative correct intensity feature that, when coupled with theory, may ease the difficulty in transition assignment and facilitate dynamic chemical studies of the experiment. Molecules studied on this spectrometer have, in turn, been analyzed and assigned using common rotational spectroscopic analysis. Detailed theory on the analysis of these molecules has been provided. Structural parameters such as rotational constants and centrifugal distortion constants have been determined and reported for most molecules in the document. Where possible, comparisons have been made amongst groups of similar molecules to try and get insight into the nature of the bonds those molecules are forming. This has been achieved the the comparisons of nuclear electric quadrupole and nuclear magnetic coupling constants, and the results therein have been determined and reported. digital.library.unt.edu/ark:/67531/metadc67988/
Investigation of Novel Electrochemical Synthesis of Bioapatites and Use in Elemental Bone Analysis
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In this research, electrochemical methods are used to synthesize the inorganic fraction of bone, hydroxyapatite, for application in biological implants and as a calibration material for elemental analysis in human bone. Optimal conditions of electrochemically deposited uniform apatite coatings on stainless steel were investigated. Apatite is a ceramic with many different phases and compositions that have beneficial characteristics for biomedical applications. Of those phases hydroxyapatite (HA) is the most biocompatible and is the primary constituent of the inorganic material in bones. HA coatings on metals and metal alloys have the ability to bridge the growth between human tissues and implant interface, where the metal provides the strength and HA provides the needed bioactivity. The calcium apatites were electrochemically deposited using a modified simulated body fluid adjusted to pH 4-10, for 1-3 hours at varying temperature of 25-65°C while maintaining cathodic potentials of -1.0 to -1.5V. It was observed that the composition and morphology of HA coatings change during deposition by the concentration of counter ions in solution, pH, temperature, applied potential, and post-sintering. The coatings were characterized by powder x-ray diffraction, Fourier transform infrared spectroscopy, and scanning electron microscopy. The precipitated powders from the experiment were also characterized, with results showing similarities to biological apatite. There is a need for quantitative elemental analysis of calcified biological matrices such as bone and teeth; however there are no suitable calibration materials commercially available for quantitative analysis. Matrix-matched standards are electrochemically synthesized for LA-ICP-MS analysis of human bone. The synthetic bioapatite is produced via a hydrothermal electrochemical process using a simulated body fluid solution to form hydroxyapatite. Additional bioapatite standards are synthesized containing trace amounts of metals. The x-ray diffraction of the synthesized standards shows an increase in cell volume for the crystal structure from 0.534 to 0.542 nm3 with the substitution of metals into the crystal structure. The analyte concentration and recoveries for the synthesized standards and reference materials were determined by ICP-MS with % RSD below 6.3% and limits of detection below 1.2 ng/mL for trace metals. The electrochemically synthesized bioapatite was also compared to standard reference materials with X-ray diffraction, FTIR, and Raman spectroscopy. Optimum laser ablation parameters were determined for the standards and human bone. The synthesized standards were homogeneous and the reproducibility for the isotope concentrations determined by LA-ICP-MS was between 3-10 % compared to 10-35% for SRM 1486 Bone Meal and SRM 1486 Bone Ash. A quantitative method has been developed for 2D mapping using LA-ICP-MS and the matrix-matched standards of metal-doped biopaptite to characterize metal concentrations in human bone. Laser ablation parameters for the method are refined resulting in concentration (ug/g) contour map measurements for each isotope measured in the human bone. Essential and non-essential metals, Al, Ca, Cu, Fe, Pb, and Zn are quantitatively mapped using these parameters. Limit of detection for the metals in the bone range from 0.001 to 0.08 ug/g. The LA-ICP-MS analysis method developed proves to be a straightforward and simple method for quantitative analysis of human bone. digital.library.unt.edu/ark:/67531/metadc177191/
Kinetic Investigation of Atomic Hydrogen with Sulfur-containing Species
