Non-Fermi-liquid theory for disordered metals near two dimensions

We consider the Finkelstein action describing a system of spin-polarized or spinless electrons in 2+2epsilon dimensions, in the presence of disorder as well as the Coulomb interactions. We extend the renormalization-group analysis of our previous work and evaluate the metal-insulator transition of the electron gas to second order in an epsilon expansion. We obtain the complete scaling behavior of physical observables like the conductivity and the specific heat with varying frequency, temperature, and/or electron density. We extend the results for the interacting electron gas in 2+2epsilon dimensions to include the quantum critical behavior of the plateau transitions in the quantum Hall regime. Although these transitions have a very different microscopic origin and are controlled by a topological term in the action (theta term), the quantum critical behavior is in many ways the same in both cases. We show that the two independent critical exponents of the quantum Hall plateau transitions, previously denoted as nu and p, control not only the scaling behavior of the conductances sigma(xx) and sigma(xy) at finite temperatures T, but also the non-Fermi-liquid behavior of the specific heat (c(v)proportional toT(p)). To extract the numerical values of nu and p it is necessary to extend the experiments on transport to include the specific heat of the electron gas.

density matrix renormalization group study of polyacene

We study the nature of excited states of long polyacene oligomers within a Pariser-Parr-Pople (PPP) Hamiltonian using the Symmetrized Density Matrix Renormalization Group (SDMRG) technique. We find a crossover between the two-photon state and the lowest dipole allowed excited state as the system size is increased from tetracene to pentacene. The spin-gap is the smallest gap. We also study the equilibrium geome tries in the ground and excited states from bond orders and bond-bond correlation functions. We find that the Peierls instability in the ground state of polyacene is conditional both from energetics and structure factors computed froth correlation functions.

Gibbs energies of formation of intermetallic phases in the systems Pt Mg, Pt Ca and Pt Ba and some applications

The standard Gibbs energies of formation of platinum-rich intermetallic compounds in the systems Pt-Mg, Pt-Ca, and Pt-Ba have been measured in the temperature range of 950 to 1200 K using solid-state galvanic cells based on MgF2, CaF2, and BaF2 as solid electrolytes. The results are summarized by the following equations: ΔG° (MgPt7) = −256,100 + 16.5T (±2000) J/mol ΔG° (MgPt3) = −217,400 + 10.7T (±2000) J/mol ΔG° (CaPt5) = −297,500 + 13.0T (±5000) J/mol ΔG° (Ca2Pt7) = −551,800 + 22.3T (±5000) J/mol ΔG° (CaPt2) = −245,400 + 9.3T (±5000) J/mol ΔG° (BaPt5) = −238,700 + 8.1T (±4000) J/mol ΔG° (BaPt2) = −197,300 + 4.0T (±4000) J/mol where solid platinum and liquid alkaline earth metals are selected as the standard states. The relatively large error estimates reflect the uncertainties in the auxiliary thermodynamic data used in the calculation. Because of the strong interaction between platinum and alkaline earth metals, it is possible to reduce oxides of Group ILA metals by hydrogen at high temperature in the presence of platinum. The alkaline earth metals can be recovered from the resulting intermetallic compounds by distillation, regenerating platinum for recycling. The platinum-slag-gas equilibration technique for the study of the activities of FeO, MnO, or Cr2O3 in slags containing MgO, CaO, or BaO is feasible provided oxygen partial pressure in the gas is maintained above that corresponding to the coexistence of Fe and “FeO.”

