New symmetrical dinucleating ligand based assembly of bridged dicopper(II) and dizinc(II) centers: Synthesis, structure, spectroscopy, magnetic properties and glycoside hydrolysis

Two dinuclear copper(II) complexes Li(H2O)(3)(CH3OH)](4)Cu2Br4]Cu-2(cpdp)(mu-O2CCH3)](4)(OH)(2) (1), Cu (H2O)(4)]Cu-2(cpdp)(mu-O2CC6H5)](2)Cl-2 center dot 5H(2)O (2), and a dinuclear zinc(II) complex Zn-2(cpdp)(mu-O2CCH3)] (3) have been synthesized using pyridine and benzoate functionality based new symmetrical dinucleating ligand, N, N'-Bis2-carboxybenzomethyl]-N, N'-Bis2-pyridylmethyl]-1,3-diaminopropan-2-ol (H(3)cpdp). Complexes 1, 2 and 3 have been synthesized by carrying out reaction of the ligand H3cpdp with stoichiometric amounts of Cu-2(O2CCH3)(4)(H2O)(2)], CuCl2 center dot 2H(2)O/C6H5COONa, and Zn(CH3COO)(2)center dot 2H(2)O, respectively, in methanol in the presence of NaOH at ambient temperature. Characterizations of the complexes have been done using various analytical techniques including single crystal X-ray structure determination. The X-ray crystal structure analyses reveal that the copper(II) ions in complexes 1 and 2 are in a distorted square pyramidal geometry with Cu-Cu separation of 3.455(8) angstrom and 3.492(1)angstrom, respectively. The DFT optimized structure of complex 3 indicates that two zinc(II) ions are in a distorted square pyramidal geometry with Zn-Zn separation of 3.492(8)angstrom. UV-Vis and mass spectrometric analyses of the complexes confirm their dimeric nature in solution. Furthermore, H-1 and C-13 NMR spectroscopic investigations authenticate the integrity of complex 3 in solution. Variable-temperature (2-300 K) magnetic susceptibility measurements show the presence of antiferromagnetic interactions between the copper centers, with J = -26.0 cm(-1) and -23.9 cm(-1) ((H) over cap = -2JS(1)S(2)) in complexes 1 and 2, respectively. In addition, glycosidase-like activity of the complexes has been investigated in aqueous solution at pH similar to 10.5 by UV-Vis spectrophotometric technique using p-nitrophenyl-alpha-D-glucopyranoside (4) and p-nitrophenyl-beta-D-glucopyranoside (5) as model substrates. (C) 2015 Elsevier B.V. All rights reserved.

Gal(1-x)Mn(1-x)Sb Grown on GaSb with Mass-Analyzed Low-Energy Dual Ion Beam Deposition

The Ga1-xMnxSb samples were fabricated by the implantation of Mn ions into GaSb (1 0 0) substrate with mass-analyzed low-energy dual ion beam deposition system, and post-annealing. Auger electron spectroscopy depth profile of the Ga1-xMnxSb samples showed

FexSi grown with mass-analyzed low-energy dual ion beam deposition

Heavily iron-implanted silicon was prepared by mass-analyzed low-energy dual ion beam deposition technique. Auger electron spectroscopy depth profiles indicate that iron ions are shallowly implanted into the single-crystal silicon substrate and formed 35 nm thick FexSi films. X-ray diffraction measurements show that as-implanted sample is amorphous and the structure of crystal is partially restored after as-implanted sample was annealed at 400degreesC. There are no new phases formed. Carrier concentration depth profile of annealed sample was measured by Electrochemical C-V method and indicated that FexSi film shows n-type conductivity while silicon substrate is p-type. The p-n junction is formed between FexSi film and silicon substrate showing rectifying effect. (C) 2003 Elsevier B.V. All rights reserved.

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.

