Investigations of the Band Structure and Morphology of Nanostructured Surfaces

Two-dimensional electronic systems have long attracted interest in the physics and material science communities due to the exotic physics that arises from low-dimensional confinement. Studying the electronic behavior of 2D systems can provide insight into a variety of phenomena that are important to condensed-matter physics, including epitaxial growth, two-dimensional electron scattering and many-body physics. Correlation effects are strongly influenced by dimensionality, which determines the many-body excitations available to a system. In this dissertation, I examine the electronic structure of two very dierent types of two-dimensional systems: valence band electrons in single layer graphene and electronic states created at the vacuum interface of single crystal copper surfaces.The characteristics of both electronic systems depend intimately on the morphology of the surfaces they inhabit. Thus, in addition to discussing the respective band structures of these systems, a significant portion of this dissertation will be devoted to measurements of the surface morphology of these systems. Free-standing exfoliated monolayer graphene is an ultra-thin flexible membrane and, as such, is known to exhibit large out-of-plane deformation due to substrate and adsorbate interaction as well as thermal vibrations and, possibly, intrinsic buckling. Such crystal deformation is known to limit mobility and increase local chemical reactivity. Additionally, deformations present a measurement challenge to researchers wishing to determine the band structure by angle-resolved photoemission since they limit electron coherence in such measurements. In this dissertation, I present low energy electron microscopy and microprobe diffraction measurements, which are used to image and characterize corrugation in SiO2-supported and suspended exfoliated graphene at nanometer length scales. Diffraction line-shape analysis reveals quantitative differences in surface roughness on length scales below 20 nm which depend on film thickness and interaction with the substrate. Corrugation decreases with increasing film thickness, reflecting the increased stiffness of multilayer films. Specifically, single-layer graphene shows a markedly larger short range roughness than multilayer graphene. Due to the absence of interactions with the substrate, suspended graphene displays a smoother morphology and texture than supported graphene. A specific feature of suspended single-layer films is the dependence of corrugation on both adsorbate load and temperature, which is manifested by variations in the diffraction lineshape. The effects of both intrinsic and extrinsic corrugation factors will be discussed. Through a carefully coordinated study I show how these surface morphology measurements can be combined with angle resolved photoemission measurements to understand the role of surface corrugation in the ARPES measurement process. The measurements described here rely on the development of an analytical formulation for relating the crystal corrugation to the photoemission linewidth. I present ARPES measurements that show that, despite signicant deviation from planarity of the crystal, the electronic structure of exfoliated suspended graphene is nearly that of ideal, undoped graphene; the Dirac point is measured to be within 25 meV of EF . Further, I show that suspended graphene behaves as a marginal Fermi-liquid, with a quasiparticle lifetime which scales as (E - EF)-1; comparison with other graphene and graphite data is discussed. Image and surface states formed at the vacuum interface of a single crystal provide another example of a two dimensional electronic system. As with graphene, the surface quality and morphology strongly inuence the physics in this 2D electronic system. However, in contrast to graphene, which must be treated as a flexible membrane with continuous height variation, roughness in clean single crystal surfaces arises from lattice dislocations, which introduce discrete height variations. Such height variations can be exploited to generate a self assembled nano-structured surface. In particular, by making a vicinal cut on a single crystal surface, a nanoscale step array can be formed. A model system for such nanoscale self assembly is Cu(111). Cu(775) is formed by making an 8.5° viscinal cut of Cu(111) along the [11 -2] axis. The electronic states formed on the surface of this system, with a nanoscale step array of 14 Å terraces, shows markedly different behavior those formed on Cu(111). In this dissertation, I show that the tunability of a femtosecond optical parametric oscillator, combined with its high-repetition rate and short pulse length, provides a powerful tool for resonant band mapping of the sp surface and image states on flat and vicinal Cu(111)- Cu (775) surfaces, over the photon energy range from 3.9 to 5 eV. Since the time scale for excitation of the metal image state from the Cu surface state is comparable with the electron-electron equilibration time scale, sharp features are measured due to resonant excitation in the photoelectron energy distribution curves. In addition, I explore the range of photon energies and optical intensities which may be used for this approach and show that, despite the relatively high pump intensity, the 250 kHz repetition rate of this laser ameliorates the space-charge broadening and electron-energy shifting even for photon energies close to the vacuum edge. The strong excitation conditions generated by a femtosecond laser pulse applied to a Cu surface also allow the excitation and observation of a recently measured bulk state. In this dissertation I show that angle-resolved, tunable, two-photon photoemission (2PPE) can be used to map a bulk unoccupied band, viz. the Cu sp band 0 to 1 eV below the vacuum level, in the vicinity of the L point. This short-lived bulk band can be accessed using our setup due to the strong optical pump rate. I describe how photoemission from this state can be distinguished from photoemission from 2D states which is also present in the data. In particular, the variation of the initial-state energy with photon energy has a measured slope of ~ 1.64 in contrast with values of 1 or 2 observed for 2PPE from two-dimensional (2D) states. This unique variation illustrates the significant role of the perpendicular momentum of initial and final states in interpreting 2PPE data

