There was a fame time for silicon in condensed matter physics, then the graphene era came and now topological insulators are gaining lot of attention, but magnetism in condensed matter physics has remained always fascinating starting from the ancient days up to now and it will remain as one of the core topic in basic or applied physics. The improvement in the modern techniques allows one to explore magnetism in different length scales as well as in different time scales. As an effect of the improvement in experimental techniques, different magnetic anomalies are unearthed. As a result theories are getting refined and the area of magnetism progresses. From the material point of view, oxides carry the most diverse nature in condensed matter starting from high temperature superconductivity (HTS), colossal magnetoresistance, metal insulator transition etc. to ferromagnetism (FM), anti-ferromagnetism (AFM), spin glass (SG) and so on. Among this list, SG and HTS are one of the least understood topics in magnetism till today. A large research community is involved in understanding the underlying physics behind these two, especially in transition metal oxides. It has drawn attention not only due to fundamental aspects but also due to various applications in day to day life. This thesis is an attempt to understand these two phenomena in transition metal oxides. As the title of this thesis suggest, it is all about magnetic and magneto-transport properties of certain transition metal oxide (crystalline) addressing the interplay between two competing order parameters to understand the underlying physics behind it from an experimental point of view. We have studied two different kinds of competing interactions: (i) the FM/AFM interplay either in bulk or at the interface of the two layers in thin films; (ii) the interplay between FM and superconductivity (SC) in superconductor (S)/ferromagnet (F) heterostructures. Basically both of these two kinds lead to non-equilibrium phenomena in these oxides. One of such competition is between FM and AFM leading to slow dynamics (glassy physics). Disorder and frustrations are the key ingredients for such slow dynamics. The spin frustration arises either due to geometry or due to competing interactions. For example, in a triangular antiferromagnet due to the triangular geometry spins gets frustrated. Now, if it prevails spin disorder as well then it satisfies both the criteria for a spin glass and hence it gives birth to glassiness. Another kind of competition is the interplay among SC and FM. It is known that SC and FM are two antagonistic quantum phenomena thus in a single material SC (singlet pairing) and FM does not co-exist. However one can realize this by making F/S heterostructures and observe the battle between these two competing order parameters. The spin polarized quasiparticle injection from F creates non equilibrium spin density inside S and thereby suppressing the order parameter of S. Also by choosing an appropriate ferromagnet the vortex motion inside S can be arrested to certain extent which can enhance the critical current density of S. Thus FM/SC interplay has become an alternative way to look at the high temperature superconductivity. This thesis is categorized into nine chapters. The summary of each chapter is as follows: Chapter: 1 contains certain concepts of magnetism and superconductivity which is useful to understand the topics and experiments described in this thesis. Chapter: 2 gives the underlying principles of the various experimental techniques used in this thesis. Chapter: 3 describes the magnetic properties of successfully synthesized five compositions of LixNi(2-x)O2 (0.67<x<0.99) which has five distinct ground states namely antiferromagnet (AF), spin glass (SG), cluster glass (CG), re-entrant spin glass (RSG) and ferromagnet (FM). The SG and CG ground state has been well described by the frequency dependent peak shift. From the power-law divergence of critical slowing down the estimated value of relaxation time indicates the presence of interacting macro spins (spin cluster) rather than individual spins in certain LixNi(2-x)O2 samples possessing CG ground state which is also supported by the Arrhenius law. The shift in the spin freezing temperature with the application of dc field obeys Almeida-Thouless line. It also exhibits memory effect which is generic to the slow dynamics. The remnant magnetization relaxation follows logarithmic decay. Interestingly, the sample having RSG ground state shows memory effect up-to 50K and behaves like a FM above that temperature. FC-ZFC M(T) curve shows a splitting at the ordering temperature. The critical analysis across the ferromagnetic-paramagnetic phase transition yields a self-consistent γ, β and δ value and the spin-spin interaction in this material follows long range mean field model. The critical exponents obey Widom scaling law: δ = 1 + γ β −1. The universality class of the scaling relations is also verified where the scaled m and scaled h collapses into two branches. Finally the magnetic phase diagram illustrates a vivid picture of the gradual evolution of ferromagnetism in LixNi(2-x)O2 through a glassy state. As a concluding remark, we think, the present study of glassy physics in magnetic insulator/semiconductor sets an