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Coupling of the 4f Electrons in Lanthanide Molecules

Description: (C5Me5)2LnOTf where Ln = La, Ce, Sm, Gd, and Yb have been synthesized and these derivatives are good starting materials for the synthesis of (C5Me5)2LnX derivatives. (C5Me5)2Ln(2,2'-bipyridine), where Ln = La, Ce, Sm, and Gd, along with several methylated bipyridine analogues have been synthesized and their magnetic moments have been measured as a function of temperature. In lanthanum, cerium, and gadolinium complexes the bipyridine ligand ligand is unequivocally the radical anion, and the observed magnetic moment is the result of intramolecular coupling of the unpaired electron on the lanthanide fragment with the unpaired electron on the bipyridine along with the intermolecular coupling between radicals. Comparison with the magnetic moments of the known compounds (C5Me5)2Sm(2,2'-bipyridine) and (C5Me5)2Yb(2,2'-bipyridine) leads to an understanding of the role of the Sm(II)/Sm(III) and Yb(II)/Yb(III) couple in the magnetic properties of (C5Me5)2Sm(2,2'-bipyridine) and (C5Me5)2Yb(2,2'-bipyridine). In addition, crystal structures of (C5Me5)2Ln(2,2'-bipyridine) and [(C5Me5)2Ln(2,2'-bipyridine)][BPh4](Ln= Ce and Gd), where the lanthanide is unequivocally in the +3 oxidation state, give the crystallographic characteristics of bipyridine as an anion and as a neutral ligand in the same coordination environment, respectively. Substituted bipyridine ligands coordinated to (C5Me5)2Yb are studied to further understand how the magnetic coupling in (C5Me5)2Yb(2,2'-bipyridine) changes with substitutions. In the cases of (C5Me5)2Yb(5,5'-dimethyl-2,2'-bipyridine) and (C5Me5)2Yb(6-methyl-2,2'-bipyridine), the valence, as measured by XANES, changes as a function of temperature. In general, the magnetism in complexes of the type (C5Me5)2Yb(bipy.-), where bipyo represents 2,2'-bipyridine and substituted 2,2'-bipyridine ligands, is described by a multiconfiguration model, in which the ground state is an open-shell singlet composed of two configurations: Yb(III, f13)(bipy.-) and Yb(II, f14)(bipyo). The relative contributions of the two configurations depends on the substituents on the bipyridine ligand.[(C5H4Me)3Ln]2(L) (Ln = Ce, Tb; L = 4,4'-bipyridine, 1,4-benzoquinone) are synthesized in order to study the effect of these ligands on the oxidation states of the metal ...
Date: September 12, 2008
Creator: Kazhdan, Daniel
Partner: UNT Libraries Government Documents Department

Phase transformation near the classical limit of stability

Description: Successful theories of phase transformation processes include classical nucleation theory (CNT), which envisions a local equilibrium between coexisting phases, and non--equilibrium kinetic cluster theories. Using computer simulations of the magnetization reversal of the Ising model in three different ensembles we make quantitative connections between these physical pictures. We show that the critical nucleus size of CNT is strongly correlated with a dynamical measure of metastability, and that the metastable phase persists to thermodynamic conditions previously thought of as unstable.
Date: November 6, 2008
Creator: Maibaum, Lutz
Partner: UNT Libraries Government Documents Department

The Estimation of Heats of Formation

Description: The procedure for estimation of heats of formation of compounds is illustrated by discussion of compounds of several of the elements of the actinide series. The procedure is particularly suited for lanthanide and actinide elements because of the similarity of the ionic radii and types of bonding.
Date: February 2, 1948
Creator: Brewer, Leo
Partner: UNT Libraries Government Documents Department

Rational Ligand Design for U(VI) and Pu(IV)