Making ARPES Measurements on Corrugated Monolayer Crystals: Suspended Exfoliated Single-Crystal Graphene

Free-standing exfoliated monolayer graphene is an ultra-thin flexible membrane, which exhibits out of plane deformation or corrugation. In this paper, a technique is described to measure the band structure of such free-standing graphene by angle-resolved photoemission. Our results show that photoelectron coherence is limited by the crystal corrugation. However, by combining surface morphology measurements of the graphene roughness with angle-resolved photoemission, energy dependent quasiparticle lifetime and bandstructure measurements can be extracted. Our measurements rely on our development of an analytical formulation for relating the crystal corrugation to the photoemission linewidth. Our ARPES measurements show that, despite significant deviation from planarity of the crystal, the electronic structure of exfoliated suspended graphene is nearly that of ideal, undoped graphene; we measure the Dirac point to be within 25 meV of $E_F$ . Further, we show that suspended graphene behaves as a marginal Fermi-liquid, with a quasiparticle lifetime which scales as $(E - E_F)^{-1}$; comparison with other graphene and graphite data is discussed

Kisspeptin Signalling in the Hypothalamic Arcuate Nucleus Regulates GnRH Pulse Generator Frequency in the Rat

Kisspeptin and its G protein-coupled receptor (GPR) 54 are essential for activation of the hypothalamo-pituitary-gonadal axis. In the rat, the kisspeptin neurons critical for gonadotropin secretion are located in the hypothalamic arcuate (ARC) and anteroventral periventricular (AVPV) nuclei. As the ARC is known to be the site of the gonadotropin-releasing hormone (GnRH) pulse generator we explored whether kisspeptin-GPR54 signalling in the ARC regulates GnRH pulses.We examined the effects of kisspeptin-10 or a selective kisspeptin antagonist administration intra-ARC or intra-medial preoptic area (mPOA), (which includes the AVPV), on pulsatile luteinizing hormone (LH) secretion in the rat. Ovariectomized rats with subcutaneous 17β-estradiol capsules were chronically implanted with bilateral intra-ARC or intra-mPOA cannulae, or intra-cerebroventricular (icv) cannulae and intravenous catheters. Blood samples were collected every 5 min for 5–8 h for LH measurement. After 2 h of control blood sampling, kisspeptin-10 or kisspeptin antagonist was administered via pre-implanted cannulae. Intranuclear administration of kisspeptin-10 resulted in a dose-dependent increase in circulating levels of LH lasting approximately 1 h, before recovering to a normal pulsatile pattern of circulating LH. Both icv and intra-ARC administration of kisspeptin antagonist suppressed LH pulse frequency profoundly. However, intra-mPOA administration of kisspeptin antagonist did not affect pulsatile LH secretion.These data are the first to identify the arcuate nucleus as a key site for kisspeptin modulation of LH pulse frequency, supporting the notion that kisspeptin-GPR54 signalling in this region of the mediobasal hypothalamus is a critical neural component of the hypothalamic GnRH pulse generator