Effect of substrate surface roughness on electric current induced flow of liquid metals

Electric current can induce long-range flow of liquid metals over a conducting substrate. This work reports on the effect of the substrate surface roughness on the liquid metal-front velocity during such a flow. Experiments were conducted by passing electric current through liquid gallium placed over similar to 170 nm thick, 500 mu m wide gold and platinum films of varying roughness. The ensuing flow, thus, resembles micro-fluidics behavior in an open-channel. The liquid-front velocity decreased linearly with the substrate surface roughness; this is attributed to the reduction in the effective electric field along the liquid metal-substrate interface with the substrate surface roughness. (C) 2013 American Institute of Physics. http://dx.doi.org/10.1063/1.4790182]

Majorana modes and transport across junctions of superconductors and normal metals

We study Majorana modes and transport in one-dimensional systems with a p-wave superconductor (SC) and normal metal leads. For a system with an SC lying between two leads, it is known that there is a Majorana mode at the junction between the SC and each lead. If the p-wave pairing Delta changes sign or if a strong impurity is present at some point inside the SC, two additional Majorana modes appear near that point. We study the effect of all these modes on the sub-gap conductance between the leads and the SC. We derive an analytical expression as a function of Delta and the length L of the SC for the energy shifts of the Majorana modes at the junctions due to hybridization between them; the shifts oscillate and decay exponentially as L is increased. The energy shifts exactly match the location of the peaks in the conductance. Using bosonization and the renormalization group method, we study the effect of interactions between the electrons on Delta and the strengths of an impurity inside the SC or the barriers between the SC and the leads; this in turn affects the Majorana modes and the conductance. Finally, we propose a novel experimental realization of these systems, in particular of a system where Delta changes sign at one point inside the SC.

Potential Application of Adsorptive Media to Enhance Phosphorus Uptake in Stormwater Basins and Wetlands at Lake Tahoe : literature review. Report to the University of California Davis Tahoe Research Group

Phosphorus removal by wetlands and basins in Lake Tahoe may be improved through designing these systems to filter storm water through media having higher phosphorus removal capabilities than local parent material. Substrates rich in iron, aluminum and calcium oftentimes have enhanced phosphorus removal. These substrates can be naturally occurring, byproducts of industrial or water treatment processes, or engineered. Phosphorus removal fundamentally occurs through chemical adsorption and/or precipitation and much of the phosphorus can be irreversibly bound. In addition to these standard media, other engineered substrates are available to enhance P removal. One such substrate is locally available in Reno and uses lanthanum coated diatomaceous earth for arsenate removal. This material, which has a high positive surface charge, can also irreversibly remove phosphorus. Physical factors also affect P removal. Specifically, specific surface area and particle shape affect filtration capacity, contact area between water and the surface area, and likelihood of clogging and blinding. A number of substrates have been shown to effectively remove P in case studies. Based upon these studies, promising substrates include WTRs, blast furnace slag, steel furnace slag, OPC, calcite, marble Utelite and other LWAs, zeolite and shale. However, other nonperformance factors such as environmental considerations, application logistics, costs, and potential for cementification narrow the list of possible media for application at Tahoe. Industrial byproducts such as slags risk possible leaching of heavy metals and this potential cannot be easily predicted. Fly ash and other fine particle substrates would be more difficult to apply because they would need to be blended, making them less desirable and more costly to apply than larger diameter media. High transportation costs rule out non-local products. Finally, amorphous calcium products will eventually cementify reducing their effectiveness in filtration systems. Based upon these considerations, bauxite, LWAs and expanded shales/clays, iron-rich sands, activated alumina, marble and dolomite, and natural and lanthanum activated diatomaceous earth are the products most likely to be tested for application at Tahoe. These materials are typically iron, calcium or aluminum based; many have a high specific surface area; and all have low transportation costs. (PDF contains 21 pages)

Reactions of platinum(II) complexes with dioxygen: progress toward alkane functionalization

Whereas stoichiometric activation of C-H bonds by complexes of transition metals is becoming increasingly common, selective functionalization of alkanes remains a formidable challenge in organometallic chemistry. The recent advances in catalytic alkane functionalization by transition-metal complexes are summarized in Chapter I.

