Electronic structure investigations of titanium oxide nanoclusters, boron-nitrogen heterocycles, and reaction products of lanthanides with oxygen difluoride and lanthanides with water

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dc.contributor Bakker, Martin G.
dc.contributor Street, Shane C.
dc.contributor Gupta, Arunava
dc.contributor Schad, Rainer
dc.contributor.advisor Dixon, David A.
dc.contributor.author Mikulas, Tanya C.
dc.date.accessioned 2017-03-01T17:23:43Z
dc.date.available 2017-03-01T17:23:43Z
dc.date.issued 2015
dc.identifier.other u0015_0000001_0001918
dc.identifier.other Mikulas_alatus_0004D_12314
dc.identifier.uri https://ir.ua.edu/handle/123456789/2343
dc.description Electronic Thesis or Dissertation
dc.description.abstract Advanced electronic structure methods on high performance computers have been used to predict the reactions of lanthanides, properties of liquid chemical hydrogen storage systems, and Fe doped TiO2 nanoclusters. Chapter 2 describes a detailed experimental matrix isolation and computational study of the reactions of lanthanide atoms with F2O. The experimental data is analyzed in terms of the results of density functional theory and CCSD(T) calculations. The products OlnF and OLnF2 are observed, with most Ln in the +III oxidation state for both products. The bonding in these molecules is strongly dependent on the oxidation state of the lanthanide. The coupling of the spin on the O with that on the Ln is important in determining the Ln-O frequency. Chapter 3 describes the reactions of the lanthanides with H2O. The dominant products are LnO + H2 and HLnOH with the Ln in the +II oxidation state. The difference in the reactions of F2O and H2O are due to the differences in the reactant and product bond strengths. Chapter 4 describes combined experimental and computational studies of the liquid chemical hydrogen storage systems based on substituting a C-C with a B-N. Experimental structural analysis and high level electronic structure calculations suggest that the aromaticity of the 1,3-dihydro-1,3-azaborine heterocycle is intermediate between that of benzene and that of 1,2-dihydro-1,2-azaborine. The development of the first reported parental BN isostere of cyclohexane featuring two BN units is thermally stable up to 150 °C with a H2 storage capacity of 4.7 weight% is described. High level computations have been used to predict the reaction energetics of the formation of two cage compounds from the H2 desorption reactions. The photophysical properties resulting from BN/CC isosterism for 10 1,2-azaborine-based BN isosteres of stilbenes have been explained by using high level electronic structure calculations. Chapter 5 describes computational and experimental evidence for facile charge transfer from the transition metal ion Fe(II) to titanium sites in nanoscale TiO2 and its oxynitride, TiO2-xNx. The transfer has been characterized through core level and valance band photoelectron spectroscopies and detailed electronic structure calculations.
dc.format.extent 303 p.
dc.format.medium electronic
dc.format.mimetype application/pdf
dc.language English
dc.language.iso en_US
dc.publisher University of Alabama Libraries
dc.relation.ispartof The University of Alabama Electronic Theses and Dissertations
dc.relation.ispartof The University of Alabama Libraries Digital Collections
dc.relation.hasversion born digital
dc.rights All rights reserved by the author unless otherwise indicated.
dc.subject.other Physical chemistry
dc.subject.other Chemistry
dc.title Electronic structure investigations of titanium oxide nanoclusters, boron-nitrogen heterocycles, and reaction products of lanthanides with oxygen difluoride and lanthanides with water
dc.type thesis
dc.type text
etdms.degree.department University of Alabama. Dept. of Chemistry
etdms.degree.discipline Chemistry
etdms.degree.grantor The University of Alabama
etdms.degree.level doctoral
etdms.degree.name Ph.D.


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