Planning for Sustainability in Small Municipalities: The Influence of Interest Groups, Growth Patterns, and Institutional Characteristics

How and why small municipalities promote sustainability through planning efforts is poorly understood. We analyzed ordinances in 451 Maine municipalities and tested theories of policy adoption using regression analysis.We found that smaller communities do adopt programs that contribute to sustainability relevant to their scale and context. In line with the political market theory, we found that municipalities with strong environmental interests, higher growth, and more formal governments were more likely to adopt these policies. Consideration of context and capacity in planning for sustainability will help planners better identify and benefit from collaboration, training, and outreach opportunities

Uncertainty in United States coastal wetland greenhouse gas inventorying

© The Author(s), 2018. This article is distributed under the terms of the Creative Commons Attribution License. The definitive version was published in Environmental Research Letters 13 (2018): 115005, doi:10.1088/1748-9326/aae157.Coastal wetlands store carbon dioxide (CO2) and emit CO2 and methane (CH4) making them an important part of greenhouse gas (GHG) inventorying. In the contiguous United States (CONUS), a coastal wetland inventory was recently calculated by combining maps of wetland type and change with soil, biomass, and CH4 flux data from a literature review. We assess uncertainty in this developing carbon monitoring system to quantify confidence in the inventory process itself and to prioritize future research. We provide a value-added analysis by defining types and scales of uncertainty for assumptions, burial and emissions datasets, and wetland maps, simulating 10 000 iterations of a simplified version of the inventory, and performing a sensitivity analysis. Coastal wetlands were likely a source of net-CO2-equivalent (CO2e) emissions from 2006–2011. Although stable estuarine wetlands were likely a CO2e sink, this effect was counteracted by catastrophic soil losses in the Gulf Coast, and CH4 emissions from tidal freshwater wetlands. The direction and magnitude of total CONUS CO2e flux were most sensitive to uncertainty in emissions and burial data, and assumptions about how to calculate the inventory. Critical data uncertainties included CH4 emissions for stable freshwater wetlands and carbon burial rates for all coastal wetlands. Critical assumptions included the average depth of soil affected by erosion events, the method used to convert CH4 fluxes to CO2e, and the fraction of carbon lost to the atmosphere following an erosion event. The inventory was relatively insensitive to mapping uncertainties. Future versions could be improved by collecting additional data, especially the depth affected by loss events, and by better mapping salinity and inundation gradients relevant to key GHG fluxes. Social Media Abstract: US coastal wetlands were a recent and uncertain source of greenhouse gasses because of CH4 and erosion.Financial support was provided primarily by NASA Carbon Monitoring Systems (NNH14AY67I) and the USGS Land Carbon Program, with additional support from The Smithsonian Institution, The Coastal Carbon Research Coordination Network (DEB-1655622), and NOAA Grant: NA16NMF4630103

Evaluation of an Atmosphere Revitalization Subsystem for Deep Space Exploration Missions

An Atmosphere Revitalization Subsystem (ARS) suitable for deployment aboard deep space exploration mission vehicles has been developed and functionally demonstrated. This modified ARS process design architecture was derived from the International Space Station's (ISS) basic ARS. Primary functions considered in the architecture include trace contaminant control, carbon dioxide removal, carbon dioxide reduction, and oxygen generation. Candidate environmental monitoring instruments were also evaluated. The process architecture rearranges unit operations and employs equipment operational changes to reduce mass, simplify, and improve the functional performance for trace contaminant control, carbon dioxide removal, and oxygen generation. Results from integrated functional demonstration are summarized and compared to the performance observed during previous testing conducted on an ISS-like subsystem architecture and a similarly evolved process architecture. Considerations for further subsystem architecture and process technology development are discussed

Organization specific predictors of job satisfaction: findings from a Canadian multi-site quality of work life cross-sectional survey

