Mechanism And Selectivity In The Epoxidation Of Ethylene Over Silver: The Results Of Single Crystal Measurements

The silver-catalysed oxidation of ethylene has been examined on the (III) face of a single crystal by a combination of electron spectroscopy and kinetic measurements at pressures of up to 50 Torr. The necessary and sufficient conditions for ethylene oxide formation are established, reaction intermediates are identified, kinetic isotope effects are observed and the role of Cs in modifying reaction selectivity is examined. It is shown that surface alkali exhibits opposite effects on the reactions which lead to the further oxidation of ethylene oxide and on the direct combustion of ethylene. © 1984.

Photographic investigations in molecular spectroscopy

The determination of the energy levels and the probabilities of transition between them, by the formal analysis of observed electronic, vibrational, and rotational band structures, forms the direct goal of all investigations of molecular spectra, but the significance of such data lies in the possibility of relating them theoretically to more concrete properties of molecules and the radiation field. From the well developed electronic spectra of diatomic molecules, it has been possible, with the aid of the non-relativistic quantum mechanics, to obtain accurate moments of inertia, molecular potential functions, electronic structures, and detailed information concerning the coupling of spin and orbital angular monenta with the angular momentum of nuclear rotation. The silicon fluori1e molecule has been investigated in this laboratory, and is found to emit bands whose vibrational and rotational structures can be analyzed in this detailed fashion.

Like silicon fluoride, however, the great majority of diatomic molecules are formed only under the unusual conditions of electrical discharge, or in high temperature furnaces, so that although their spectra are of great theoretical interest, the chemist is eager to proceed to a study of polyatomic molecules, in the hope that their more practically interesting structures might also be determined with the accuracy and assurance which characterize the spectroscopic determinations of the constants of diatomic molecules. Some progress has been made in the determination of molecule potential functions from the vibrational term values deduced from Raman and infrared spectra, but in no case can the calculations be carried out with great generality, since the number of known term values is always small compared with the total number of potential constants in even so restricted a potential function as the simple quadratic type. For the determination of nuclear configurations and bond distances, however, a knowledge of the rotational terms is required. The spectra of about twelve of the simpler polyatomic molecules have been subjected to rotational analyses, and a number of bond distances are known with considerable accuracy, yet the number of molecules whose rotational fine structure has been resolved even with the most powerful instruments is small. Consequently, it was felt desirable to investigate the spectra of a number of other promising polyatomic molecules, with the purpose of carrying out complete rotational analyses of all resolvable bands, and ascertaining the value of the unresolved band envelopes in determining the structures of such molecules, in the cases in which resolution is no longer possible. Although many of the compounds investigated absorbed too feebly to be photographed under high dispersion with the present infrared sensitizations, the location and relative intensities of their bands, determined by low dispersion measurements, will be reported in the hope that these compounds may be reinvestigated in the future with improved techniques.

Understanding planet formation through high precision photometry and spectroscopy

From studies of protoplanetary disks to extrasolar planets and planetary debris, we aim to understand the full evolution of a planetary system. Observational constraints from ground- and space-based instrumentation allows us to measure the properties of objects near and far and are central to developing this understanding. We present here three observational campaigns that, when combined with theoretical models, reveal characteristics of different stages and remnants of planet formation. The Kuiper Belt provides evidence of chemical and dynamical activity that reveals clues to its primordial environment and subsequent evolution. Large samples of this population can only be assembled at optical wavelengths, with thermal measurements at infrared and sub-mm wavelengths currently available for only the largest and closest bodies. We measure the size and shape of one particular object precisely here, in hopes of better understanding its unique dynamical history and layered composition.

Molecular organic chemistry is one of the most fundamental and widespread facets of the universe, and plays a key role in planet formation. A host of carbon-containing molecules vibrationally emit in the near-infrared when excited by warm gas, T~1000 K. The NIRSPEC instrument at the W.M. Keck Observatory is uniquely configured to study large ranges of this wavelength region at high spectral resolution. Using this facility we present studies of warm CO gas in protoplanetary disks, with a new code for precise excitation modeling. A parameterized suite of models demonstrates the abilities of the code and matches observational constraints such as line strength and shape. We use the models to probe various disk parameters as well, which are easily extensible to others with known disk emission spectra such as water, carbon dioxide, acetylene, and hydrogen cyanide.

