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.

Talbot-SNOM method for non-contact evaluation of high-density gratings

A Talbot scanning near-field optical microscopy (SNOM) method for non-contact evaluating of high-density gratings was described. This method combines the Talbot self-imaging effect of the gratings and the conventional SNOM technique without damage. The significant advantages of this method are its simple structure, reliable and fast measurement for the surface quality of the tested gratings. Experimental results of three different kinds of gratings were demonstrated to indicate that this method is effective for evaluation surface quality of high-density gratings. (c) 2004 Elsevier B.V. All rights reserved.

Effects of density differences on lateral mixing in open-channel flows

This study investigates lateral mixing of tracer fluids in turbulent open-channel flows when the tracer and ambient fluids have different densities. Longitudinal dispersion in flows with longitudinal density gradients is investigated also.

Lateral mixing was studied in a laboratory flume by introducing fluid tracers at the ambient flow velocity continuously and uniformly across a fraction of the flume width and over the entire depth of the ambient flow. Fluid samples were taken to obtain concentration distributions in cross-sections at various distances, x, downstream from the tracer source. The data were used to calculate variances of the lateral distributions of the depth-averaged concentration. When there was a difference in density between the tracer and the ambient fluids, lateral mixing close to the source was enhanced by density-induced secondary flows; however, far downstream where the density gradients were small, lateral mixing rates were independent of the initial density difference. A dimensional analysis of the problem and the data show that the normalized variance is a function of only three dimensionless numbers, which represent: (1) the x-coordinate, (2) the source width, and (3) the buoyancy flux from the source.

A simplified set of equations of motion for a fluid with a horizontal density gradient was integrated to give an expression for the density-induced velocity distribution. The dispersion coefficient due to this velocity distribution was also obtained. Using this dispersion coefficient in an analysis for predicting lateral mixing rates in the experiments of this investigation gave only qualitative agreement with the data. However, predicted longitudinal salinity distributions in an idealized laboratory estuary agree well with published data.

Deep-etched high-density fused-silica transmission gratings with high efficiency at a wavelength of 1550 nm

We describe the design, fabrication, and excellent performance of an optimized deep-etched high-density fused-silica transmission grating for use in dense wavelength division multiplexing (DWDM) systems. The fabricated optimized transmission grating exhibits an efficiency of 87.1% at a wavelength of 1550 nm. Inductively coupled plasma-etching technology was used to fabricate the grating. The deep-etched high-density fused-silica transmission grating is suitable for use in a DWDM system because of its high efficiency, low polarization-dependent loss, parallel demultiplexing, and stable optical performance. The fabricated deep-etched high-density fused-silica transmission gratings should play an important role in DWDM systems. (c) 2006 Optical Society of America.

Spectral density of first order Piecewise linear systems excited by white noise

The Fokker-Planck (FP) equation is used to develop a general method for finding the spectral density for a class of randomly excited first order systems. This class consists of systems satisfying stochastic differential equations of form ẋ + f(x) = m/Ʃ/j = 1 h_j(x)n_j(t) where f and the h_j are piecewise linear functions (not necessarily continuous), and the n_j are stationary Gaussian white noise. For such systems, it is shown how the Laplace-transformed FP equation can be solved for the transformed transition probability density. By manipulation of the FP equation and its adjoint, a formula is derived for the transformed autocorrelation function in terms of the transformed transition density. From this, the spectral density is readily obtained. The method generalizes that of Caughey and Dienes, J. Appl. Phys., 32.11.

This method is applied to 4 subclasses: (1) m = 1, h₁ = const. (forcing function excitation); (2) m = 1, h₁ = f (parametric excitation); (3) m = 2, h₁ = const., h₂ = f, n₁ and n₂ correlated; (4) the same, uncorrelated. Many special cases, especially in subclass (1), are worked through to obtain explicit formulas for the spectral density, most of which have not been obtained before. Some results are graphed.

Dealing with parametrically excited first order systems leads to two complications. There is some controversy concerning the form of the FP equation involved (see Gray and Caughey, J. Math. Phys., 44.3); and the conditions which apply at irregular points, where the second order coefficient of the FP equation vanishes, are not obvious but require use of the mathematical theory of diffusion processes developed by Feller and others. These points are discussed in the first chapter, relevant results from various sources being summarized and applied. Also discussed is the steady-state density (the limit of the transition density as t → ∞).