Description: Nuclear power is an attractive alternative to hydrocarbon-based energy production at a time when moving away from carbon-producing processes is widely accepted as a significant developmental need. Hence, the radioactive actinide power sources for this industry are necessarily becoming more widespread, which is accompanied by the increased risk of exposure to both biological and environmental systems. This, in turn, requires the development of technology designed to remove such radioactive threats efficiently and selectively from contaminated material, whether that be contained nuclear waste streams or the human body. Raymond and coworkers (University of California, Berkeley) have for decades investigated the interaction of biologically-inspired, hard Lewis-base ligands with high-valent, early-actinide cations. It has been established that such ligands bind strongly to the hard Lewis-acidic early actinides, and many poly-bidentate ligands have been developed and shown to be effective chelators of actinide contaminants in vivo. Work reported herein explores the effect of ligand geometry on the linear U(IV) dioxo dication (uranyl, UO{sub 2}{sup 2+}). The goal is to utilize rational ligand design to develop ligands that exhibit shape selectivity towards linear dioxo cations and provides thermodynamically favorable binding interactions. The uranyl complexes with a series of tetradentate 3-hydroxy-pyridin-2-one (3,2-HOPO) ligands were studied in both the crystalline state as well as in solution. Despite significant geometric differences, the uranyl affinities of these ligands vary only slightly but are better than DTPA, the only FDA-approved chelation therapy for actinide contamination. The terepthalamide (TAM) moiety was combined into tris-beidentate ligands with 1,2- and 3,2-HOPO moieties were combined into hexadentate ligands whose structural preferences and solution thermodynamics were measured with the uranyl cation. In addition to achieving coordinative saturation, these ligands exhibited increased uranyl affinity compared to bis-Me-3,2-HOPO ligands. This result is due in part to their increased denticity, but is primarily the result of the presence ...
Date: August 12, 2009
Creator: Szigethy, Geza
Partner: UNT Libraries Government Documents Department


Description: The nuclear radiations of nuclides: U{sup 233}, Pu{sup 239}, Bk{sup 243}, Bk{sup 244}, Bk{sup 245}, Bk{sup 246}, Bk{sup 249}, Cf{sup 249}, and Fm{sup 255} were investigated with high-resolution spectrometers. The {alpha}-particle spectra of all nuclides except Bk{sup 249} were measured with 6 mm diameter surface-barrier detectors. Bk{sup 249} {alpha}-particles were analyzed with a double-focusing magnetic spectrograph. The {gamma}-singles were examined with the recently developed Ge(Li) and Si(Li) detectors coupled with very-low noise 'internal FET' preamplifiers. Weak alpha groups were observed in coincidence with {gamma}-rays, detected with a NaI(Tl) scintillation spectrometer. To improve the over-all coincidence efficiency a new coincidence apparatus was designed and built. This instrument consisted of a cooled 4.5 cm diameter semiconductor detector for {alpha}-particle detection and a 3 cm diameter by 2.7 cm long Ge(Li) detector for {gamma}-ray analysis. The Ge(Li) detector could also be replaced with a NaI(Tl) detector. Cf{sup 249} conversion electrons were measured with a cooled Si(Li) detector coupled with an internal FET preamplifier. On the basis of the present work and previous information, energy-level diagrams of the daughter nuclei have been constructed. The levels have been grouped into rotational bands built on Nilsson single-particle states. Because of identification of several rotational members of the bands, definite Nilsson quantum number assignments have been made in most cases. The alpha intensity calculations of Poggenburg were found quite helpful in making these assignments. A strong Coriolis effect was observed in the Am{sup 245} levels populated by the alpha groups of Bk{sup 249}. Calculations were made with Nilsson wave-functions, and these were found to agree with the experimental results. The Coriolis interaction was found important in almost all cases; the effect was very noticeable in the level spacings between the rotational members of the bands. High-lying bands in Cm{sup 245} (at 644 keV) and cf{sup 251} (at ...
Date: September 20, 1966
Creator: Ahmad, Irshad
Partner: UNT Libraries Government Documents Department