Magnetic trapping of atomic tritium for neutrino mass measurement

Improved measurement of the neutrino mass via β decay spectroscopy requires the development of new energy measurement techniques and a new β decay source. A promising proposal is to measure the β energy by the frequency of the cyclotron radiation emitted in a magnetic field and to use a high purity atomic tritium source. This thesis examines the feasibility of using a magnetic trap to create and maintain such a source. We demonstrate that the loss rate due to β decay heating is not a limiting factor for the design. We also calculate the loss rate due to evaporative cooling and propose that the tritium can be cooled sufficiently during trap loading as to render this negligible. We further demonstrate a design for the magnetic field which produces a highly uniform field over a large fraction of the trap volume as needed for cyclotron frequency spectroscopy while still providing effective trapping.

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.

Density, sp3 content and internal layering of DLC films by X-ray reflectivity and electron energy loss spectroscopy

A variety of hydrogenated and non-hydrogenated amorphous carbon thin films have been characterized by means of grazing-incidence X-ray reflectivity (XRR) to give information about their density, thickness, surface roughness and layering. We used XRR to validate the density of ta-C, ta-C:H and a-C:H films derived from the valence plasmon in electron energy loss spectroscopy measurements, up to 3.26 and 2.39 g/cm3 for ta-C and ta-C:H, respectively. By comparing XRR and electron energy loss spectroscopy (EELS) data, we have been able for the first time to fit a common electron effective mass of m*/me = 0.87 for all amorphous carbons and diamond, validating the `quasi-free' electron approach to density from valence plasmon energy. While hydrogenated films are found to be substantially uniform in density across the film, ta-C films grown by the filtered cathodic vacuum arc (FCVA) show a multilayer structure. However, ta-C films grown with an S-bend filter show a high uniformity and only a slight dependence on the substrate bias of both sp3 and layering.

Low temperature growth of ultra-high mass density carbon nanotube forests on conductive supports

We grow ultra-high mass density carbon nanotube forests at 450°C on Ti-coated Cu supports using Co-Mo co-catalyst. X-ray photoelectron spectroscopy shows Mo strongly interacts with Ti and Co, suppressing both aggregation and lifting off of Co particles and, thus, promoting the root growth mechanism. The forests average a height of 0.38 μm and a mass density of 1.6 g cm -3. This mass density is the highest reported so far, even at higher temperatures or on insulators. The forests and Cu supports show ohmic conductivity (lowest resistance ∼22 kΩ), suggesting Co-Mo is useful for applications requiring forest growth on conductors. © 2013 AIP Publishing LLC.

FexSi grown with mass-analyzed low-energy dual ion beam deposition

Heavily iron-implanted silicon was prepared by mass-analyzed low-energy dual ion beam deposition technique. Auger electron spectroscopy depth profiles indicate that iron ions are shallowly implanted into the single-crystal silicon substrate and formed 35 nm thick FexSi films. X-ray diffraction measurements show that as-implanted sample is amorphous and the structure of crystal is partially restored after as-implanted sample was annealed at 400degreesC. There are no new phases formed. Carrier concentration depth profile of annealed sample was measured by Electrochemical C-V method and indicated that FexSi film shows n-type conductivity while silicon substrate is p-type. The p-n junction is formed between FexSi film and silicon substrate showing rectifying effect. (C) 2003 Elsevier B.V. All rights reserved.

Gal(1-x)Mn(1-x)Sb grown on GaSb with mass-analyzed low-energy dual ion beam deposition

The Ga1-xMnxSb samples were fabricated by the implantation of Mn ions into GaSb (1 0 0) substrate with mass-analyzed low-energy dual ion beam deposition system, and post-annealing. Auger electron spectroscopy depth profile of the Ga1-xMnxSb samples showed that the Mn ions were successfully implanted into GaSb substrate. Clear double-crystal X-ray diffraction patterns of the Ga1-xMnxSb samples indicate that the Ga1-xMnxSb epilayers have the zinc-blende structure without detectable second phase. Magnetic hysteresis-loop of the Ga1-xMnxSb epilayers were obtained at room temperature (293 K) with alternating gradient magnetometry. (c) 2005 Elsevier B.V. All rights reserved.

