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At least 1,495 records · Page 83

Au and Pt Remain Unoxidized on a CeO 2 -Based Catalyst during the Water–Gas Shift Reaction

The active form of Au and Pt in CeO 2 based catalysts for the WGS reaction is an issue that although it has been widely studied remains unclear. On one hand, ionic species might be responsible of weakening the Ce-O bonds increasing the oxygen mobility and WGS activity. On the other hand, the close contact of Au or Pt atoms with CeO 2 oxygen vacancies at the metal/CeO 2 interface might provide the active sites for an efficient reaction. In this work, by using in-situ X-ray absorption spectroscopy, we demonstrate that both Au and Pt remain unoxidized during the reaction. Here, remarkable differences involving the dynamics established by both species under WGS atmospheres were recognized. For the pre-reduced Pt catalyst, an increase of the conversion coincided with a re-structuration of the Pt atoms into cuboctahedrical metallic particles without significant variations on the overall particle size. Contrary to the relatively static behavior of Pt 0 , Au 0 nanoparticles exhibited a sequence of particle splitting and agglomeration whilst maintaining a zero oxidation state, even though not being located in a metallic environment during the process. High WGS activity was obtained when Au atoms were surrounded by oxygen. The fact that Au preserves its unoxidized state indicates that the chemical interaction between Au and oxygen must be necessarily electrostatic being such electrostatic interaction fundamental for a top performance in the WGS process.

36 MATERIALS SCIENCE↗

Red shift in the photoluminescence of colloidal carbon quantum dots induced by photon reabsorption

We synthesize the colloidal carbon/graphene quantum dots 1–9 nm in diameter and study their photoluminescence properties. Surprisingly, the luminescence properties of a fixed collection of colloidal carbon quantum dots can be systematically changed as the concentration varies. A model based on photon reabsorption is proposed which explains well the experiment. Infrared spectral study indicates that the surfaces of the carbon quantum dots are substantially terminated by oxygen atoms, which causes their ultra-high hydrophilicity. Our result clarifies the mystery of distinct emission colors in carbon quantum dots and indicates that photon reabsorption can strongly affect the luminescence properties of colloidal nanocrystals.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Transformation of potential energy surfaces for estimating isotopic shifts in anharmonic vibrational frequency calculations

A transformation of potential energy surfaces (PES) being represented by multi-mode expansions is introduced, which allows for the calculation of anharmonic vibrational spectra of any isotopologue from a single PES. This simplifies the analysis of infrared spectra due to significant CPU-time savings. An investigation of remaining deviations due to truncations and the so-called multi-level approximation is provided. The importance of vibrational-rotational couplings for small molecules is discussed in detail. In addition, an analysis is proposed, which provides information about the quality of the transformation prior to its execution. Benchmark calculations are provided for a set of small molecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Highly coherent red-shifted dispersive wave generation around 1.3 μm for efficient wavelength conversion

This research investigates the mechanism of the optical dispersive wave (DW) and proposes a scheme that can realize an efficient wavelength conversion. In an elaborately designed photonic crystal fiber, a readily available ytterbium laser operating at ∼1 μm can be transferred to the valuable 1.3 μm wavelength range. A low-order soliton is produced to concentrate the energy of the DW into the target wavelength range and improve the degree of coherence. The input chirp is demonstrated to be a factor that enhances the wavelength conversion efficiency. With a positive initial chirp, 76.6% of the pump energy in the fiber can be transferred into a spectral range between 1.24 and 1.4 μm. With the use of a grating compressor, it is possible to compress the generated coherent DW of several picoseconds into less than 90 fs.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Lamb Shift of n = 1 and n = 2 States of Hydrogen-like Atoms, 1 ≤ Z ≤ 110

Theoretical energy levels of the n = 1 and n = 2 states of hydrogen-like atoms with the nuclear charge numbers 1 ≤ Z ≤ 110 are tabulated. The tabulation is based on ab initio quantum electrodynamics calculations performed to all orders in the nuclear binding strength parameter Zα, where α is the fine structure constant. Theoretical errors due to various effects are critically examined and estimated.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗

Electrochromic shift supports the membrane destabilization model of Tat-mediated transport and shows ion leakage during Sec transport