The effect of temperature on the speciation of U(VI) in sulfate solutions

Description: Sulfate, one of the inorganic constituents that could be present in the nuclear waste repository, forms complexes with U(VI) and affects its migration in the environment. Results show that the complexation of U(VI) with sulfate is enhanced by the increase in temperature. The effect of temperature on the complexation and speciation of U(VI) in sulfate solutions is discussed.
Date: September 15, 2008
Creator: Rao, Linfeng & Tian, Guoxin
Partner: UNT Libraries Government Documents Department

Formic Acid Dehydrogenation on Au-Based Catalysts at Near-Ambient Temperatures

Description: Formic acid (HCOOH) is a convenient hydrogen carrier in fuel cells designed for portable use. Recent studies have shown that HCOOH decomposition is catalyzed with Ru-based complexes in the aqueous phase at near-ambient temperatures. HCOOH decomposition reactions are used frequently to probe the effects of alloying and cluster size and of geometric and electronic factors in catalysis. These studies have concluded that Pt is the most active metal for HCOOH decomposition, at least as large crystallites and extended surfaces. The identity and oxidation state of surface metal atoms influence the relative rates of dehydrogenation (HCOOH {yields} H{sub 2} + CO{sub 2}) and dehydration (HCOOH {yields} H{sub 2}O + CO) routes, a selectivity requirement for the synthesis of CO-free H{sub 2} streams for low-temperature fuel cells. Group Ib and Group VIII noble metals catalyze dehydrogenation selectively, while base metals and metal oxides catalyze both routes, either directly or indirectly via subsequent water-gas shift (WGS) reactions.
Date: November 24, 2008
Creator: Ojeda, Manuel & Iglesia, Enrique
Partner: UNT Libraries Government Documents Department

Two-photon Photoemission of Organic Semiconductor Molecules on Ag(111)

Description: Angle- and time-resolved two-photon photoemission (2PPE) was used to study systems of organic semiconductors on Ag(111). The 2PPE studies focused on electronic behavior specific to interfaces and ultrathin films. Electron time dynamics and band dispersions were characterized for ultrathin films of a prototypical n-type planar aromatic hydrocarbon, PTCDA, and representatives from a family of p-type oligothiophenes.In PTCDA, electronic behavior was correlated with film morphology and growth modes. Within a fewmonolayers of the interface, image potential states and a LUMO+1 state were detected. The degree to which the LUMO+1 state exhibited a band mass less than a free electron mass depended on the crystallinity of the layer. Similarly, image potential states were measured to have free electron-like effective masses on ordered surfaces, and the effective masses increased with disorder within the thin film. Electron lifetimes were correlated with film growth modes, such that the lifetimes of electrons excited into systems created by layer-by-layer, amorphous film growth increased by orders of magnitude by only a few monolayers from the surface. Conversely, the decay dynamics of electrons in Stranski-Krastanov systems were limited by interaction with the exposed wetting layer, which limited the barrier to decay back into the metal.Oligothiophenes including monothiophene, quaterthiophene, and sexithiophene were deposited on Ag(111), and their electronic energy levels and effective masses were studied as a function of oligothiophene length. The energy gap between HOMO and LUMO decreased with increasing chain length, but effective mass was found to depend on domains from high- or low-temperature growth conditions rather than chain length. In addition, the geometry of the molecule on the surface, e.g., tilted or planar, substantially affected the electronic structure.
Date: May 15, 2008
Creator: Yang, Aram & Yang, Aram
Partner: UNT Libraries Government Documents Department