(Ga,Mn,N) compounds growth with mass-analyzed low energy dual ion beam deposition

The (Ga,Mn,N) samples were grown by the implantation of low-energy Mn ions into GaN/Al2O3 substrate at different elevated substrate temperatures with mass-analyzed low-energy dual ion beam deposition system. Auger electron spectroscopy depth profile of samples grown at different substrate temperatures indicates that the Mn ions reach deeper in samples with higher substrate temperatures. Clear X-ray diffraction peak from (Ga,Mn)N is observed in samples grown at the higher substrate temperature. It indicates that under optimized substrate temperature and annealing conditions the solid solution (Ga,Mn)N phase in samples was formed with the same lattice structure as GaN and different lattice constant. (C) 2003 Elsevier Science B.V. All rights reserved.

GdxSi grown with mass-analyzed low energy dual ion beam epitaxy technique

Semiconducting gadolinium silicide GdxSi samples were prepared by mass-analyzed low-energy dual ion beam epitaxy technique. Auger electron spectroscopy depth profiles indicate that the gadolinium ions are implanted into the single-crystal silicon substrate and formed 20 nm thick GdxSi film. X-ray double-crystal diffraction measurement shows that there is no new phase formed. The XPS spectra show that one type of silicon peaks whose binding energy is between that of silicide and silicon dioxide, and the gadolinium peak of binding energy is between that of metal Gd and Gd2O3. All of these results indicate that an amorphous semiconductor is formed. (C) 2002 Elsevier Science B.V. All rights reserved.

(Ga,Mn,As) compounds grown on semi-insulating GaAs with mass-analyzed low energy dual ion beam depositionw

The (Ga,Mn,As) compounds were obtained by the implantation of Mn ions into semi-insulating GaAs substrate with mass-analyzed low energy dual ion beam deposition technique. Auger electron spectroscopy depth profile of a typical sample grown at the substrate temperature of 250degreesC showed that the Mn ions were successfully implanted into GaAs substrate with the implantation depth of 160 nm. X-ray diffraction was employed for the structural analyses of all samples. The experimental results were greatly affected by the substrate temperature. Ga5.2Mn was obtained in the sample grown at the substrate temperature of 250degreesC. Ga5.2Mn, Ga5Mn8 and Mn3Ga were obtained in the sample grown at the substrate temperature of 400degreesC. However, there is no new phase in the sample grown at the substrate temperature of 200degreesC. The sample grown at 400degreesC was annealed at 840degreesC. In this annealed sample Mn3Ga disappeared, Ga5Mn8 tended to disappear,Ga5.2Mn crystallized better and a new phase of Mn2As was generated. (C) 2002 Elsevier Science B,V. All rights reserved.

MnSi similar to 1.73 grown on silicon with mass-analyzed low energy dual ion beam epitaxy technique

Semiconducting manganese silicide, Mn27Si47 and Mn15Si26, were obtained using mass-analyzed low energy dual ion beam epitaxy technique, Auger electron spectroscopy depth profiles showed that some of the Mn ions were deposited on single-crystal silicon substrate and formed a 37.5 nm thick Mn film, and the other Mn ions were successfully implanted into the Si substrate with the implantation depth of 618 nm. Some samples were annealed in the atmosphere of flowing N-2 at 840 degreesC. X-ray diffraction measurements showed that the annealing was beneficial to the formation of Mn27Si47 and Mn15Si26 (C) 2001 Published by Elsevier Science B.V.

Carbon film deposited by mass-selected low energy ion beam technique and ion bombardment effect

By mass-selected low energy ion beam deposition, amorphous carbon film was obtained. X-ray diffraction, Raman and Auger electron spectroscopy depth line shape measurements showed that such carbon films contained diamond particles. The main growth mechanism is subsurface implantation. Furthermore, it was indicated in a different way that ion bombardment played a decisive role in bias enhanced nucleation of chemical vapor deposition diamond.