example to compare them with the conventional metallic spin glass system. Chapter: 4 exhibits the results of the structural, magnetic and transport measurements to elucidate some of the most striking unusual physical responses of bulk SrRuO3. Two set of polycrystalline SrRuO3 samples with unique ordering temperature have been synthesized. In one case, we have taken the stoichiometric weight ratio of precursors that eventually resulted in Ru-deficient SrRuO3(SROD). In the other case, we have taken extra 2% wt. RuO2 deliberately to form stoichiometric SrRuO3(SRO). Both the samples are found to crystallize in orthorhombic crystal structure with Pnma space group. The low temperature magnetization is found to be well described by the Bloch T3/2 law and the magnetization near Tc is found to follow the scaling law; M~(Tc-T)β with β=0.35 and β=0.30 for SRO and SROD respectively, apparently showing the 3D Ising behaviour. This aspect will be elaborated in the next chapter. The magnetic ac susceptibility study exhibits a broad hump far below the ferromagnetic ordering temperature and the frequency dependence of this hump position exhibits the characteristics of multiple relaxations. Most strikingly, we notice a low temperature glassy magnetic behaviour clearly demonstrated by the time dependent memory effect. This is very surprising and unlikely to happen in systems, which have itinerant ferromagnetic character. However, we conjecture that slow domain growth and spin canting could be the cause for such effect. The transport study evidences a crossover from Fermi liquid (FL) to non-Fermi liquid (NFL) behaviour around 40 K and a slope change in dρ/dT vs. T plot in the vicinity of that temperature. Astonishingly, we observe two distinct dips (one around ferromagnetic ordering temperature and the other far below the ferromagnetic ordering temperature) in the temperature dependent MR response. In addition, we also observe the signature of an unusual dip in the temperature dependent coercive field towards low temperature side. The emergence of such unusual magnetic and transport response is strongly believed to be connected with hidden magnetic interactions. Our effort on neutron diffraction study has been able to trace the cause of such cryptic magnetic interaction. The findings of neutron diffraction study evidence the change in the unit cell lattice parameters around 75 K and that could be the central cause behind such anomalous low temperature magnetic responses. It also demonstrates that the octahedral tilt freezes around the FM transition and has a minimum around the low temperature glass transition temperature. Most remarkably we observe a decline in the total integrated magnetic intensity towards the low temperature side indicating the presence of antiferromagnetic like interaction in SrRuO3. Chapter: 5 resolves the ambiguity in determining the crritical exponents in SrRuO3. Most remarkably, the application of scaling law in the FC magnetization leads a systematic change in the values of critical exponent with the measuring field in SRO. The β value changes from 0 to o.44 to to 0.29 (corresponds to mean field to Ising) with the increase in the measurement field from 10 to 2500 Oe. However, the H→0 extrapolation fields β=0.5. In order to substantiate the actual nature, the critical behavior is studied across the phase transition from the M-H isotherms. The critical analysis yields a self-consistent β, γ and δ values and the spin-spin interaction follows long range mean field δ=γ β model 1+. The critical exponents also obey Widom scaling law: δ = 1 + γ β-1 The universality class of the scaling relations is verified where the scaled m and scaled h collapses into two branches. We have also found that Ru deficiency does not affect the nature of the spin-spin interaction (though ferromagnetism gets reduced). Further the directional dependence of the critical exponent reflects the isotropic nature of the magnetic interaction. In other words the spin-spin interaction found to be: i) three dimensional, ii) long range, iii) mean field type and iv) isotropic in SrRuO3. We have also found magnetocaloric effect (calculated from the M-H isotherms) that across the phase transition. The specific heat measurements find sharp jump at the ferromagnetic transition due to the magnetic contribution of the specific heat. Chapter: 6 describes the magnetism at the SrRuO3 (SRO)/LaAlO3 (LAO) interface where SRO is an itinerant ferromagnet (FM) and LAO is non-magnetic (NM) (rather diamagnetic). Most surprisingly SRO/LAO exhibits pronounced exchange bias (EB) effect realized by observing a shift in the field cooled M-H hysteresis. Further investigation results an increasing trend of the strength of the EB with the decreases in the thickness of ferromagnetic layer. This system also displays the training effect which essentially confirms that this effect is due to EB. EB arises due to the uncompensated spins at the FM/AFM interface hence the EB effect in SRO/LAO system is unconventional. However, the origin of such AFM interaction (responsible for EB effect in FM/NM system) at SRO/LAO interface is realized and explained through the temperature dependence of the EB effect. Further, we have extensively investigated EB effect in other analogous ferromagnets, FM/FM bilayers