Monodisperse Platinum and Rhodium Nanoparticles as Model Heterogeneous Catalysts

Description: Model heterogeneous catalysts have been synthesized and studied to better understand how the surface structure of noble metal nanoparticles affects catalytic performance. In this project, monodisperse rhodium and platinum nanoparticles of controlled size and shape have been synthesized by solution phase polyol reduction, stabilized by polyvinylpyrrolidone (PVP). Model catalysts have been developed using these nanoparticles by two methods: synthesis of mesoporous silica (SBA-15) in the presence of nanoparticles (nanoparticle encapsulation, NE) to form a composite of metal nanoparticles supported on SBA-15 and by deposition of the particles onto a silicon wafer using Langmuir-Blodgett (LB) monolayer deposition. The particle shapes were analyzed by transmission electron microscopy (TEM) and high resolution TEM (HRTEM) and the sizes were determined by TEM, X-ray diffraction (XRD), and in the case of NE samples, room temperature H2 and CO adsorption isotherms. Catalytic studies were carried out in homebuilt gas-phase reactors. For the nanoparticles supported on SBA-15, the catalysts are in powder form and were studied using the homebuilt systems as plug-flow reactors. In the case of nanoparticles deposited on silicon wafers, the same systems were operated as batch reactors. This dissertation has focused on the synthesis, characterization, and reaction studies of model noble metal heterogeneous catalysts. Careful control of particle size and shape has been accomplished though solution phase synthesis of Pt and Rh nanoparticles in order to elucidate further structure-reactivity relationships in noble metal catalysis.
Date: August 15, 2008
Creator: Coble, Inger M
Partner: UNT Libraries Government Documents Department

Comment on"Elucidating the Mechanism of Nucleation near the Gas-Liquid Spinodal"

Description: In a recent Letter [1], Bhimalapuram, Chakrabarty and Bagchi (BCB) study the phase transformation mechanism of the Lennard-Jones fluid and the non-conserved Ising model. They compute the free energy as a function of the size of the largest droplet of the stable phase. In apparent contradiction to classical nucleation theory (CNT), they find that in both systems the free energy develops a minimum at subcritical cluster sizes. In this Comment we argue that this minimum is specific to the chosen order parameter, and that the observed behavior is in fact consistent with CNT. CNT states that the free energy F(N) of a single cluster of size N is a concave function with a maximum at the critical nucleus size N{sub c}. BCB, on the other hand, calculate the probability distribution of N*, the size of the largest cluster in the system, and compute the free energy {beta}F*(N*) = -ln P(N*), where {beta} = 1/k{sub B}T. This order parameter does not measure the size of a single cluster. Instead, when sampling small values of N*, one measures the statistical weight of configurations in which all clusters are at most N* in size. Hence a free energy penalty is incurred when one constrains N* to values smaller than the largest average cluster in the simulation volume V. It is this penalty that causes the sudden increase of F* as N* {yields} 0 and the minimum at intermediate values of N*. We now illustrate how F(N) can be calculated from simulations. Our argument is intuitive but not exact, a formal derivation that yields an equivalent result can be found in Ref. 2. We choose the Ising model for concreteness. We aim to compute the probability that a given cluster has size N, where we imagine the center of the cluster to be fixed ...
Date: June 18, 2008
Creator: Maibaum, Lutz & Maibaum, Lutz
Partner: UNT Libraries Government Documents Department

Complexation of Lanthanides with Nitrate at Variable Temperatures: Thermodynamics and Coordination Modes

Description: Complexation of neodymium(III) with nitrate was studied at variable temperatures (25, 40, 55 and 70 C) by spectrophotometry and microcalorimetry. The NdNO{sub 3}{sup 2+} complex is weak and becomes slightly stronger as the temperature is increased. The enthalpy of complexation at 25 C was determined by microcalorimetry to be small and positive, (1.5 {+-} 0.2) kJ {center_dot} mol{sup -1}, in good agreement with the trend of the stability constant at variable temperatures. Luminescence emission spectra and lifetime of Eu(III) in nitrate solutions suggest that inner-sphere and bidentate complexes form between trivalent lanthanides (Nd{sup 3+} and Eu{sup 3+}) and nitrate in aqueous solutions. Specific Ion Interaction approach (SIT) was used to obtain the stability constants of NdNO{sub 3}{sup 2+} at infinite dilution and variable temperatures.
Date: December 10, 2008
Creator: Rao, Linfeng & Tian, Guoxin
Partner: UNT Libraries Government Documents Department