Lastly, the existence of molecules in extrasolar planets can also be studied with NIRSPEC and reveals a great deal about the evolution of the protoplanetary gas. The species we observe in protoplanetary disks are also often present in exoplanet atmospheres, and are abundant in Earth's atmosphere as well. Thus, a sophisticated telluric removal code is necessary to analyze these high dynamic range, high-resolution spectra. We present observations of a hot Jupiter, revealing water in its atmosphere and demonstrating a new technique for exoplanet mass determination and atmospheric characterization. We will also be applying this atmospheric removal code to the aforementioned disk observations, to improve our data analysis and probe less abundant species. Guiding models using observations is the only way to develop an accurate understanding of the timescales and processes involved. The futures of the modeling and of the observations are bright, and the end goal of realizing a unified model of planet formation will require both theory and data, from a diverse collection of sources.

Deep near-infrared spectroscopy of high-redshift galaxies: the physical growth of passive systems

The assembly history of massive galaxies is one of the most important aspects of galaxy formation and evolution. Although we have a broad idea of what physical processes govern the early phases of galaxy evolution, there are still many open questions. In this thesis I demonstrate the crucial role that spectroscopy can play in a physical understanding of galaxy evolution. I present deep near-infrared spectroscopy for a sample of high-redshift galaxies, from which I derive important physical properties and their evolution with cosmic time. I take advantage of the recent arrival of efficient near-infrared detectors to target the rest-frame optical spectra of z > 1 galaxies, from which many physical quantities can be derived. After illustrating the applications of near-infrared deep spectroscopy with a study of star-forming galaxies, I focus on the evolution of massive quiescent systems.

Most of this thesis is based on two samples collected at the W. M. Keck Observatory that represent a significant step forward in the spectroscopic study of z > 1 quiescent galaxies. All previous spectroscopic samples at this redshift were either limited to a few objects, or much shallower in terms of depth. Our first sample is composed of 56 quiescent galaxies at 1 < z < 1.6 collected using the upgraded red arm of the Low Resolution Imaging Spectrometer (LRIS). The second consists of 24 deep spectra of 1.5 < z < 2.5 quiescent objects observed with the Multi-Object Spectrometer For Infra-Red Exploration (MOSFIRE). Together, these spectra span the critical epoch 1 < z < 2.5, where most of the red sequence is formed, and where the sizes of quiescent systems are observed to increase significantly.

We measure stellar velocity dispersions and dynamical masses for the largest number of z > 1 quiescent galaxies to date. By assuming that the velocity dispersion of a massive galaxy does not change throughout its lifetime, as suggested by theoretical studies, we match galaxies in the local universe with their high-redshift progenitors. This allows us to derive the physical growth in mass and size experienced by individual systems, which represents a substantial advance over photometric inferences based on the overall galaxy population. We find a significant physical growth among quiescent galaxies over 0 < z < 2.5 and, by comparing the slope of growth in the mass-size plane dlogR_e/dlogM_∗ with the results of numerical simulations, we can constrain the physical process responsible for the evolution. Our results show that the slope of growth becomes steeper at higher redshifts, yet is broadly consistent with minor mergers being the main process by which individual objects evolve in mass and size.

By fitting stellar population models to the observed spectroscopy and photometry we derive reliable ages and other stellar population properties. We show that the addition of the spectroscopic data helps break the degeneracy between age and dust extinction, and yields significantly more robust results compared to fitting models to the photometry alone. We detect a clear relation between size and age, where larger galaxies are younger. Therefore, over time the average size of the quiescent population will increase because of the contribution of large galaxies recently arrived to the red sequence. This effect, called progenitor bias, is different from the physical size growth discussed above, but represents another contribution to the observed difference between the typical sizes of low- and high-redshift quiescent galaxies. By reconstructing the evolution of the red sequence starting at z ∼ 1.25 and using our stellar population histories to infer the past behavior to z ∼ 2, we demonstrate that progenitor bias accounts for only half of the observed growth of the population. The remaining size evolution must be due to physical growth of individual systems, in agreement with our dynamical study.

Finally, we use the stellar population properties to explore the earliest periods which led to the formation of massive quiescent galaxies. We find tentative evidence for two channels of star formation quenching, which suggests the existence of two independent physical mechanisms. We also detect a mass downsizing, where more massive galaxies form at higher redshift, and then evolve passively. By analyzing in depth the star formation history of the brightest object at z > 2 in our sample, we are able to put constraints on the quenching timescale and on the properties of its progenitor.