The studies of the displacement of pentafluoropyridine in [(tmeda)Pt(CH_3)(NC_5F_5)][BAr^f_4] (1) with γ- tetrafluoropicoline, a very poor nucleophile, are reported in Chapter II. The ligand substitution occurs by a dissociative interchange mechanism. This result implies that dissociative loss of pentafluoropyridine is the rate-limiting step in the C-H activation reactions of 1.

Oxidation of dimethylplatinum(II) complexes (N-N)Pt(CH_3)_2 (N-N = tmeda(1), α-diimines) by dioxygen is described in Chapter III. Mechanistic studies suggest a two-step mechanism. First, a hydroperoxoplatinum(IV) complex is formed in a reaction between (N-N)Pt(CH_3)_2 and dioxygen. Next, the hydroperoxy complex reacts with a second equivalent of (N-N)Pt(CH_3)_2 to afford the final product, (N-N)Pt(OH)(OCH_3)(CH_3)_2. The hydroperoxy intermediate, (tmeda)Pt(OOH)(OCH_3)(CH_3)_2 (2), was isolated and characterized. The reactivity of 2 with several dime thylplatinum(II) complexes is reported.

The studies described in Chapter IV are directed toward the development of a platinum(II)-catalyzed oxidative alkane dehydrogenation. Stoichiometric conversion of alkanes (cyclohexane, ethane) to olefins (cyclohexene, ethylene) is achieved by C-H activation with [(N-N)Pt(CH_3)(CF_3CH_2OH)]BF_4 (1, N-N is N,N'-bis(3,5-di-t- butylphenyl)-1,4-diazabutadiene) which results in the formation of olefin hydride complexes. The first step in the C-H activation reaction is formation of a platinum(II) alkyl which undergoes β-hydrogen elimination to afford the olefin hydride complex. The cationic ethylplatinum(II) intermediate can be generated in situ by treating diethylplatinum(II) compounds with acids. Treatment of (phen)PtEt_2 with [H(OEt_2)_2]Bar^f_4 at low temperatures resulted in the formation of a mixture of [(phen)PtEt(OEt_2)]Bar^f_4 (8) and [(phen)Pt(C_2H_4)H] Bar^f_4 (7). The cationic olefin complexes are unreactive toward dioxygen or hydrogen peroxide. Since the success of the overall catalytic cycle depends on our ability to oxidize the olefin hydride complexes, a series of neutral olefin complexes of platinum(II) with monoanionic ligands (derivatives of pyrrole-2-carboxyaldehyde N-aryl imines) was prepared. Unfortunately, these are also stable to oxidation.

Light-matter Interactions in Semiconductors and Metals: From Nitride Optoelectronics to Quantum Plasmonics

This thesis puts forth a theory-directed approach coupled with spectroscopy aimed at the discovery and understanding of light-matter interactions in semiconductors and metals.

The first part of the thesis presents the discovery and development of Zn-IV nitride materials.The commercial prominence in the optoelectronics industry of tunable semiconductor alloy materials based on nitride semiconductor devices, specifically InGaN, motivates the search for earth-abundant alternatives for use in efficient, high-quality optoelectronic devices. II-IV-N2 compounds, which are closely related to the wurtzite-structured III-N semiconductors, have similar electronic and optical properties to InGaN namely direct band gaps, high quantum efficiencies and large optical absorption coefficients. The choice of different group II and group IV elements provides chemical diversity that can be exploited to tune the structural and electronic properties through the series of alloys. The first theoretical and experimental investigation of the ZnSnxGe1−xN2 series as a replacement for III-nitrides is discussed here.

The second half of the thesis shows ab−initio calculations for surface plasmons and plasmonic hot carrier dynamics. Surface plasmons, electromagnetic modes confined to the surface of a conductor-dielectric interface, have sparked renewed interest because of their quantum nature and their broad range of applications. The decay of surface plasmons is usually a detriment in the field of plasmonics, but the possibility to capture the energy normally lost to heat would open new opportunities in photon sensors, energy conversion devices and switching. A theoretical understanding of plasmon-driven hot carrier generation and relaxation dynamics in the ultrafast regime is presented here. Additionally calculations for plasmon-mediated upconversion as well as an energy-dependent transport model for these non-equilibrium carriers are shown.