Electronically Nonadiabatic Dynamics via Semiclassical Initial Value Methods

Description: In the late 1970's Meyer and Miller (MM) [J. Chem. Phys. 70, 3214 (1979)] presented a classical Hamiltonian corresponding to a finite set of electronic states of a molecular system (i.e., the various potential energy surfaces and their couplings), so that classical trajectory simulations could be carried out treating the nuclear and electronic degrees of freedom (DOF) in an equivalent dynamical framework (i.e., by classical mechanics), thereby describing non-adiabatic dynamics in a more unified manner. Much later Stock and Thoss (ST) [Phys. Rev. Lett. 78, 578 (1997)] showed that the MM model is actually not a 'model', but rather a 'representation' of the nuclear-electronic system; i.e., were the MMST nuclear-electronic Hamiltonian taken as a Hamiltonian operator and used in the Schroedinger equation, the exact (quantum) nuclear-electronic dynamics would be obtained. In recent years various initial value representations (IVRs) of semiclassical (SC) theory have been used with the MMST Hamiltonian to describe electronically non-adiabatic processes. Of special interest is the fact that though the classical trajectories generated by the MMST Hamiltonian (and which are the 'input' for an SC-IVR treatment) are 'Ehrenfest trajectories', when they are used within the SC-IVR framework the nuclear motion emerges from regions of non-adiabaticity on one potential energy surface (PES) or another, and not on an average PES as in the traditional Ehrenfest model. Examples are presented to illustrate and (hopefully) illuminate this behavior.
Date: December 11, 2008
Creator: Miller, William H.
Partner: UNT Libraries Government Documents Department

Effect of temperature on the complexation of Uranium(VI) with fluoride in aqueous solutions

Description: Complexation of U(VI) with fluoride at elevated temperatures in aqueous solutions was studied by spectrophotometry. Four successive complexes, UO{sub 2}F{sup +}, UO{sub 2}F{sub 2}(aq), UO{sub 2}F{sub 3}{sup -}, and UO{sub 2}F{sub 4}{sup 2-}, were identified, and the stability constants at 25, 40, 55, and 70 C were calculated. The stability of the complexes increased as the temperature was elevated. The enthalpies of complexation at 25 C were determined by microcalorimetry. Thermodynamic parameters indicate that the complexation of U(VI) with fluoride in aqueous solutions at 25 to 70 C is slightly endothermic and entropy-driven. The Specific Ion Interaction (SIT) approach was used to obtain the thermodynamic parameters of complexation at infinite dilution. Structural information on the U(VI)/fluoride complexes was obtained by extended X-ray absorption fine structure spectroscopy.
Date: May 18, 2009
Creator: Tian, Guoxin & Rao, Linfeng
Partner: UNT Libraries Government Documents Department

Isomorphic classical molecular dynamics model for an excess electronin a supercritical fluid

Description: Ring polymer molecular dynamics (RPMD) is used to directly simulate the dynamics of an excess electron in a supercritical fluid over a broad range of densities. The accuracy of the RPMD model is tested against numerically exact path integral statistics through the use of analytical continuation techniques. At low fluid densities, the RPMD model substantially underestimates the contribution of delocalized states to the dynamics of the excess electron. However, with increasing solvent density, the RPMD model improves, nearly satisfying analytical continuation constraints at densities approaching those of typical liquids. In the high density regime, quantum dispersion substantially decreases the self-diffusion of the solvated electron. In this regime where the dynamics of the electron is strongly coupled to the dynamics of the atoms in the fluid, trajectories that can reveal diffusive motion of the electron are long in comparison to {beta}{h_bar}.
Date: August 4, 2008
Creator: Miller III, Thomas F.
Partner: UNT Libraries Government Documents Department