and FM/FM superlattices. We found that La0.7Sr0.3MnO3 (LSMO) grown on LAO exhibits the signature of EB. In contrast to that La0.5Sr0.5CoO3 (LSCO) does not show any signature of EB. All the bilayers (LSMO/SRO, LSMO/LSCO and LSCO/SRO) exhibit EB and have similar kind of temperature dependence. In order to gain more insight we have grown a (LSMO/SRO)8 superlattice and observed a complex magnetic behaviour. It exhibits partial inverted magnetic hysteresis. But the system shows EB effect characterized by the shift in the FC hysteresis and training effect. All these observations essentially demonstrate that the magnetic nature of various ferromagnetisms at the interfaces can be changed by choosing a proper partner (acts like adding perturbations into one of those system which lies close to the instability region). Chapter: 7 presents the magneto-transport properties of three SRO films grown on LAO (100) of thicknesses of 12, 24 and 48 nm are studied extensively. For a one to one comparison one of the sample is also grown on STO(100). The coercivity vs. temperature in SRO(48 nm)/LAO exhibits a plateau at ~40 K. The dR/dT exhibits the low temperature hump in all the samples which very much replicates with the bulk scenario that we observed in SRO. Most strikingly the 12 nm SRO sample exhibits NFL behaviour throughout the temperature range of measurement (10-150 K). Our careful investigation reveals a cross-over from FL to NFL in all SRO thin films. The cross-over temperature increases with the increase in thickness and eventually shifts towards the bulk cross-over value. It is apt to remind that in bulk SRO we have demonstrated (by employing temperature dependent neutron diffraction) that there is a presence of antiferromagnetic like interaction at low temperature giving birth to glassiness in bulk SRO. Further, an attempt is made to understand the low temperature magneto-transport anomaly by looking into the spin fluctuation through the low frequency 1/f noise measurements. It conveys a message that there are two types of magnetic ordering present in SRO giving rise to two peaks in the temperature dependence of the relative variance. Application of magnetic field suppresses both the peaks in the relative variance. This certainly indicates that the origin of such peak is caused by the spin fluctuations and thereby it is of magnetic origin. Further we have looked into the Hall effect of a structured (Hall patterned) SRO thin film and observed regular Hall effect (RHE) as well as anomalous Hall effect (AHE) in it. Most remarkably the temperature dependence of the RHE coefficient changes its sign close to the ferromagnetic transition temperature of SRO. This implies a change of the type of the carrier as the temperature is varied. Based on these results, the carrier concentration of SRO as a function of temperature is determined. Chapter: 8 is about the magnetic and magnetotransport studies on the successfully grown high quality S/F heterostructures. The oxygen content plays a vital role in superconductivity of oxide materials thus for studying FM/SC interplay in oxides we have discussed how to achieve a high quality sample (oxygen stoichiometric). We have observed a great influence of a FM in suppressing the superconductivity in YBa2Cu3O(7-δ) (YBCO) in FM/SC heterostructures. The analysis of the out of plane M-H hysteresis reveals a significant reduction of the critical fields (HC1 and HC2) of the SC (in SRO/YBCO bilayer) which might have a great significance to understand the superconductivity in a better way (from both the perspectives: theory and experiments). Most remarkably we have found 40% enhancement of the critical current density of YBCO in SRO/YBCO bilayer. We have demonstrated that in order to see the effect of spin polarizes quasiparticle (SPQP) injection into YBCO, one should not apply more than 20mA current since Joule heating contribution wins over pair breaking effect. The SPQP injection from SRO into YBCO exhibits pair breaking effect as the TC (of the SC) shift follows I2/3 law. The resistive transitions under various applied magnetic fields and the field dependence of the activation energy confirms that the vortices are in the 2D regimes (it follows power law, U0~Hα withα=0.5) in SRO/YBCO. To get a better insight into the FM/SC interplay we have looked into two of the FM/YBCO combinations (LSCO/YBCO and LSMO/YBCO). We observe that the degree of the spin polarizations of the FMs scales with the suppression of superconductivity in YBCO which means more the spin polarization more is the suppression. We have also found out that spin polarization is not the sole parameter in suppressing superconductivity in SRO/YBCO bilayers. It also depends upon the state of magnetization of the ferromagnet. Further, we observed a significant reduction (one order) of the activation energy in LSCO/YBCO compared to SRO/YBCO which clearly indicates that the vortex dynamics might depend on other aspects as well (of the FM). It also reveals the formation of decoupled pancake vortices (pure 2D regime) in LSCO/YBCO and LSMO/YBCO bilayers whereas in case of YBCO and SRO/YBCO it is of 2D coupled type. Chapter: 9 summarizes the whole work presented in this thesis. It also discusses about few research problems which one need to look at in future.

