Synthesis, Oxidation and Photophysics of Perfluoroborated Tetrakis(pyrophosphito)diplatinate (II) and Density Functional Theory (DFT) Study of Electrochemical CO2 Reduction by Mn Catalysts

In the first part of this thesis (Chapters I and II), the synthesis, characterization, reactivity and photophysics of per(difluoroborated) tetrakis(pyrophosphito)diplatinate(II) (Pt(POPBF₂)) are discussed. Pt(POP-BF₂) was obtained by reaction of [Pt₂(POP)₄]^4- with neat boron trifluoride diethyl etherate (BF₃·Et₂O). While Pt(POP-BF₂) and [Pt₂(POP)₄]^4- have similar structures and absorption spectra, they differ in significant ways. Firstly, as discussed in Chapter I, the former is less susceptible to oxidation, as evidenced by the reversibility of its oxidation by I2. Secondly, while the first excited triplet states (T₁) of both Pt(POP-BF₂) and [Pt₂(POP)₄]^4- exhibit long lifetimes (ca. 0.01 ms at room temperature) and substantial zero-field splitting (40 cm^-1), Pt(POP-BF₂) also has a remarkably long-lived (1.6 ns at room temperature) singlet excited state (S₁), indicating slow intersystem crossing (ISC). Fluorescence lifetime and quantum yield (QY) of Pt(POP-BF₂) were measured over a range of temperatures, providing insight into the slow ISC process. The remarkable spectroscopic and photophysical properties of Pt(POP-BF₂), both in solution and as a microcrystalline powder, form the theme of Chapter II.

In the second part of the thesis (Chapters III and IV), the electrochemical reduction of CO₂ to CO by [(L)Mn(CO)₃]^- catalysts is investigated using density functional theory (DFT). As discussed in Chapter III, the turnover frequency (TOF)-limiting step is the dehydroxylation of [(bpy)Mn(CO)₃(CO₂H)]^0/- (bpy = bipyridine) by trifluoroethanol (TFEH) to form [(bpy)Mn(CO)₄]^+/0. Because the dehydroxylation of [(bpy)Mn(CO)₃(CO₂H)]^- is faster, maximum TOF (TOF_max) is achieved at potentials sufficient to completely reduce [(bpy)Mn(CO)₃(CO₂H)]⁰ to [(bpy)Mn(CO)₃(CO₂H)]^-. Substitution of bipyridine with bipyrimidine reduces the overpotential needed, but at the expense of TOF_max. In Chapter IV, the decoration of the bipyrimidine ligand with a pendant alcohol is discussed as a strategy to increase CO₂ reduction activity. Our calculations predict that the pendant alcohol acts in concert with an external TFEH molecule, the latter acidifying the former, resulting in a ~ 80,000-fold improvement in the rate of TOF-limiting dehydroxylation of [(L)Mn(CO)₃(CO₂H)]^-.

An interesting strategy for the co-upgrading of light olefins and alkanes into heavier alkanes is the subject of Appendix B. The proposed scheme involves dimerization of the light olefin, operating in tandem with transfer hydrogenation between the olefin dimer and the light alkane. The work presented therein involved a Ta olefin dimerization catalyst and a silica-supported Ir transfer hydrogenation catalyst. Olefin dimer was formed under reaction conditions; however, this did not undergo transfer hydrogenation with the light alkane. A significant challenge is that the Ta catalyst selectively produces highly branched dimers, which are unable to undergo transfer hydrogenation.

Measurement of the Polarization of the Cosmic Microwave Background with the BICEP2 and Keck Array Telescopes

Precision polarimetry of the cosmic microwave background (CMB) has become a mainstay of observational cosmology. The ΛCDM model predicts a polarization of the CMB at the level of a few μK, with a characteristic E-mode pattern. On small angular scales, a B-mode pattern arises from the gravitational lensing of E-mode power by the large scale structure of the universe. Inflationary gravitational waves (IGW) may be a source of B-mode power on large angular scales, and their relative contribution to primordial fluctuations is parameterized by a tensor-to-scalar ratio r. BICEP2 and Keck Array are a pair of CMB polarimeters at the South Pole designed and built for optimal sensitivity to the primordial B-mode peak around multipole l ~ 100. The BICEP2/Keck Array program intends to achieve a sensitivity to r ≥ 0.02. Auxiliary science goals include the study of gravitational lensing of E-mode into B-mode signal at medium angular scales and a high precision survey of Galactic polarization. These goals require low noise and tight control of systematics. We describe the design and calibration of the instrument. We also describe the analysis of the first three years of science data. BICEP2 observes a significant B-mode signal at 150 GHz in excess of the level predicted by the lensed-ΛCDM model, and Keck Array confirms the excess signal at > 5σ. We combine the maps from the two experiments to produce 150 GHz Q and U maps which have a depth of 57 nK deg (3.4 μK arcmin) over an effective area of 400 deg² for an equivalent survey weight of 248000 μK². We also show preliminary Keck Array 95 GHz maps. A joint analysis with the Planck collaboration reveals that much of BICEP2/Keck Array's observed 150 GHz signal at low l is more likely a Galactic dust foreground than a measurement of r. Marginalizing over dust and r, lensing B-modes are detected at 7.0σ significance.