Coarse Grained Modeling of The Interface BetweenWater and Heterogeneous Surfaces

Description: Using coarse grained models we investigate the behavior of water adjacent to an extended hydrophobic surface peppered with various fractions of hydrophilic patches of different sizes. We study the spatial dependence of the mean interface height, the solvent density fluctuations related to drying the patchy substrate, and the spatial dependence of interfacial fluctuations. We find that adding small uniform attractive interactions between the substrate and solvent cause the mean position of the interface to be very close to the substrate. Nevertheless, the interfacial fluctuations are large and spatially heterogeneous in response to the underlying patchy substrate. We discuss the implications of these findings to the assembly of heterogeneous surfaces.
Date: June 23, 2008
Creator: Willard, Adam & Chandler, David
Partner: UNT Libraries Government Documents Department

One- and two-dimensional infrared spectroscopic studies of solution-phase homogeneous catalysis and spin-forbidden reactions

Description: Understanding chemical reactions requires the knowledge of the elementary steps of breaking and making bonds, and often a variety of experimental techniques are needed to achieve this goal. The initial steps occur on the femto- through picosecond time-scales, requiring the use of ultrafast spectroscopic methods, while the rate-limiting steps often occur more slowly, requiring alternative techniques. Ultrafast one and two-dimensional infrared and step-scan FTIR spectroscopies are used to investigate the photochemical reactions of four organometallic complexes. The analysis leads to a detailed understanding of mechanisms that are general in nature and may be applicable to a variety of reactions.
Date: December 12, 2008
Creator: Sawyer, Karma Rae
Partner: UNT Libraries Government Documents Department

The Siderocalin/Enterobactin Interaction: A Link between Mammalian Immunity and Bacterial Iron Transport

Description: The siderophore enterobactin (Ent) is produced by enteric bacteria to mediate iron uptake. Ent scavenges iron and is taken up by the bacteria as the highly stable ferric complex [Fe{sup III}(Ent)]{sup 3-}. This complex is also a specific target of the mammalian innate immune system protein, Siderocalin (Scn), which acts as an anti-bacterial agent by specifically sequestering siderophores and their ferric complexes during infection. Recent literature suggesting that Scn may also be involved in cellular iron transport has increased the importance of understanding the mechanism of siderophore interception and clearance by Scn; Scn is observed to release iron in acidic endosomes and [Fe{sup III}(Ent)]{sup 3-} is known to undergo a change from catecholate to salicylate coordination in acidic conditions, which is predicted to be sterically incompatible with the Scn binding pocket (also referred to as the calyx). To investigate the interactions between the ferric Ent complex and Scn at different pH values, two recombinant forms of Scn with mutations in three residues lining the calyx were prepared: Scn-W79A/R81A and Scn-Y106F. Binding studies and crystal structures of the Scn-W79A/R81A:[Fe{sup III}(Ent)]{sup 3-} and Scn-Y106F:[Fe{sup III}(Ent)]{sup 3-} complexes confirm that such mutations do not affect the overall conformation of the protein but do weaken significantly its affinity for [Fe{sup III}(Ent)]{sup 3-}. Fluorescence, UV-Vis and EXAFS spectroscopies were used to determine Scn/siderophore dissociation constants and to characterize the coordination mode of iron over a wide pH range, in the presence of both mutant proteins and synthetic salicylate analogs of Ent. While Scn binding hinders salicylate coordination transformation, strong acidification results in the release of iron and degraded siderophore. Iron release may therefore result from a combination of Ent degradation and coordination change.
Date: May 12, 2008
Creator: Meux, Susan C.
Partner: UNT Libraries Government Documents Department