CoordenaÃÃo de AperfeiÃoamento de NÃvel Superior

Thesis (M.Sc. (Physics)) -- University of Limpopo, 2021 / The stead-fast demand for sustainable lithium-ion batteries (LIB) with competitive electrochemical properties, safety, reduced costs, and long-life cycle, calls for intensive efforts towards the development of new battery cathode materials. The layered transition metal oxides formulated LiMO2 (M: Mn, Ni and Co) have attracted considerable attention due to their capability to optimize the discharge capacity, cycling rate, electrochemical stability and lifetime. The transition metals Mn, Ni and Co (NMC) have been reported to contribute towards enhancement of the performance of NMC based lithium-ion batteries. In this work, the electronic properties of transition metal oxides LiMO2 (M: Mn, Ni and Co) as individual crystal structures are studied using density functional theory (DFT+U) in the local density and generalized gradient approximation (LDA and GGA). The Hubbard U values together with the low spin transition metal in 3+ charge state (Mn3+, Ni3+ and Co3+) predicts the electrical conductivity of the materials. The conductivity is associated predominantly with 3d states of the transition metals (Mn, Ni and Co) and 2d character in oxygen. The LiNiO2 material is high in conductivity, while both LiMnO2 and LiCoO2 are low in electrical conductivity. All independent elastic constants satisfy the mechanical stability criterion of orthorhombic materials implying stability of the materials. However, the phonon dispersion curves display imaginary vibration along high symmetry direction for LiCoO2. The heats of formations predict that the LiNiO2 is the most thermodynamically stable material while the LiMnO2 is the least thermodynamically stable material. The derived interatomic potentials produced NiO and CoO structures with a difference of less than 1% and 9% respectively, from the experimental structures. The structures were melted at temperatures close to their experimental values from molecular dynamics. The radial distribution curves and Nano architectures presented the melting point of NiO and CoO at 2250K and 2000K respectively. All independent elastic constants satisfy the mechanical stability criterion of cubic materials implying stability of the materials. The high electrical conductivity and thermodynamic favourability LiNiO2 suggests that the material can be the most recommendable material as a cathode material and further improved through doping. This will add the overall enhancement of the electrochemical performance while stabilizing structural stability of the cathode material in high energy density Li-ion batteries. / National Research Foundation (NRF)

Mesoporous monocrystalline metal oxides (e.g. Co₃O₄, Cr₂O₃, NiO, CeO₂, In₂O₃ and WO₃) templated by SBA-15 or KIT-6 were synthesised successfully by using a simple solvent-free approach, the so-called solid-liquid method, which was the principal development of methodology in this project. A metal-containing precursor, whose melting point is lower than its decomposition temperature, was directly ground with a mesoporous silica and impregnated into the pores of the silica template after melting when the temperature was increased above its melting point. The liquid precursor then decomposed to form metal oxide inside the silica pores when the temperature was further increased to its decomposition temperature and crystallization temperature of the oxide. The structural characterisations of these porous metal oxides were performed by using TEM, XRD and N₂ adsorption/desorption techniques. The solid-liquid method is convenient and solvent-free. On the other hand, its limitation is that the precursor must have a melting point lower than its decomposition temperature. A novel porous single crystal of rutile TiO₂ as well