10 resultados para GAMMA-ALUMINA SURFACES
em CaltechTHESIS
Resumo:
We perform a measurement of direct CP violation in b to s+gamma Acp, and the measurement of a difference between Acp for neutral B and charged B mesons, Delta A_{X_s\gamma}, using 429 inverse femtobarn of data recorded at the Upsilon(4S) resonance with the BABAR detector. B mesons are reconstructed from 16 exclusive final states. Particle identification is done using an algorithm based on Error Correcting Output Code with an exhaustive matrix. Background rejection and best candidate selection are done using two decision tree-based classifiers. We found $\acp = 1.73%+-1.93%+-1.02% and Delta A_X_sgamma = 4.97%+-3.90%+-1.45% where the uncertainties are statistical and systematic respectively. Based on the measured value of Delta A_X_sgamma, we determine a 90% confidence interval for Im C_8g/C_7gamma, where C_7gamma and C_8g are Wilson coefficients for New Physics amplitudes, at -1.64 < Im C_8g/C_7gamma < 6.52.
Resumo:
Blazars are active galaxies with a jet closely oriented to our line of sight. They are powerful, variable emitters from radio to gamma-ray wavelengths. Although the general picture of synchrotron emission at low energies and inverse Compton at high energies is well established, important aspects of blazars are not well understood. In particular, the location of the gamma-ray emission region is not clearly established, with some theories favoring a location close to the central engine, while others place it at parsec scales in the radio jet.
We developed a program to locate the gamma-ray emission site in blazars, through the study of correlated variations between their gamma-ray and radio-wave emission. Correlated variations are expected when there is a relation between emission processes at both bands, while delays tell us about the relative location of their energy generation zones. Monitoring at 15 GHz using the Owens Valley Radio Observatory 40 meter telescope started in mid-2007. The program monitors 1593 blazars twice per week, including all blazars detected by the Fermi Gamma-ray Space Telescope (Fermi) north of -20 degrees declination. This program complements the continuous monitoring of gamma-rays by Fermi.
Three year long gamma-ray light curves for bright Fermi blazars are cross-correlated with four years of radio monitoring. The significance of cross-correlation peaks is investigated using simulations that account for the uneven sampling and noise properties of the light curves, which are modeled as red-noise processes with a simple power-law power spectral density. We found that out of 86 sources with high quality data, only three show significant correlations (AO 0235+164, B2 2308+34 and PKS 1502+106). Additionally, we find a significant correlation for Mrk 421 when including the strong gamma-ray/radio flare of late 2012. In all four cases radio variations lag gamma-ray variations, suggesting that the gamma-ray emission originates upstream of the radio emission. For PKS 1502+106 we locate the gamma-ray emission site parsecs away from the central engine, thus disfavoring the model of Blandford and Levinson (1995), while other cases are inconclusive. These findings show that continuous monitoring over long time periods is required to understand the cross-correlation between gamma-ray and radio-wave variability in most blazars.
Resumo:
In this thesis, we provide a statistical theory for the vibrational pooling and fluorescence time dependence observed in infrared laser excitation of CO on an NaCl surface. The pooling is seen in experiment and in computer simulations. In the theory, we assume a rapid equilibration of the quanta in the substrate and minimize the free energy subject to the constraint at any time t of a fixed number of vibrational quanta N(t). At low incident intensity, the distribution is limited to one- quantum exchanges with the solid and so the Debye frequency of the solid plays a key role in limiting the range of this one-quantum domain. The resulting inverted vibrational equilibrium population depends only on fundamental parameters of the oscillator (ωe and ωeχe) and the surface (ωD and T). Possible applications and relation to the Treanor gas phase treatment are discussed. Unlike the solid phase system, the gas phase system has no Debye-constraining maximum. We discuss the possible distributions for arbitrary N-conserving diatom-surface pairs, and include application to H:Si(111) as an example.
Computations are presented to describe and analyze the high levels of infrared laser-induced vibrational excitation of a monolayer of absorbed 13CO on a NaCl(100) surface. The calculations confirm that, for situations where the Debye frequency limited n domain restriction approximately holds, the vibrational state population deviates from a Boltzmann population linearly in n. Nonetheless, the full kinetic calculation is necessary to capture the result in detail.
We discuss the one-to-one relationship between N and γ and the examine the state space of the new distribution function for varied γ. We derive the Free Energy, F = NγkT − kTln(∑Pn), and effective chemical potential, μn ≈ γkT, for the vibrational pool. We also find the anti correlation of neighbor vibrations leads to an emergent correlation that appears to extend further than nearest neighbor.
Resumo:
The work described in this dissertation includes fundamental investigations into three surface processes, namely inorganic film growth, water-induced oxidation, and organic functionalization/passivation, on the GaP and GaAs(001) surfaces. The techniques used to carry out this work include scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations. Atomic structure, electronic structure, reaction mechanisms, and energetics related to these surface processes are discussed at atomic or molecular levels.