Segue between Favorable and Unfavorable Solvation

Description: Solvation of small and large clusters are studied by simulation, considering a range of solvent-solute attractive energy strengths. Over a wide range of conditions, both for solvation in the Lennard-Jones liquid and in the SPC model of water, it is shown that the mean solvent density varies linearly with changes in solvent-solute adhesion or attractive energy strength. This behavior is understood from the perspective of Weeks theory of solvation [Ann. Rev. Phys. Chem. 2002, 53, 533] and supports theories based upon that perspective.
Date: March 21, 2007
Creator: Maibaum, Lutz & Chandler, David
Partner: UNT Libraries Government Documents Department

Spectrophotometric and Calorimetric Studies of U(VI) Complexation with Sulfate at 25-70oC

Description: Sulfate, one of the inorganic constituents in the groundwater of nuclear waste repository, could affect the migration of radioactive materials by forming complexes. Spectrophotometric and microcalorimetric titrations were performed to identify the U(VI)/sulfate complexes and determine the equilibrium constants and enthalpy of complexation at 25-70 C. Results show that U(VI) forms moderately strong complexes with sulfate, i.e., UO{sub 2}SO{sub 4}(aq) and UO{sub 2}(SO{sub 4}){sub 2}{sup 2-}, in this temperature range and the complexes become stronger as the temperature is increased: 2-fold and 10-fold increases in the stability constants of UO{sub 2}SO{sub 4}(aq) and UO{sub 2}(SO{sub 4}{sub 2}{sup 2-}), respectively, when the temperature is increased from 25 C to 70 C. The complexation is endothermic and entropy-driven, showing typical characteristics of inner-sphere complexation and 'hard acid'/'hard base' interactions. The thermodynamic trends are discussed in terms of dehydration of both the cation (UO{sub 2}{sup 2+}) and the anion (SO{sub 4}{sup 2-}) as well as the effect of temperature on the structure of water.
Date: October 30, 2008
Creator: Tian, Guoxin & Rao, Linfeng
Partner: UNT Libraries Government Documents Department

Gd-HOPO Based High Relaxivity MRI Contrast Agents

Description: Tris-bidentate HOPO-based ligands developed in our laboratory were designed to complement the coordination preferences of Gd{sup 3+}, especially its oxophilicity. The HOPO ligands provide a hexadentate coordination environment for Gd{sup 3+} in which all he donor atoms are oxygen. Because Gd{sup 3+} favors eight or nine coordination, this design provides two to three open sites for inner-sphere water molecules. These water molecules rapidly exchange with bulk solution, hence affecting the relaxation rates of bulk water olecules. The parameters affecting the efficiency of these contrast agents have been tuned to improve contrast while still maintaining a high thermodynamic stability for Gd{sup 3+} binding. The Gd- HOPO-based contrast agents surpass current commercially available agents ecause of a higher number of inner-sphere water molecules, rapid exchange of inner-sphere water molecules via an associative mechanism, and a long electronic relaxation time. The contrast enhancement provided by these agents is at least twice that of commercial contrast gents, which are based on polyaminocarboxylate ligands.
Date: November 6, 2008
Creator: Datta, Ankona & Raymond, Kenneth
Partner: UNT Libraries Government Documents Department

Two-electron time-delay interference in atomic double ionization by attosecond pulses

Description: A two-color two-photon atomic double ionization experiment using subfemtosecond UV pulses can be designed such that the sequential two-color process dominates and one electron is ejected by each pulse. Nonetheless, ab initio calculations show that, for sufficiently short pulses, a prominent interference pattern in the joint energy distribution of the sequentially ejected electrons can be observed that is due to their indistinguishability and the exchange symmetry of the wave function.
Date: October 4, 2009
Creator: Rescigno, Thomas N
Partner: UNT Libraries Government Documents Department