A consistent picture emerges from our analyses: massive galaxies form at very early epochs, are quenched on short timescales, and then evolve passively. The evolution is passive in the sense that no new stars are formed, but significant mass and size growth is achieved by accreting smaller, gas-poor systems. At the same time the population of quiescent galaxies grows in number due to the quenching of larger star-forming galaxies. This picture is in agreement with other observational studies, such as measurements of the merger rate and analyses of galaxy evolution at fixed number density.

Fluorescence cross-correlation spectroscopy to study hemodynamics

[EN] In the recent years a series of optical correlation techniques have been developed in order to be able to measure flow velocity with high spatial resolution while being non-invasive in order to be employed in-vivo on biological organisms. The technique employed in my thesis work, scanning laser image correlation (SLIC), is a powerful approach for the detection of flow motions because it overcomes some limitations of the classical spectroscopy techniques. SLIC method consists in repeated laser scans over a linear pattern and on the cross correlation of the signal emitted by the excited fluorophores in different positions along the scan line. Therefore, the resulting measurements for flow velocity are really accurate.

Optical emission spectroscopy of the plasma during sputter deposition of YBCO films for microwave applications

YBCO thin films are currently used in several HTS-based electronics applications. The performance of devices, which may include microwave passive components (filters, resonators), grain boundary junctions or spintronic multilayer structures, is determined by film quality, which in turn depends on the deposition technology used and growth parameters. We report on results from nonintrusive Optical Emission Spectroscopy of the plasma during YBCO thin film deposition in a high-pressure on-axis sputtering system under different conditions, including small trace gas additions to the sputtering gas. We correlate these results with the compositional and structural changes which affect the DC and microwave properties of YBCO films. Film morphology, composition, structure and in- and out-of-plane orientation were assessed; T, and microwave surface resistance measurements were made using inductive and resonator techniques. Comparison was made with films sputtered in an off-axis 2-opposing magnetron system.

Gamma-ray spectroscopy at TRIUMF-ISAC

The 8π spectrometer at TRIUMF-ISAC consists of 20 Compton-suppressed germanium detectors and various auxiliary devices. The Ge array, once used for studies of nuclei at high angular momentum, has been transformed into the world's most powerful device dedicated to radioactive-decay studies. Many improvements in the spectrometer have been made, including a high-throughput data acquisition system, installation of a moving tape collector, incorporation of an array of 20 plastic scintillators for β-particle tagging, 5 Si(Li) detectors for conversion electrons, and 10 BaF2 detectors for fast-lifetime measurements. Experiments can be performed where data from all detectors are collected simultaneously, resulting in a very detailed view of the nucleus through radioactive decay. A number of experimental programmes have been launched that take advantage of the versatility of the spectrometer, and the intense beams available at TRIUMF-ISAC. © 2006 American Institute of Physics.

Raman spectroscopy of shear and layer breathing modes in multilayer MoS2

We study by Raman scattering the shear and layer breathing modes in multilayer MoS2. These are identified by polarization measurements and symmetry analysis. Their positions change significantly with the number of layers, with different scaling for odd and even layers. A chain model can explain the results, with general applicability to any layered material, allowing a reliable diagnostic of their thickness. © 2013 American Physical Society.

Ultralow surface recombination velocity in InP nanowires probed by terahertz spectroscopy.

Using transient terahertz photoconductivity measurements, we have made noncontact, room temperature measurements of the ultrafast charge carrier dynamics in InP nanowires. InP nanowires exhibited a very long photoconductivity lifetime of over 1 ns, and carrier lifetimes were remarkably insensitive to surface states despite the large nanowire surface area-to-volume ratio. An exceptionally low surface recombination velocity (170 cm/s) was recorded at room temperature. These results suggest that InP nanowires are prime candidates for optoelectronic devices, particularly photovoltaic devices, without the need for surface passivation. We found that the carrier mobility is not limited by nanowire diameter but is strongly limited by the presence of planar crystallographic defects such as stacking faults in these predominantly wurtzite nanowires. These findings show the great potential of very narrow InP nanowires for electronic devices but indicate that improvements in the crystallographic uniformity of InP nanowires will be critical for future nanowire device engineering.