Significance Due to the transient nature of the active Tat complex, much of the knowledge available has been hard won. Electric-field-indicating absorbance transients allow investigation of transmembrane ion movement using native electric potential in thylakoids while circumventing challenges of reconstitution. Electrical behavior of transiently and/or constitutively assembled complexes suggests that Sec translocation occurs through a barrel-stave-type proteinaceous pore, while Tat translocation likely occurs through a toroidal pore. This would be the first instance of toroidal pores being exploited by a general protein translocation system. Our electrochemical analysis offers insight into how protein transport might be linked to light stimulation. Localized membrane destabilization presents a rational link between the proton motive force, membrane thinning, and Tat-mediated transport of substrates critical to photosynthesis.

59 BASIC BIOLOGICAL SCIENCES↗

TEMPORAL SPECTRAL SHIFT AND POLARIZATION OF A BAND-SPLITTING SOLAR TYPE II RADIO BURST

In many type II solar radio bursts, the fundamental and/or the harmonic branches of the bursts can split into two almost parallel bands with similar spectral shapes and frequency drifts. However, the mechanisms accounting for this intriguing phenomenon remain elusive. In this study, we report a special band-splitting type II event in which spectral features appear systematically earlier on the upper band (with higher frequencies) than on the lower band (with lower frequencies) by several seconds. Furthermore, the emissions carried by the splitting band are moderately polarized with the left-hand polarized signals stronger than the right-hand ones. The polarization degree varies in a range of –0.3 to –0.6. These novel observational findings provide important constraints on the underlying physical mechanisms of band-splitting of type II radio bursts.

79 ASTRONOMY AND ASTROPHYSICS↗

Prediction of L70 Life and Assessment of Color Shift for Solid-State Lighting Using Kalman Filter and Extended Kalman Filter-Based Models

Solid-state lighting (SSL) luminaires containing light-emitting diodes (LEDs) have the potential of seeing excessive temperatures when being transported across country or being stored in nonclimate controlled warehouses. They are also being used in outdoor applications in desert environments that see little or no humidity but will experience extremely high temperatures during the day. This makes it important to increase our understanding of what effects high temperature exposure for a prolonged period of time will have on the usability and survivability of these devices. Traditional light sources “burn out” at the end of life. For an incandescent bulb, the lamp life is defined by B50 life. However, the LEDs have no filament to “burn“. The LEDs continually degrade, and the light output decreases eventually below useful levels causing failure. Currently, the TM-21 test standard is used to predict the L70 life of LEDs from LM-80 test data. Several failure mechanisms may be active in a LED at a single time, causing lumen depreciation. The underlying TM-21 model may not capture the failure physics in presence of multiple failure mechanisms. The correlation of lumen maintenance with underlying physics of degradation at system level is needed. In this paper, Kalman filter (KF) and extended Kalman Filters (EKF) have been used to develop a 70% Lumen Maintenance Life Prediction Model for LEDs used in SSL luminaires. Ten-thousand-hour LM-80 test data for various LEDs are used for model development. System state at each future time has been computed based on the state space at preceding time step, system dynamics matrix, control vector, control matrix, measurement matrix, measured vector, process noise, and measurement noise. The future state of the lumen depreciation are estimated based on a second-order Kalman Filter model and a Bayesian Framework. The measured state variable are related to the underlying damage using physics-b- sed models. Life prediction of L70 life for the LEDs used in SSL luminaires from KF- and EKF-based models are also compared with the TM-21 model predictions and experimental data.

32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATI↗

Back to the future: using historical climate variation to project near-term shifts in habitat suitable for coast redwood