Influence of birefringence dispersion on distributed measurement of polarization coupling in birefringent fibers

A white light interferometer is developed to measure the distributed polarization coupling in high-birefringence polarization-maintaining fibers (PMFs). Usually the birefringence dispersion between two orthogonal eigenmodes of PMFs is neglected in such systems. Theoretical analysis and experimental results show that the birefringence dispersion becomes a nonnegligible factor in a long-fiber test. Significant broadening of interferograms and loss of longitudinal coherence are observed. The spatial resolution and measurement sensitivity of the system decrease correspondingly. Optimum spectrum width selection is presented for better spatial resolution and measurement range. c 2007 Society of Photo-Optical Instrumentation Engineers.

Avaliação da corrosão microbiológica do aço carbono 1020 em água do mar sintética na presença de bactérias redutoras de sulfato

Bactérias redutoras de sulfato (BRS) possuem um papel importante na corrosão de ligas metálicas expostas em hábitats marinhos, óleos e solos úmidos. A redução do sulfato por estas bactérias resulta na produção de H2S, podendo influenciar os processos anódico e catódico na corrosão de materiais. Neste trabalho, o comportamento da corrosão microbiológica no aço carbono AISI 1020 foi avaliada em meio Postgate C, na presença e na ausência de BRS, as quais foram isoladas da camada de ferrugem presente numa tubulação submersa da Baía de Guanabara RJ. A taxa de corrosão e o comportamento eletroquímico do aço nas duas condições foram investigados através dos métodos de perda de massa e de polarização potenciodinâmica. A formação do biofilme e dos produtos de corrosão na superfície do aço foram observados por microscopia eletrônica de varredura (MEV) e por espectroscopia de energia dispersiva (EDS). Em complementação, foi realizada a quantificação das BRS (planctônicas e sésseis) pelo método do número mais provável (NMP). A presença de BRS no meio ocasionou o deslocamento do potencial de corrosão para valores mais negativos em todos os tempos de ensaio estudados, indicando um aumento no processo corrosivo. Nos ensaios de perda de massa, a taxa de corrosão do aço carbono foi maior na ausência de BRS, provavelmente devido à formação de um biofilme na superfície do metal nos ensaios com inóculo, e a uma menor tendência de haver corrosão generalizada neste tipo de meio. As micrografias de MEV revelaram a presença de agregado celular na superfície do aço carbono durante o experimento, e a presença de pites profundos após remoção do biofilme, mostrando prevalência deste tipo de corrosão. Com 35 dias de ensaio, a densidade de corrente de corrosão aumentou na presença de BRS

The polarization of the recoil proton in ETA photoproduction

We measured the recoil proton polarization in the process γp → pη at the 1.5 GeV Caltech electron synchrotron, at photon energies from 0.8 to 1.1 GeV, and at center-of-mass production angles around 90°. A counter-spark chamber array was used to determine the kinematics of all particles in the final state of the partial mode γp → pη (η → 2γ). The protons' polarization was determined by measuring an asymmetry in scattering off carbon. Analysis of 280,000 pictures yielded 2400 useful scatters with a background which was 30% of the foreground. The polarization results show a sizeable opposite parity interference at 830 MeV, 950 MeV, and 1100 MeV.

Analysis of a second-order polarization-independent filter made of a single ring resonator and a Sagnac interferometer

A novel second-order polarization-independent filter made of a single ring resonator and a Sagnac interferometer (SRRSI) is proposed, and its filtering characteristics are investigated. By using birefringence in waveguide, a single ring resonator can be used to synthesize a filter with second-order response. Analytical formulas are derived for characteristics of the SRRSI varied with waveguide parameters.. such as the coupling coefficient; and the critical condition of a second-order Butterworth filter is given. The influence of loss in the ring resonator is also analyzed. (c) 2005 Elsevier B.V. All rights reserved.

Polarization analysis and experimental implementation of PLZT electro-optical switch using fiber Sagnac interferometers

The polarization characteristics of electro-optical (EO) switches using fiber Sagnac interferometer (FSI) structures are theoretically investigated. Analytical solutions of output fields are presented when the twists and birefringence in a Sagnac loop are considered. Numerical calculations show that the twists of fiber, the orientation of the inserted phase retarder, and the splitting ratio of the coupler will influence both the output intensity and the output polarization properties of the proposed switch. A polarization-independent EO switch based on a Sagnac interferometer and a PUT bar was experimentally implemented, which showed good coincidence with the analytical results. The experiment showed a switch with 22 dB extinction ratio and less than 31.1 ns switching time. (c) 2006 Optical Society of America.