as anatase nanocrystal-silica composite was also synthesised successfully for the first time using SBA-15 and KIT-6 as templates. These materials have interesting properties of proton conductivity, Li insertion and photoactivity. Likewise, the characterisation of porous TiO₂ was achieved by using XRD, TEM, SAED and N₂ adsorption/desorption. The residual SiO₂ component in porous TiO₂ was detected by using the EDX technique. Porous cubic metal oxides of Co₃O₄, NiO, CeO₂ and In₂O₃ were prepared using novel mesoporous silicas FDU-12 and SBA-16, which contain spherical nanocavities linked together by smaller windows. These porous materials have larger surface areas than those templated by SBA-15 and KIT-6. Unlike the cubic metal oxides, syntheses of porous crystals of non-cubic metal oxides such as rhombohedral Cr₂O₃, Fe₂O₃ and hexagonal TiO₂, WO₃ were not successful when using cage-containing mesoporous silicas as templates. The three-dimensional arrangements of nanospheres in porous crystals of cubic oxides mentioned above were observed by TEM and the corresponding larger surface areas were confirmed by N₂ adsorption/desorption technique. Additionally, fabrication of porous crystals of other metal oxides such as MgO, ZnO and ZrO₂ were unsuccessful by using either mesoporous silicas or mesoporous carbons as templates. Possible drawbacks of using mesoporous silica and carbon as templates were discussed.

published_or_final_version / abstract / Physics / Doctoral / Doctor of Philosophy

In the 4d transition metal oxides, the extension of the 4d orbitals leads to comparable and thus competitive kinetic and coulomb energies. As a result, small perturbations can induce significant changes in their physical properties, giving rise to a class of exotic phenomena that are rarely found in other materials. The ruthenates materials with readily tunable parameters open an avenue to study the strong electronic correlation in the rarely explored territory: the 4d transition metal oxides. The bilayered system, Ca3Ru2O7, belongs to the Ruddlesden-Popper series in which the physical properties are intimately linked to the lattice degrees of freedom. Ca3Ru2O7, with its quasi-2D and severe structure distortion, is believed to be placed in a unique position at which the role of orbital degrees of freedom is highlighted. The system displays strikingly different behaviors when the field is applied along different crystalline axes. A ferromagnetic (FM) state with full spin polarization is achieved for B||a-axis, but colossal magnetoresistance is realized only for B||b-axis by avoiding the ferromagnetic state. In addition, for B rotating within the ac-plane, slow and strong SdH oscillations periodic in 1/B are observed for T.1.5 K in the presence of metamagnetism. For B|| [110], oscillations are also observed but periodic in B (rather than 1/B) and persist up to 15 K. These properties together with highly unusual spin-charge-lattice coupling near the Mott transition (48 K) are driven by the orbital degrees of freedom. Complex thermodynamic properties are also observed in the other ruthenates system such as Sr4Ru3O10 and Pr3RuO7. The Sr4Ru3O10 is a triple-layered system that shows a dedicate balance between fluctuations and order. Besides the anomaly at TC=102K, anomalous behavior at low temperatures are also observed in the thermal study, indicative of an unusual magnetic order in this material. The Pr3RuO7 shows one-dimensional structure with zig-zag chain of corner sharing RuO6 octahedra running in parallel with the rows of edge-shared PrO8 pseudo-cubes. Magnetic and thermal properties studies on its single crystals indicate that the exchange interaction is strongly anisotropic. A Schottky-type anomaly at low temperature suggests that the gorderedh chain Pr ions are still sensitive to a crystal field.