The reactions of atomic hydrogen with methanethiol and that of atomic hydrogen with carbon disulfide were studied experimentally using flash-photolysis resonance-fluorescence techniques. Rate constants were determined over a range of temperatures and pressures, and through analysis and comparison to theoretical work details of the reactions were ascertained. digital.library.unt.edu/ark:/67531/metadc699887/
Kinetic Investigation of the Gas Phase Atomic Sulfur and Nitrogen Dioxide Reaction
The kinetics of the reaction of atomic sulfur and nitrogen dioxide have been investigated over the temperature range 298 to 650 K and pressures from 14 - 405 mbar using the laser flash photolysis - resonance fluorescence technique. The overall bimolecular rate expression k (T) = (1.88 ± 0.49) x10-11 exp-(4.14 ± 0.10 kJ mol-1)/RT cm3 molecule-1 s-1 is derived. Ab initio calculations were performed at the CCSD(T)/CBS level of theory and a potential energy surface has been derived. RRKM theory calculations were performed on the system. It is found that an initially formed SNO2 is vibrationally excited and the rate of collisional stabilization is slower than the rate of dissociation to SO + NO products by a factor of 100 - 1000, under the experimental conditions. digital.library.unt.edu/ark:/67531/metadc68055/
Kinetic Studies on C‐h Bond Activation in the Reaction of Triosmium Clusters with Diphosphine and Amidine Ligands
The reaction of 1-(diphenylphosphino)-2-(diphenylphosphito)benzene (PP*) and Os3(CO)10(ACN) has been investigated. A combined experimental and computational study on the isomerization of 1,2-Os3(CO)10[μ-1,2-Ph2P(C6H4)P(OPh)2] (A) and 1,1-Os3(CO)10[μ-1,2-Ph2P(C6H4)P(OPh)2] (B) and reversible ortho-metalation exhibited by the triosmium cluster B are reported. The subsequent conversion of cluster B to the hydrido cluster HOs3(CO)9[μ-1,2-PhP(C6H4-η1)C6H4P(OPh)2] (E) and the benzyne-substituted cluster HOs3(CO)8(µ3-C6H4)[μ-1,2-PhP(C6H4)P(OPh)2] (N) has been established. All of these new clusters have been isolated and fully characterized in solution by IR and NMR spectroscopy; in addition, X-ray diffraction analyses have been performed on the clusters A, B, J, and N. The ortho-metalation reaction that gives cluster E is shown to be reversible, and the mechanism has been probed using selectively deuterated PP* isotopomers. Kinetic and thermodynamic isotope data, in conjunction with DFT calculations, are presented that support the existence of an intermediate unsaturated cluster in the ortho-metalation reaction. Due to interest in the coordination chemistry of formamidines, the non-symmetric amidine ligands PhNC(Me)NHPri, PhNC(Et)NHPri, and (2,4,6-Me3C6H2)NC(Me)NHPri, have been synthesized, and their reaction with Os3(CO)10(MeCN)2 has been investigated. Of the twelve new clusters prepared in section, seven have been structurally characterized by X-ray crystallography. digital.library.unt.edu/ark:/67531/metadc699850/
Kinetics of Sulfur: Experimental Study of the Reaction of Atomic Sulfur with Acetylene and Theoretical Study of the Cn + So Potential Energy Surface
The kinetics of the reaction of atomic sulfur with acetylene (S (3P) + C2H2) were investigated experimentally via the flash photolysis resonance fluorescence method, and the theoretical potential energy surface for the reaction CN + SO was modeled via the density functional and configuration interaction computational methods. Sulfur is of interest in modern chemistry due to its relevance in combustion and atmospheric chemistry, in the Claus process, in soot and diamond-film formation and in astrochemistry. Experimental conditions ranged from 295 – 1015 K and 10 – 400 Torr of argon. Pressure-dependence was shown at all experimental temperatures. The room temperature high-pressure limit second order rate constant was (2.10 ± 0.08) × 10-13 cm3 molecule-1 s-1. The Arrhenius plot of the high-pressure limit rate constants gave an Ea of (11.34 ± 0.03) kJ mol-1 and a pre-exponential factor of (2.14 ± 0.19) × 10-11 cm3 molecule-1 s-1. S (3P) + C2H2 is likely an adduct forming reaction due to pressure-dependence (also supported by a statistical mechanics analysis) which involves intersystem crossing. The potential energy surface for CN + SO was calculated at the B3LYP/6-311G(d) level and refined at the QCISD/6-311G(d) level. The PES was compared to that of the analogous reaction CN + O2. Notable energetically favorable products are NCS + O, CO + NS, and CS + NO. The completed PES will ultimately be modeled at the CCSD(T) level (extrapolated to infinite basis set limit) for theoretical reaction rate analysis (RRKM). digital.library.unt.edu/ark:/67531/metadc271774/
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