First, we investigate epitaxial Zn3P2 films grown on the Ga-rich GaAs(001)(6×6) surface. The film growth mechanism, electronic properties, and atomic structure of the Zn3P2/GaAs(001) system are discussed based on experimental and theoretical observations. We discover that a P-rich amorphous layer covers the crystalline Zn3P2 film during and after growth. We also propose more accurate picture of the GaP interfacial layer between Zn3P2 and GaAs, based on the atomic structure, chemical bonding, band diagram, and P-replacement energetics, than was previously anticipated.
Second, DFT calculations are carried out in order to understand water-induced oxidation mechanisms on the Ga-rich GaP(001)(2×4) surface. Structural and energetic information of every step in the gaseous water-induced GaP oxidation reactions are elucidated at the atomic level in great detail. We explore all reasonable ground states involved in most of the possible adsorption and decomposition pathways. We also investigate structures and energies of the transition states in the first hydrogen dissociation of a water molecule on the (2×4) surface.
Finally, adsorption structures and thermal decomposition reactions of 1-propanethiol on the Ga-rich GaP(001)(2×4) surface are investigated using high resolution STM, XPS, and DFT simulations. We elucidate adsorption locations and their associated atomic structures of a single 1-propanethiol molecule on the (2×4) surface as a function of annealing temperature. DFT calculations are carried out to optimize ground state structures and search transition states. XPS is used to investigate variations of the chemical bonding nature and coverage of the adsorbate species.
Resumo:
The functionalization of silicon surfaces with molecular catalysts for proton reduction is an important part of the development of a solar-powered, water-splitting device for solar fuel formation. The covalent attachment of these catalysts to silicon without damaging the underlying electronic properties of silicon that make it a good photocathode has proven difficult. We report the formation of mixed monolayer-functionalized surfaces that incor- porate both methyl and vinylferrocenyl or vinylbipyridyl (vbpy) moieties. The silicon was functionalized using reaction conditions analogous to those of hydrosilylation, but instead of a H-terminated Si surface, a chlorine-terminated Si precursor surface was used to produce the linked vinyl-modified functional group. The functionalized surfaces were characterized by time-resolved photoconductivity decay, X-ray photoelectron spectroscopy (XPS), electro- chemical, and photoelectrochemical measurements. The functionalized Si surfaces were well passivated, exhibited high surface coverage and few remaining reactive Si atop sites, had a very low surface recombination velocity, and displayed little initial surface oxidation. The surfaces were stable toward atmospheric and electrochemical oxidation. The surface coverage of ferrocene or bipyridine was controllably varied from 0 up to 30% of a monolayer without loss of the underlying electronic properties of the silicon. Interfacial charge transfer to the attached ferrocene group was relatively rapid, and a photovoltage of 0.4 V was generated upon illumination of functionalized n-type silicon surfaces in CH3CN. The immobilized bipyridine ligands bound transition metal ions, and thus enabled the assembly of metal complexes on the silicon surface. XPS studies demonstrated that [Cp∗Rh(vbpy)Cl]Cl, [Cp∗Ir(vbpy)Cl]Cl, and Ru(acac)2vbpy were assembled on the surface. For the surface prepared with iridium, x-ray absorption spectroscopy at the Ir LIII edge showed an edge energy and post-edge features virtually identical to a powder sample of [Cp∗Ir(bipy)Cl]Cl (bipy is 2,2 ́-bipyridyl). Electrochemical studies on these surfaces confirmed that the assembled complexes were electrochemically active.
Resumo:
The coarsening kinetics of Ni3 Si(γ') precipitate in a binary Ni-Si alloy containing 6.5 wt. % silicon was studied by magnetic techniques and transmission electronmicroscopy. A calibration curve was established to determine the concentration of silicon in the matrix. The variation of the Si content of the Ni-rich matrix as a function of time follows Lifshitz and Wagner theory for diffusion controlled coarsening phenomena. The estimated values of equilibrium solubility of silicon in the matrix represent the true coherent equilibrium solubilities.
The experimental particle-size distributions and average particle size were determined from dark field electron micrographs. The average particle size varies linearly with t-1/3 as suggested by Lifshitz and Wagner. The experimental distributions of particle sizes differ slightly from the theoretical curve at the early stages of aging, but the agreement is satisfactory at the later stages. The values of diffusion coefficient of silicon, interfacial free energy and activation energy were calculated from the results of coarsening kinetics. The experimental value of effective diffusion coefficient is in satisfactory agreement with the value predicted by the application of irreversible the rmodynamics to the process of volume constrained growth of coherent precipitate during coarsening. The coherent γ' particles in Ni-Sialloy unlike those in Ni-Al and Ni-Ti seem to lose coherency at high temperature. A mechanism for the formation of semi-coherent precipitate is suggested.