FDTD analysis of Talbot effect of a high density grating

Talbot effect of a grating with different flaws is analyzed with the finite-difference time-domain (FDTD) method. The FDTD method can show the exact near-field distribution of different flaws in a high-density grating, which is impossible to obtain with the conventional Fourier transform method. The numerical results indicate that if a grating is perfect, its Talbot imaging should also be perfect; if the grating is distorted, its Talbot imaging would also be distorted. Furthermore, we can evaluate high density gratings by detecting the near-field distribution.

Double-line-density gratings structure for compression and generation of double femtosecond laser pulses

Grating pairs are widely used for pulse compression and stretching. Normally, the two gratings are identical. We propose a very simple structure with double-line-density reflective gratings for pulse compression and generation of double pulses, which has the advantages of no material dispersion, compact in volume, simple in structure, etc. The use of reflective Dammann gratings fully demonstrated the principle of this structure. The output pulses are well verified by a standard frequency-resolved optical gating apparatus. This structure will be highly interesting in ultrashort pulse compression and other more practical applications of femtosecond laser pulses. (c) 2007 Optical Society of America.

Phase interpretation for polarization-dependent near-field images of high-density gratings

It has been described that the near-field images of a high-density grating at the half self-imaging distance could be different for TE and TM polarization states. We propose that the phases of the diffraction orders play an important role in such polarization dependence. The view is verified through the coincidence of the numerical result of finite-difference time-domain method and the reconstructed results from the rigorous coupled-wave analysis. Field distributions of TE and TM polarizations are given numerically for a grating with period d = 2.3 lambda, which are verified through experiments with the scanning near-field optical microscopy technique. The concept of phase interpretation not only explains the polarization dependence at the half self-imaging distance of gratings with a physical view, but also, it could be widely used to describe the near-field diffraction of a variety of periodic diffractive optical elements whose feature size comparable to the wavelength. (C) 2008 Elsevier B.V. All rights reserved.

I. The structure and properties of closed circular duplex DNA. II. Chemically interacting systems at equilibrium in a buoyant density gradient

I. The binding of the intercalating dye ethidium bromide to closed circular SV 40 DNA causes an unwinding of the duplex structure and a simultaneous and quantitatively equivalent unwinding of the superhelices. The buoyant densities and sedimentation velocities of both intact (I) and singly nicked (II) SV 40 DNAs were measured as a function of free dye concentration. The buoyant density data were used to determine the binding isotherms over a dye concentration range extending from 0 to 600 µg/m1 in 5.8 M CsCl. At high dye concentrations all of the binding sites in II, but not in I, are saturated. At free dye concentrations less than 5.4 µg/ml, I has a greater affinity for dye than II. At a critical amount of dye bound I and II have equal affinities, and at higher dye concentration I has a lower affinity than II. The number of superhelical turns, τ, present in I is calculated at each dye concentration using Fuller and Waring's (1964) estimate of the angle of duplex unwinding per intercalation. The results reveal that SV 40 DNA I contains about -13 superhelical turns in concentrated salt solutions.

The free energy of superhelix formation is calculated as a function of τ from a consideration of the effect of the superhelical turns upon the binding isotherm of ethidium bromide to SV 40 DNA I. The value of the free energy is about 100 kcal/mole DNA in the native molecule. The free energy estimates are used to calculate the pitch and radius of the superhelix as a function of the number of superhelical turns. The pitch and radius of the native I superhelix are 430 Å and 135 Å, respectively.

A buoyant density method for the isolation and detection of closed circular DNA is described. The method is based upon the reduced binding of the intercalating dye, ethidium bromide, by closed circular DNA. In an application of this method it is found that HeLa cells contain in addition to closed circular mitochondrial DNA of mean length 4.81 microns, a heterogeneous group of smaller DNA molecules which vary in size from 0.2 to 3.5 microns and a paucidisperse group of multiples of the mitochondrial length.