Carrier lifetime and mobility enhancement in nearly defect-free core-shell nanowires measured using time-resolved terahertz spectroscopy.

We have used transient terahertz photoconductivity measurements to assess the efficacy of two-temperature growth and core-shell encapsulation techniques on the electronic properties of GaAs nanowires. We demonstrate that two-temperature growth of the GaAs core leads to an almost doubling in charge-carrier mobility and a tripling of carrier lifetime. In addition, overcoating the GaAs core with a larger-bandgap material is shown to reduce the density of surface traps by 82%, thereby enhancing the charge conductivity.

Measuring the electrical properties of semiconductor nanowires using terahertz conductivity spectroscopy

Accurately measuring the electronic properties of nanowires is a crucial step in the development of novel semiconductor nanowire-based devices. With this in mind, optical pump-terahertz probe (OPTP) spectroscopy is ideally suited to studies of nanowires: it provides non-contact measurement of carrier transport and dynamics at room temperature. OPTP spectroscopy has been used to assess key electrical properties, including carrier lifetime and carrier mobility, of GaAs, InAs and InP nanowires. The measurements revealed that InAs nanowires exhibited the highest mobilities and InP nanowires exhibited the lowest surface recombination velocity. © 2013 Copyright SPIE.

Direct observation of coherent spin transfer processes in an InGaAs/GaAs quantum well via two-color time-resolved Kerr rotation measurements

A two-color time-resolved Kerr rotation spectroscopy system was built, with a femtosecond Ti:sapphire laser and a photonic crystal fiber, to study coherent spin transfer processes in an InGaAs/GaAs quantum well sample. The femtosecond Ti:sapphire laser plays two roles: besides providing a pump beam with a tunable wavelength, it also excites the photonic crystal fiber to generate supercontinuum light ranging from 500 nm to 1600 nm, from which a probe beam with a desirable wavelength is selected with a suitable interference filter. With such a system, we studied spin transfer processes between two semiconductors of different gaps in an InGaAs/GaAs quantum well sample. We found that electron spins generated in the GaAs barrier were transferred coherently into the InGaAs quantum well. A model based on rate equations and Bloch-Torrey equations is used to describe the coherent spin transfer processes quantitatively. With this model, we obtain an effective electron spin accumulation time of 21 ps in the InGaAs quantum well.

Proton irradiation-induced defects in undoped GaSb studied by positron lifetime spectroscopy and photoluminescence

Undoped GaSb was irradiated by 2.6 MeV protons. The irradiation-induced defects were studied by positron lifetime spectroscopy (PLS) and photoluminescence (PL). Positron lifetime measurements showed that vacancy-type defects were introduced after irradiation, and divacancies were formed at higher irradiation dose. Annealing experiments revealed there were different annealing steps between the as grown and proton-irradiated samples, the reason for which was tentatively attributed to the formation of divacancies in the proton-irradiated samples during annealing. All the vacancy defects could be annealed out at around 500 degrees C. The PL intensity quickly fell down after proton irradiation and decreased with increasing irradiation dose, indicating that irradiation induced non-irradiative recombination centers, whose candidates were assigned to the vacancy defects induced by proton irradiation.

Defects in GaSb studied by coincidence Doppler broadening measurements

Undoped, Zn-doped and Te-doped GaSb with different concentrations were investigated by positron lifetime spectroscopy (PAS) and the Doppler broadening technique. Detection sensitivity of the latter technique was improved by using a second Ge-detector for the coincident detection of the second annihilation photon. PAS measurement indicated that there were vacancies in these samples. By combining the Doppler broadening measurements, the native acceptor defects in GaSb were identified to be predominantly Ga vacancy (V-Ga) related defects.

Identification of vacancies in electron irradiated GaSb by coincidence Doppler broadening spectroscopy

In this paper we present the results of coincidence Doppler broadening (CDB) measurements and positron lifetime spectroscopy (PLS) on the semiconductor material GaSb. Gallium vacancy with positron lifetime of about 283 ps (V-Ga, (283 ps)) was identified in as-grown sample by CDB technique and PAS technique. For electron irradiated samples with dosages of 10(17) cm(-2) and 10(18) cm(-2), the PAS showed almost the same defectrelated positron lifetime of about 285 ps. CDB experiments indicated that defects in irradiated samples were related to Ga vacancies. (c) 2006 Published by Elsevier B.V.