Finally, this thesis gives an outlook on the potential of non-equilibrium phenomena in metals and semiconductors for future light-based technologies.

Late Transition Metals Supported by Aryl Ethers and Phenoxides Bearing Pendant Phosphines: Mechanistic Insights Relevant to Ether C-O Bond Cleavage

Terphenyl diphosphines bearing pendant ethers were prepared to provide mechanistic insight into the mechanism of activation of aryl C–O bonds with Group 9 and Group 10 transition metals. Chapters 2 and 3 of this dissertation describe the reactivity of compounds supported by the model phosphine and extension of this chemistry to heterogenous C–O bond activation.

Chapter 2 describes the synthesis and reactivity of aryl-methyl and aryl-aryl model systems. The metallation of these compounds with Ni, Pd, Pt, Co, Rh, and Ir is described. Intramolecular bond activation pathways are described. In the case of the aryl-methyl ether, aryl C–O bond activation was observed only for Ni, Rh, and Ir.

Chapter 3 outlines the reactivity of heterogenous Rh and Ir catalysts for aryl ether C–O bond cleavage. Using Rh/C and an organometallic Ir precursor, aryl ethers were treated with H2 and heat to afford products of hydrogenolysis and hydrogenation. Conditions were modified to optimize the yield of hydrogenolysis product. Hydrogenation could not be fully suppressed in these systems.

Appendix A describes initial investigations of bisphenoxyiminoquinoline dichromium compounds for selective C2H4 oligomerization to afford α-olefins. The synthesis of monometallic and bimetallic Cr complexes is described. These compounds are compared to literature examples and found to be less active and non-selective for production of α-olefins.

Appendix B describes the coordination chemistry of terphenyl diphosphines, terphenyl bisphosphinophenols, and biphenyl phosphinophenols proligands with molybdenum, cobalt, and nickel. Since their synthesis, terphenyl diphosphine molybdenum compounds have been reported to be good catalysts for the dehydrogenation of ammonia borane. Biphenyl phosphinophenols are demonstrated provide both phosphine and arene donors to transition metals while maintaining a sterically accessible coordination sphere. Such ligands may be promising in the context of the activation of other small molecules.

Appendix C contains relevant NMR spectra for the compounds presented in the preceding sections.

Helminth parasites of Caspian kilka (genus Clupeonella) as bioindicators of heavy metals

In the present study, intestinal helminth parasite fauna of 398 specimens of three species of kilkas, C. engrauliformis (N= 92), C. grimmi (N= 136) and C. cultriventris (N= 170) from Babolsar harbor were investigated. Five parasite species were found including: Corynosoma strumosum (Acanthocephala), Pronoprymna ventricosa (Trematoda), Contracaecum sp. (Nematoda), Raphidascaris sp. (Nematoda) and Anisakis sp. (Nematoda). The highest prevalence and abundance were observed in C. strumosum and P. ventricosa. The prevalence and abundance of C. strumosum in C. grimmi was significantly higher than C. engrauliformis. The prevalence and abundance of P. ventricosa in C. cultriventris was significantly higher than C. engrauliformis. The prevalence, mean intensity and mean abundance of the parasites were compared according to the sex, length group and season also effect of parasite on host growth parameters was considered. The diversity, equability, similarity, species richness, dominance Indices and specificity indices of helminth parasites of the three host species were studied. Also the lead and cadmium concentrations in the intestine, muscle, liver, kidney and gonad of kilkas and their parasites C. strumosum and P. ventricosa were measured and compared. The results revealed that lead and cadmium concentrations in C. strumosum and P. ventricosa were significantly higher than kidney, liver, intestine, gonad and muscle. The lead and cadmium concentrations of the parasites were compared according to the sex, parasitism and season.