Studies that mimic the effect of climate change on terrestrial ecosystems often use climate projections from downscaled global climate models (GCMs). These simulations are generally too coarse to capture patterns of fine-scale climate variation, such as the sharp coastal energy and moisture gradients associated with wind-driven upwelling of cold water. Coastal upwelling may limit future increases in coastal temperatures, compromising GCMs' ability to provide realistic scenarios of future climate in these coastal ecosystems. Taking advantage of naturally occurring variability in the high-resolution historic climatic record, we developed multiple fine-scale scenarios of California climate that maintain coherent relationships between regional climate and coastal upwelling. We compared these scenarios against coarse resolution GCM projections at a regional scale to evaluate their temporal equivalency. We utilized these historically based scenarios to estimate potential suitable habitat for coast redwood (Sequoia sempervirens D. Don) under 'normal' combinations of temperature and precipitation, and under anomalous combinations representative of potential future climates. We found that a scenario of warmer temperature with historically normal precipitation is equivalent to climate projected by GCMs for California by 2020-2030 and that under these conditions, climatically suitable habitat for coast redwood significantly contracts at the southern end of its current range. Our results indicate that historical climate data provide a high-resolution alternative to downscaled GCM outputs for near-term ecological forecasts. This method may be particularly useful in other regions where local climate is strongly influenced by ocean-atmosphere dynamics that are not represented by coarse-scale GCMs.

59 BASIC BIOLOGICAL SCIENCES↗

Natural soil microbiome variation affects spring foliar phenology with consequences for plant productivity and climate-driven range shifts

Identifying the potential for natural soil microbial communities to predictably affect complex plant traits is an important frontier in climate change research. Plant phenology varies with environmental and genetic factors, but few studies have examined if the soil microbiome interacts with plant population differentiation to affect phenology and ecosystem function. We compared soil microbial variation in a widespread tree species (Populus angustifolia) with different soil inoculum treatments in a common garden environment to test how the soil microbiome affects spring foliar phenology and subsequent biomass growth. We hypothesized and show that: 1) soil bacterial and fungal communities vary with tree conditioning from different populations and elevations, 2) this soil community variation influences patterns of foliar phenology and plant growth across populations and elevation gradients, and 3) transferring lower elevation plant genotypes to higher elevation soil communities delayed foliar phenology, thereby shortening the growing season and reducing annual biomass production. Our findings show the importance of plant-soil interactions that help shape the timing of tree foliar phenology and productivity. Here, these geographic patterns in plant population x microbiome interactions also broaden our understanding of how soil communities impact plant phenotypic variation across key climate change gradients, with consequences for ecosystem functioning.

59 BASIC BIOLOGICAL SCIENCES↗

Spectral Shifting in Nondestructive Assay Instrumentation

This project involves spectrum tailoring research that endeavors to better distinguish energies of gamma rays using different spectral material thicknesses and determine neutron energies by coating detectors with various materials.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Final Report: Development of High Light Output Plastic Scintillating and Wavelength-Shifting Fibers

Scintillating plastic optical fibers have increasingly been used as radiation detectors in nuclear and high energy physics research since they were first made in 1965. It is proposed to make fibers which are at least a factor of 2 brighter and thereby improve detection efficiency, spatial resolution and energy resolution. When radiation strikes existing plastic scintillator only the singlet excited states rather than the triplet excited states are used to produce scintillation light. This means only 25% of the deposited energy is available to produce scintillation light. Utilization of phosphorescent molecules should therefore drastically improve the light output. This process has been called “triplet harvesting” and has been successfully demonstrated in improving the light output of “Organic Light Emitting Diodes, OLEDs”. The objective of this proposal is to produce a bright scintillating fiber using triplet harvesting and a light output time constant of a few nanoseconds. In addition, an increase in the light containment will be achieved by using a new low refractive index cladding material. In Phase 1, polystyrene plastic material will be used. Organo-metallic phosphorescent and conventional dyes will be dissolved in the plastic to demonstrate both the desired brightness and fast decay time. Photophysical properties will be measured. Scintillating fiber will be made. Commercial benefits of this new material include providing improved detection of rare events such as the HIGGS BOSON at the billion dollar high energy facilities. and monitoring stored radioactive material. The new material will also play an important role in making improved imaging detection facilities for protecting civilians and facilities against CBRN-E threats. In addition, the resolution will be improved for medical brachytherapy. The results of selected organic dyes dissolved in a polystyrene matrix performing as scintillating samples are presented. The proposed organo-metallic phosphorescent dyes were not used due to lengthy synthesis times and cost. Rather, an attempt was made to harvest triplet energy from polystyrene using appropriately wavelength-matched dyes. Samples studied include films and blocks. Fibers were not manufactured as a suitable set of dyes was not determined.

07 ISOTOPE AND RADIATION SOURCES↗