II. The general theory is presented for the sedimentation equilibrium of a macromolecule in a concentrated binary solvent in the presence of an additional reacting small molecule. Equations are derived for the calculation of the buoyant density of the complex and for the determination of the binding isotherm of the reagent to the macrospecies. The standard buoyant density, a thermodynamic function, is defined and the density gradients which characterize the four component system are derived. The theory is applied to the specific cases of the binding of ethidium bromide to SV 40 DNA and of the binding of mercury and silver to DNA.

Talbot effect of a high-density grating under femtosecond laser illumination

The Talbot effect of a high-density grating under femtosecond laser illumination is analyzed with rigorous electromagnetic theory which is based on the Fourier decomposition and the rigorous coupled-wave analysis (RCWA). Numerical simulations show that the contrast of the Talbot images steadily decreases as the transmitted femtosecond laser pulses propagate forward and with wider spectrum width of the femtosecond laser pulses. The Talbot images of high-density gratings have much higher sensitivity of the spectrum widths of the incident laser pulses than those of the traditional low-density gratings. In experiments, the spectrums and the pulse widths of the incident pulses are measured with a frequency-resolved optical grating (FROG) apparatus. The Talbot images are detected by using a Talbot scanning near-field optical microscopy (Talbot-SNOM) technique, which are in coincidence with the numerical simulations. This effect should be useful for developing new femtosecond laser techniques and devices. (C) 2008 Elsevier B.V. All rights reserved.

DEVELOPMENT AND APPLICATIONS OF TIME-DEPENDENT DENSITY MATRIX FUNCTIONAL THEORY

En esta tesis estudiamos las teorías sobre la Matriz Densidad Reducida (MDR) como un marco prometedor. Nos enfocamos sobre esta teorías desde dos aspectos: Primero, usamos algunos modelos sencillos hechos con dos partículas las cuales estan armónicamente confinadas como una base para ilustrar la utilidad de la matriz densidad. Para tales sistemas, usamos la MDR de un cuerpo para calcular algunas cantidades de interés tales como densidad de momentum. Posteriormente obtenemos los orbitales naturales y su número de ocupación para algunos de los modelos, y en uno de los casos expresamos la MDR de dos cuerpos de manera exacta en términos de la MDR de un cuerpo. También usamos el teorema diferencial del virial para establecer una descripción unificada de la familia entera de estos sistemas modelo en términos de la densidad. En la seguna parte cambiamos a casos fuera del equilibrio y analizamos la así llamada jerarquía BBGKY de ecuaciones para describir la evolución temporal de un sistema de muchos cuerpos en términos de sus MDRs (a todos los órdenes). Proveemos un exhaustivo estudio de los desafíos y problemas abiertos ligados a la truncación de tales jerarquías de ecuaciones para hacerlas aplicables. Restringimos nuestro análisis a la evolución acoplada de la MDR de uno y dos cuerpos, donde los efectos de correlación de alto orden estan embebidos dentro de la aproximación usada para cerrar las ecuaciones. Probamos que dentro de esta aproximación, el número de electrones y la energía total se conservan, sin importar la aproximación usada. Luego, demostramos que aplicando los esquemas de truncación de estado base para llevar los electrones a comportamientos indeseables y no físicos, tales como la violación e incluso la divergencia en la densidad electrónica local, tanto en regímenes correlacionados débiles y fuertes.

Split-aperture laser pulse compressor design tolerant to alignment and line-density differences

We introduce a four-pass laser pulse compressor design based on two grating apertures with two gratings per aperture that is tolerant to some alignment errors and, importantly, to grating-to-grating period variations. Each half-beam samples each grating in a diamond-shaped compressor that is symmetric about a central bisecting plane. For any given grating, the two half-beams impinge on opposite sides of its surface normal. It is shown that the two split beams have no pointing difference from paired gratings with different periods. Furthermore, no phase shift between half-beams is incurred as long as the planes containing a grating line and the surface normal for each grating of the pair are parallel. For grating pairs satisfying this condition, gratings surfaces need not be on the same plane, as changes in the gap between the two can compensate to bring the beams back in phase. © 2008 Optical Society of America.