Resumo:
The initial probabilities of activated, dissociative chemisorption of methane and ethane on Pt(110)-(1 x 2) have been measured. The surface temperature was varied from 450 to 900 K with the reactant gas temperature constant at 300 K. Under these conditions, we probe the kinetics of dissociation via trapping-mediated (as opposed to 'direct') mechanism. It was found that the probabilities of dissociation of both methane and ethane were strong functions of the surface temperature with an apparent activation energies of 14.4 kcal/mol for methane and 2.8 kcal/mol for ethane, which implys that the methane and ethane molecules have fully accommodated to the surface temperature. Kinetic isotope effects were observed for both reactions, indicating that the C-H bond cleavage was involved in the rate-limiting step. A mechanistic model based on the trapping-mediated mechanism is used to explain the observed kinetic behavior. The activation energies for C-H bond dissociation of the thermally accommodated methane and ethane on the surface extracted from the model are 18.4 and 10.3 kcal/mol, respectively.
The studies of the catalytic decomposition of formic acid on the Ru(001) surface with thermal desorption mass spectrometry following the adsorption of DCOOH and HCOOH on the surface at 130 and 310 K are described. Formic acid (DCOOH) chemisorbs dissociatively on the surface via both the cleavage of its O-H bond to form a formate and a hydrogen adatom, and the cleavage of its C-O bond to form a carbon monoxide, a deuterium adatom and an hydroxyl (OH). The former is the predominant reaction. The rate of desorption of carbon dioxide is a direct measure of the kinetics of decomposition of the surface formate. It is characterized by a kinetic isotope effect, an increasingly narrow FWHM, and an upward shift in peak temperature with Ɵ_T, the coverage of the dissociatively adsorbed formic acid. The FWHM and the peak temperature change from 18 K and 326 K at Ɵ_T = 0.04 to 8 K and 395 K at Ɵ_T = 0.89. The increase in the apparent activation energy of the C-D bond cleavage is largely a result of self-poisoning by the formate, the presence of which on the surface alters the electronic properties of the surface such that the activation energy of the decomposition of formate is increased. The variation of the activation energy for carbon dioxide formation with Ɵ_T accounts for the observed sharp carbon dioxide peak. The coverage of surface formate can be adjusted over a relatively wide range so that the activation energy for C-D bond cleavage in the case of DCOOH can be adjusted to be below, approximately equal to, or well above the activation energy for the recombinative desorption of the deuterium adatoms. Accordingly, the desorption of deuterium was observed to be governed completely by the desorption kinetics of the deuterium adatoms at low Ɵ_T, jointly by the kinetics of deuterium desorption and C-D bond cleavage at intermediate Ɵ_T, and solely by the kinetics of C-D bond cleavage at high Ɵ_T. The overall branching ratio of the formate to carbon dioxide and carbon monoxide is approximately unity, regardless the initial coverage Ɵ_T, even though the activation energy for the production of carbon dioxide varies with Ɵ_T. The desorption of water, which implies C-O bond cleavage of the formate, appears at approximately the same temperature as that of carbon dioxide. These observations suggest that the cleavage of the C-D bond and that of the C-O bond of two surface formates are coupled, possibly via the formation of a short-lived surface complex that is the precursor to to the decomposition.
The measurement of steady-state rate is demonstrated here to be valuable in determining kinetics associated with short-lived, molecularly adsorbed precursor to further reactions on the surface, by determining the kinetic parameters of the molecular precursor of formaldehyde to its dissociation on the Pt(110)-(1 x 2) surface.
Overlayers of nitrogen adatoms on Ru(001) have been characterized both by thermal desorption mass spectrometry and low-energy electron diffraction, as well as chemically via the postadsorption and desorption of ammonia and carbon monoxide.
The nitrogen-adatom overlayer was prepared by decomposing ammonia thermally on the surface at a pressure of 2.8 x 10^(-6) Torr and a temperature of 480 K. The saturated overlayer prepared under these conditions has associated with it a (√247/10 x √247/10)R22.7° LEED pattern, has two peaks in its thermal desorption spectrum, and has a fractional surface coverage of 0.40. Annealing the overlayer to approximately 535 K results in a rather sharp (√3 x √3)R30° LEED pattern with an associated fractional surface coverage of one-third. Annealing the overlayer further to 620 K results in the disappearance of the low-temperature thermal desorption peak and the appearance of a rather fuzzy p(2x2) LEED pattern with an associated fractional surface coverage of approximately one-fourth. In the low coverage limit, the presence of the (√3 x √3)R30° N overlayer alters the surface in such a way that the binding energy of ammonia is increased by 20% relative to the clean surface, whereas that of carbon monoxide is reduced by 15%.