Quantum Dynamical Behaviour in Complex Systems - A Semiclassical Approach

Description: One of the biggest challenges in Chemical Dynamics is describing the behavior of complex systems accurately. Classical MD simulations have evolved to a point where calculations involving thousands of atoms are routinely carried out. Capturing coherence, tunneling and other such quantum effects for these systems, however, has proven considerably harder. Semiclassical methods such as the Initial Value Representation (SC-IVR) provide a practical way to include quantum effects while still utilizing only classical trajectory information. For smaller systems, this method has been proven to be most effective, encouraging the hope that it can be extended to deal with a large number of degrees of freedom. Several variations upon the original idea of the SCIVR have been developed to help make these larger calculations more tractable; these range from the simplest, classical limit form, the Linearized IVR (LSC-IVR) to the quantum limit form, the Exact Forward-Backward version (EFB-IVR). In this thesis a method to tune between these limits is described which allows us to choose exactly which degrees of freedom we wish to treat in a more quantum mechanical fashion and to what extent. This formulation is called the Tuning IVR (TIVR). We further describe methodology being developed to evaluate the prefactor term that appears in the IVR formalism. The regular prefactor is composed of the Monodromy matrices (jacobians of the transformation from initial to finial coordinates and momenta) which are time evolved using the Hessian. Standard MD simulations require the potential surfaces and their gradients, but very rarely is there any information on the second derivative. We would like to be able to carry out the SC-IVR calculation without this information too. With this in mind a finite difference scheme to obtain the Hessian on-the-fly is proposed. Wealso apply the IVR formalism to a few problems of current interest. A method ...
Date: May 22, 2008
Creator: Gliebe, Cheryn E & Ananth, Nandini
Partner: UNT Libraries Government Documents Department

Direct Functionalization of Nitrogen Heterocycles via Rh-Catalyzed C-H Bond Activation

Description: Nitrogen heterocycles are present in many compounds of enormous practical importance, ranging from pharmaceutical agents and biological probes to electroactive materials. Direct funtionalization of nitrogen heterocycles through C-H bond activation constitutes a powerful means of regioselectively introducing a variety of substituents with diverse functional groups onto the heterocycle scaffold. Working together, our two groups have developed a family of Rh-catalyzed heterocycle alkylation and arylation reactions that are notable for their high level of functional-group compatibility. This Account describes their work in this area, emphasizing the relevant mechanistic insights that enabled synthetic advances and distinguished the resulting transformations from other methods. They initially discovered an intramolecular Rh-catalyzed C-2-alkylation of azoles by alkenyl groups. That reaction provided access to a number of di-, tri-, and tetracyclic azole derivatives. They then developed conditions that exploited microwave heating to expedite these reactions. While investigating the mechanism of this transformation, they discovered that a novel substrate-derived Rh-N-heterocyclic carbene (NHC) complex was involved as an intermediate. They then synthesized analogous Rh-NHC complexes directly by treating precursors to the intermediate [RhCl(PCy{sub 3}){sub 2}] with N-methylbenzimidazole, 3-methyl-3,4-dihydroquinazolein, and 1-methyl-1,4-benzodiazepine-2-one. Extensive kinetic analysis and DFT calculations supported a mechanism for carbene formation in which the catalytically active RhCl(PCy{sub 3}){sub 2} fragment coordinates to the heterocycle before intramolecular activation of the C-H bond occurs. The resulting Rh-H intermediate ultimately tautomerizes to the observed carbene complex. With this mechanistic information and the discovery that acid co-catalysts accelerate the alkylation, they developed conditions that efficiently and intermolecularly alkylate a variety of heterocycles, including azoles, azolines, dihydroquinazolines, pyridines, and quinolines, with a wide range of functionalized olefins. They demonstrated the utility of this methodology in the synthesis of natural products, drug candidates, and other biologically active molecules. In addition, they developed conditions to directly arylate these heterocycles with aryl halides. The initial conditions ...
Date: February 4, 2008
Creator: Lewis, Jared; Bergman, Robert & Ellman, Jonathan
Partner: UNT Libraries Government Documents Department