Studies on state and structure of noble metals in electrocatalyst made by coprecipitation method

The electrocatalysts of Pt/C, PtRu/C and Ru/C were prepared by the impregnation method. The facet characterization, the dispersion and the particle size for the catalysts were determined by means of X-ray diffraction and transmission electron microscopy. X-ray photoelectron spectroscopy was also used to analyze the state and the valency of the noble metals. The results show that the particle size was in nanometer range and the binary metals have come into being an alloy. The platinum in the catalysts existed in zero valency. The valency of the ruthenium on the surface is different from that in the body, while the ruthenium on the surface existed in oxide-form. PtRu/C and Pt/C are of good activity to the electrooxidation of hydrogen except Ru/C. PtRu/C is more tolerant of CO than Pt/C, and CO is only adsorbed on Pt.

Synthesis, characterization, photophysics and electrophosphorescent applications of phosphorescent platinum cyclometalated complexes with 9-arylcarbazole moieties

A series of cyclometalating platinum(II) complexes with substituted 9-arylcarbazolyl chromophores have been synthesized and characterized. These complexes are thermally stable and most of them have been characterized by X-ray crystallography. The phosphorescence emissions of the complexes are dominated by (MLCT)-M-3 excited states. The excited state properties of these complexes can be modulated by varying the electronic characteristics of the cyclometalating ligands via substituent effects, thus allowing the emission to be tuned from bright green to yellow, orange and red light. The correlation between the functional properties of these metallophosphors and the results of density functional theory calculations was made. Because of the propensity of the electron-rich carbazolyl group to facilitate hole injection/transport, the presence of such moiety can increase the highest occupied molecular orbital levels and improve the charge balance in the resulting complexes relative to the parent platinum(II) phosphor with 2-phenylpyridine ligand.

Effect of alkyl group length on the conductivity in the 2,3,7,8,12,13,17,18-octakis(alkyl-thio)tetraazaporphyrins and redox properties of the metallooctakis(hexyl-thio)tetraazaporphyrins

A series of 2,3,7,8,12,13,17,18-octakis(alkyl-thio)tetraazaporphyrins (H(2)OATTAP) with different alkyl chain lengths have been synthesized. Cyclic voltammetry and differential pulse voltammetry have been used to investigate the effect of the controlled lengths of the eight peripheral thioether tails on the redox behavior of the molecules. The electrochemical reduction of octakis(hexyl-thio)tetraazaporphyrins, MOHTTAP (where M = Cu, Ni), was studied in 1,2-dichloroethane at a platinum electrode. The Cu derivative was oxidized in one single-electron-transfer step to yield a pi-cation radical and reduced in three single-electron-transfer steps to yield a pi-anion radical, dianion and trianion, respectively. For the Ni derivative, electron transfer reactions involving both the central metal atom and the macrocyclic ring were observed. Electron transfer pathways are proposed based upon voltammetric and in situ spectroelectrochemical results.

ELECTROOXIDATION OF A CHLORIDE COMPLEX OF PLATINUM(II) AT A GLASSY-CARBON ELECTRODE

The electro-oxidation of PtCl42- was studied on a glassy carbon (GC) electrode. A Pt(IV) complex was formed on the electrode surface through coordination to the oxygen atom of an oxide functional group on the electrode, which results in its deactivation. The ferri/ferrocyanide redox couple was used as a probe to examine the activity of the GC electrode. X-ray photoelectron spectroscopy was employed to characterize the platinum on the electrode surface, and showed that the oxidation state of the Pt element changes depending on the electrochemical treatment of GC electrode. The platinum complex on the surface of the GC electrode can be transformed to Pt-0 by cycling the electrode between -0.25 and +1.65 V/SCE in 0.1 M H2SO4 solution. The above procedure can be used to disperse platinum ultramicroparticles on the surface of a GC electrode.