BACKGROUND: Organizational features can affect how staff view their quality of work life. Determining staff perceptions about quality of work life is an important consideration for employers interested in improving employee job satisfaction. The purpose of this study was to identify organization specific predictors of job satisfaction within a health care system that consisted of six independent health care organizations. METHODS: 5,486 full, part and causal time (non-physician) staff on active payroll within six organizations (2 community hospitals, 1 community hospital/long-term care facility, 1 long-term care facility, 1 tertiary care/community health centre, and 1 visiting nursing agency) located in five communities in Central West Ontario, Canada were asked to complete a 65-item quality of work life survey. The self-administered questionnaires collected staff perceptions of: co-worker and supervisor support; teamwork and communication; job demands and decision authority; organization characteristics; patient/resident care; compensation and benefits; staff training and development; and impressions of the organization. Socio-demographic data were also collected. RESULTS: Depending on the organization, between 15 and 30 (of the 40 potential predictor) variables were found to be statistically associated with job satisfaction (univariate analyses). Logistic regression analyses identified the best predictors of job satisfaction and these are presented for each of the six organizations and for all organizations combined. CONCLUSIONS: The findings indicate that job satisfaction is a multidimensional construct and although there appear to be some commonalities across organizations, some predictors of job satisfaction appear to be organization and context specific

Neonatal programming by immunological challenge: effects on ovarian function in the adult rat

Neonatal exposure to an immunological challenge (lipopolysaccharide, LPS) increases the activity of hypothalamo-pituitary–adrenal axis and sensitises the GNRH pulse generator to the inhibitory influence of stress in adult rats. We investigated the effects of neonatal exposure to LPS on various reproductive parameters during puberty and into adulthood in female rats. LPS (50 μg/kg, i.p.) or saline was administered on postnatal days 3 and 5. Vaginal opening was recorded, and oestrous cyclicity was monitored immediately post puberty and again at 8–9 weeks of age. At 10 weeks of age, the ovaries were removed and the number of follicles was counted, together with the thickness of the theca interna of the largest antral follicles. Ovarian sympathetic nerve activity was assessed immunohistochemically by measurement of the levels of ovarian low-affinity receptor of nerve growth factor (p75NGFR). In rats exposed to LPS in early life, there was a significant delay in puberty and disruption of oestrous cyclicity immediately post puberty, which persisted into adulthood. The follicle reserve was decreased, the thickness of the theca interna increased and the expression profile of ovarian p75NGFR increased in the neonatal LPS-treated animals. These data suggest that exposure to LPS during early neonatal life can have long-term dysfunctional effects on the female reproductive system, which might involve, at least in part, increased ovarian sympathetic nerve activity

LSST Science Book, Version 2.0

A survey that can cover the sky in optical bands over wide fields to faint magnitudes with a fast cadence will enable many of the exciting science opportunities of the next decade. The Large Synoptic Survey Telescope (LSST) will have an effective aperture of 6.7 meters and an imaging camera with field of view of 9.6 deg^2, and will be devoted to a ten-year imaging survey over 20,000 deg^2 south of +15 deg. Each pointing will be imaged 2000 times with fifteen second exposures in six broad bands from 0.35 to 1.1 microns, to a total point-source depth of r~27.5. The LSST Science Book describes the basic parameters of the LSST hardware, software, and observing plans. The book discusses educational and outreach opportunities, then goes on to describe a broad range of science that LSST will revolutionize: mapping the inner and outer Solar System, stellar populations in the Milky Way and nearby galaxies, the structure of the Milky Way disk and halo and other objects in the Local Volume, transient and variable objects both at low and high redshift, and the properties of normal and active galaxies at low and high redshift. It then turns to far-field cosmological topics, exploring properties of supernovae to z~1, strong and weak lensing, the large-scale distribution of galaxies and baryon oscillations, and how these different probes may be combined to constrain cosmological models and the physics of dark energy.Comment: 596 pages. Also available at full resolution at http://www.lsst.org/lsst/sciboo