A general methodology for the indirect relative determination of the absolute fractional surface coverages has been developed and was utilized to determine the saturation fractional coverage of hydrogen on Ru(001). Formaldehyde was employed as a bridge to lead us from the known reference point of the saturation fractional coverage of carbon monoxide to unknown reference point of the fractional coverage of hydrogen on Ru(001), which is then used to determine accurately the saturation fractional coverage of hydrogen. We find that ƟSAT/H = 1.02 (±0.05), i.e., the surface stoichiometry is Ru : H = 1 : 1. The relative nature of the method, which cancels systematic errors, together with the utilization of a glass envelope around the mass spectrometer, which reduces spurious contributions in the thermal desorption spectra, results in high accuracy in the determination of absolute fractional coverages.
Resumo:
We develop a logarithmic potential theory on Riemann surfaces which generalizes logarithmic potential theory on the complex plane. We show the existence of an equilibrium measure and examine its structure. This leads to a formula for the structure of the equilibrium measure which is new even in the plane. We then use our results to study quadrature domains, Laplacian growth, and Coulomb gas ensembles on Riemann surfaces. We prove that the complement of the support of the equilibrium measure satisfies a quadrature identity. Furthermore, our setup allows us to naturally realize weak solutions of Laplacian growth (for a general time-dependent source) as an evolution of the support of equilibrium measures. When applied to the Riemann sphere this approach unifies the known methods for generating interior and exterior Laplacian growth. We later narrow our focus to a special class of quadrature domains which we call Algebraic Quadrature Domains. We show that many of the properties of quadrature domains generalize to this setting. In particular, the boundary of an Algebraic Quadrature Domain is the inverse image of a planar algebraic curve under a meromorphic function. This makes the study of the topology of Algebraic Quadrature Domains an interesting problem. We briefly investigate this problem and then narrow our focus to the study of the topology of classical quadrature domains. We extend the results of Lee and Makarov and prove (for n ≥ 3) c ≤ 5n-5, where c and n denote the connectivity and degree of a (classical) quadrature domain. At the same time we obtain a new upper bound on the number of isolated points of the algebraic curve corresponding to the boundary and thus a new upper bound on the number of special points. In the final chapter we study Coulomb gas ensembles on Riemann surfaces.
Resumo:
The nuclear resonant reaction 19F(ρ,αγ)16O has been used to perform depth-sensitive analyses of fluorine in lunar samples and carbonaceous chondrites. The resonance at 0.83 MeV (center-of-mass) in this reaction is utilized to study fluorine surface films, with particular interest paid to the outer micron of Apollo 15 green glass, Apollo 17 orange glass, and lunar vesicular basalts. These results are distinguished from terrestrial contamination, and are discussed in terms of a volcanic origin for the samples of interest. Measurements of fluorine in carbonaceous chondrites are used to better define the solar system fluorine abundance. A technique for measurement of carbon on solid surfaces with applications to direct quantitative analysis of implanted solar wind carbon in lunar samples is described.
Resumo:
Energies and relative intensities of gamma transitions in 152Sm, 152Gd, 154Gd, 166Er, and 232U following radioactive decay have been measured with a Ge(Li) spectrometer. A peak fitting program has been developed to determine gamma ray energies and relative intensities with precision sufficient to give a meaningful test of nuclear models. Several previously unobserved gamma rays were placed in the nuclear level schemes. Particular attention has been paid to transitions from the beta and gamma vibrational bands, since the gamma ray branching ratios are sensitive tests of configuration mixing in the nuclear levels. As the reduced branching ratios depend on the multipolarity of the gamma transitions, experiments were performed to measure multipole mixing ratios for transitions from the gamma vibrational band. In 154Gd, angular correlation experiments showed that transitions from the gamma band to the ground state band were predominantly electric quadrupole, in agreement with the rotational model. In 232U, the internal conversion spectrum has been studied with a Si(Li) spectrometer constructed for electron spectroscopy. The strength of electric monopole transitions and the multipolarity of some gamma transitions have been determined from the measured relative electron intensities.
The results of the experiments have been compared with the rotational model and several microscopic models. Relative B(E2) strengths for transitions from the gamma band in 232U and 166Er are in good agreement with a single parameter band mixing model, with values of z2= 0.025(10) and 0.046(2), respectively. Neither the beta nor the gamma band transition strengths in 152Sm and 154Gd can be accounted for by a single parameter theory, nor can agreement be found by considering the large mixing found between the beta and gamma bands. The relative B(E2) strength for transitions from the gamma band to the beta band in 232U is found to be five times greater than the strength to the ground state band, indicating collective transitions with strength approximately 15 single particle units.