Self-assembled nonionic alkyl glycoside surfactants are of interest for creating functional adsorption and catalytic sites at the surface of mesoporous metal oxides, but they typically impart poor long-range order when used as pore templates. Improved order and control over the functional site density may be achieved by mixing them with a cationic surfactant. To confirm this hypothesis, we investigate the lyotropic liquid crystalline (LLC) phase behavior of aqueous solutions of the functional nonionic surfactant n-dodecyl β-D-maltoside (C12G2) and cationic cetyltrimethylammonium bromide (C16TAB). A ternary phase diagram of the C16TAB-C12G2-water system is developed at 50 °C. By replacing the volume of water in the phase diagram with an equivalent volume of silica, ordered mesoporous materials are prepared by nanocasting with variable C12G2/C16TAB ratios. Metal oxide mesophases can almost always be predicted from the ternary phase diagram, except that silica prepared with high C12G2/C16TAB ratios are very weakly ordered, perhaps due to differences in hydrogen bonding or rate of assembly. Based on the ternary phase diagram of the system, a systematic approach is taken to the incorporation of titania sites via complexation to the maltoside headgroup of C12G2. Complexation to a saccharide is expected not only to guide titanium to the pore surface, but also to prevent uncontrolled hydrolysis and condensation of the (usually quite reactive) titanium precursor. Tetrahedrally coordinated titanium atoms incorporated into a silica network are believed to be the active oxidation sites required for heterogeneous silica-supported titania oxidation catalysts. To promote well-ordered materials and to allow control over titania site density, the mixed C12G2 / C16TAB system is used for pore templating. Series of Si-Ti mixed oxide thin films and bulk materials are synthesized with different amounts of titanium loading by utilizing pre-complexation between C12G2 and titanium isopropoxide. The degrees of homogeneity (indicated by tetracoordinated Ti) in these films are superior to those of films synthesized with the same loading of titanium but without C12G2 or without pre-complexation. Transition metal-carbohydrate complexation provides highly dispersed, tetrahedrally coordinated titanium atoms rather than the octahedral sites found without saccharide complexation.

Neutron scattering measurements were used to investigate the magnetic and crystal structure and magnetic excitations of three compounds characterized as low-dimensional quantum magnets. The materials are frustrated systems with low spin quantum number. The first was a powder sample of AgNiO₂. The Ni ions form a triangular lattice antiferromagnet in which, according to the published crystal structure, both the orbital order and magnetic couplings are frustrated. However, it is shown here that there was a small distortion of the crystal structure at 365 K, which is proposed to result from charge disproportionation and this relieves the orbital frustration. The magnetic structure was investigated and, below 20 K, the triangular lattice of electron-rich Ni sites was observed to order into antiferromagnetic stripes. Investigations of the magnetic excitations showed that the main dispersions were within the triangular plane, indicating a strong two-dimensionality. The dispersion was larger along the stripes than between the stripes of collinear spins. The second material investigated was CoNb₂O₆, a quasi Ising-like ferromagnet. It was studied with a magnetic field applied transverse to the Ising direction. The magnetic field introduced quantum fluctuations which drove a phase transition at a field comparable to the main exchange interaction. The phase diagram of the magnetic order was mapped outs and a transition from an ordered phase to a paramagnetic phase was identified at high field. This low-temperature high-field phase transition was further investigated by inelastic neutron scattering measurements to observe the change in the energy gap and magnetic excitation spectrum on either side of the transition. The spectrum had two components in the ordered phase and had sharp magnon modes in the paramagnetic phase. The third material was the spin-half layered antiferromagnet CuSb₂O₆. It has a square lattice of Cu²⁺ ions in which the main interaction is across only one diagonal of the square. The magnetic structure was studied by neutron scattering with a field applied along the direction of the zero-field ordered moment. A spin-flop was observed at low field and there was evidence for a high-field transition. The magnetic excitation spectrum was unusual in that it had an intense resonance at 13 meV at the magnetic Brillouin zone boundary.

Doctor of Philosophy / Department of Chemistry / Christine M. Aikens / Water oxidation can be considered as the ‘holy grail’ of renewable energy research, where water is split into constituent molecular hydrogen and oxygen. Hydrogen is a very efficient energy source that is both clean and sustainable. The byproduct of hydrogen combustion is water, which in turn can be reused as the source for hydrogen generation. Natural water splitting is observed during photosynthesis in the oxygen-evolving complex of photosystem II, which consists of a CaMn₄O₄ cubane core. Herein, we report in silico approaches to understand bottom up catalytic design of model transition metal oxide complexes for water splitting. We have employed density functional theory to investigate model ligand-free architectures of cobalt and manganese oxide dimer (Mn₂(μ-OH)(μ-O)(H₂O)₃(OH)₅, Mn₂(μ-OH)₂(H₂O)₄(OH)₄, Mn₂(μ-OH)₂(H₂O)₂(OH)₂(O(CH)₃O)₂, Co₂(μ-OH)₂(H₂O)₄(OH)₄ and cubane (Co₄O₄(H₂O)₈(OH)₄, Mn₄O₄(H₂O)[subscript]x(OH)[subscript]y x = 4-8, y = 8-4) complexes. The thermodynamically lowest energy pathway on the cobalt dimer catalyst proceeds through a nucleophilic attack of a solvent water molecule to a Co(V)-O radical moiety whereas the pathway on the cubane catalyst involves a geminal coupling of a Co(V)-O radical oxo group with bridging oxo sites. The lowest energy pathway for the fully saturated Mn₂O₄•6H₂O (Mn₂(μ-OH)(μ-O)(H₂O)₃(OH)₅) and Mn₂O₃•7H₂O (Mn₂(μ-OH)₂(H₂O)₄(OH)₄) complexes occur through a nucleophilic attack of a solvent water molecule to Mn(IV½)O and Mn(V)O oxo moieties respectively. Out of all the oxidation state configurations studied for the manganese cubane, we observed that Mn₄(IV IV IV IV), Mn₄(III IV IV IV), and Mn₄(III III IV V) configurations are thermodynamically viable for water oxidation. All three of these reaction pathways proceed via nucleophilic attack of solvent water molecule to the manganese oxo species. The highest thermodynamic energy step in manganese dimer and cubane complexes corresponds to the formation of the manganese oxo species, which is a significant feature that reoccurred in all these reaction pathways. We have also employed multireference and multiconfigurational calculations to investigate the Mn₂(μ-OH)₂(H₂O)₂(OH)₂(O(CH)₃O)₂ system. The presence of Mn(IV)O[superscript]• radical moieties has been observed in this catalytic pathway. These simplest models of cobalt and manganese with water-derived ligands are essential to understand microscopic properties that can be used as descriptors in designing future catalysts.

Master of Science / Department of Chemistry / Kenneth Klabunde / Remediation of the indoor environment led to the development of novel catalysts which can absorb light in the visible range. These catalysts were prepared using the wet chemistry method known as sol-gel chemistry because preparation via sol-gel provides a homogeneous gel formation, which can be treated via supercritical drying to produce an aerogel. These aerogels have been found to have high surface areas when a combination of titania/silica is used. The increase in surface area has been shown to enhance the activity of the catalysts. Mixed metal oxide systems were prepared using titanium isopropoxide and tetraethyl orthosilicate to yield a 1:1 system of titania/silica (TiO2/SiO2). These systems were doped during the initial synthesis with transition metals (Mn or Co) to create mixed metal oxide systems which absorb light in the visible light range. These materials were assessed for potential as heterogeneous catalysts via gas-solid phase reactions with acetaldehyde. Degradation of acetaldehyde as well as the formation of CO2 was monitored via gas chromatography-mass spectrometery. To increase the activity, visible light was introduced to the system. Experiments have shown that a 10 mol % manganese doped titania/silica system, in the presence of light, can degrade acetaldehyde. The cobalt doped counterpart showed dark activity in the presence of acetaldehyde resulting in the formation of CO2 without the addition of visible light. In the hope of increasing surface area a mixed solvent (toluene/methanol) synthesis procedure was applied to the manganese doped catalyst. The resulting materials were of a low surface area but showed a significant increase in degradation of acetaldehyde. Examination of the interactions between mixed metal oxide systems and semivolatile organic compounds (SVOCs) was studied. The pollutant, triphenyl phosphate, was dissolved in n-pentane and exposed to 10 mg of a given catalyst. These reactions were monitored using UVVis. All systems but the manganese doped titania/silica system resulted in the observation of no activity with triphenyl phosphate. The manganese doped catalyst shown a peculiar activity, the increase in absorbance of the triphenyl phosphate peaks as well as the formation of a new peak.