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At least 235 records · Page 13

Effects of Wind Shear and Aerosol Conditions on the Organization of Precipitating Marine Stratocumulus Clouds

Here this study examines how wind shear affects precipitating marine stratocumulus clouds under different cloud droplet number concentrations (N d ). We performed a series of large eddy simulations (LES) of nocturnal marine stratocumulus clouds using Cloud Model 1 (CM1). The simulations show that N d is the dominant factor for cloud cellular organization in this cloud regime rather than wind shear. Low N d characterizes the open cellular structure with a high in-cloud liquid water path (LWP). When wind shear is increased, the cloud fraction tends to decrease along with LWP, suggesting the cloud top region is significantly influenced by the entrainment and mixing of dry air from the free troposphere. We also examine cold pools in open and closed cellular clouds. Open-cell clouds produce larger and deeper cold pools compared to closed-cell clouds. Interestingly, cold pools can exist without surface precipitation and are produced by evaporation of light precipitation (drizzle) below the cloud base with weak downdrafts. The evaporation of raindrops and drizzle play an important role in initiating new convection, particularly where colliding outflows occur downstream of the cloud. This secondary convection contributes to the development and maintenance of the cloud cellular organization and formation.

54 ENVIRONMENTAL SCIENCES↗

Beating the thermodynamic limit with photo-activation of n-doping in organic semiconductors

Chemical doping of organic semiconductors using molecular dopants plays a key role in the fabrication of efficient organic electronic devices. While a variety of stable molecular p-dopants have been developed and successfully deployed in devices in the past decade, air-stable molecular n-dopants suitable for materials with low electron affinity are still elusive. In this work we demonstrate that photo-activation of a cleavable air-stable dimeric dopant can result in kinetically stable and efficient n-doping of host semiconductors, whose reduction potentials are beyond the thermodynamic reach of the dimer’s effective reducing strength. Electron-transport layers doped in this manner are used to fabricate high-efficiency organic light-emitting diodes. This strategy thus enables a new paradigm for using air-stable molecular dopants to improve conductivity in, and provide ohmic contacts to, organic semiconductors with very low electron affinity.

36 MATERIALS SCIENCE↗

Energy band structure and metal-organic interactions in tetracyanoquinodimethane (TCNQ) and N,N'-dicyanoquinonediimine (DCNQI) materials

The interplay of metal orbitals in metal TCNQ (7,7,8,8-tetracyanoquinodimethane) and DCNQI (N,N'-dicyanoquinonediimine) complexes is investigated on the basis of molecular orbital calculations. For the M(TCNQ) materials, where M = Na, K, Rb, Cs, Tl, Cu, and Ag, the conductivity decreases with the increase in dimerization. Some Cu compounds, however, exhibit uniform columns and higher conducting properties, for which hybridization of the Cu 3d orbitals with the organic radicals is expected. The energy level of Tl 6s is slightly more separated from the TCNQ LUMO, but could potentially mediate similar metal–organic interactions. A simple analytical energy band model is proposed to evaluate the hybridization of the metal orbitals, providing the criteria to form a closed Fermi surface. Accordingly, semiconducting and comparatively high-conducting states of many Cu and Tl TCNQ complexes with uniform columns are to be regarded as a Mott insulating state rather than a Peierls insulating state.

Kojima, Hirotaka↗

Self-organized coherent bursts of stimulated Raman scattering and speckle interaction in multi-speckled laser beams

Nonlinear physics governing the kinetic behavior of stimulated Raman scattering (SRS) in multi-speckled laser beams has been identified in the trapping regime over a wide range of k{lambda}{sub D} values (here k is the wave number of the electron plasma waves and {lambda}{sub D} is the Debye length) in homogeneous and inhomogeneous plasmas. Hot electrons from intense speckles, both forward and side-loss hot electrons produced during SRS daughter electron plasma wave bowing and filamentation, seed and enhance the growth of SRS in neighboring speckles by reducing Landau damping. Trapping-enhanced speckle interaction through transport of hot electrons, backscatter, and sidescatter SRS light waves enable the system of speckles to self-organize and exhibit coherent, sub-ps SRS bursts with more than 100% instantaneous reflectivity, resulting in an SRS transverse coherence width much larger than a speckle width and a SRS spectrum that peaks outside the incident laser cone. SRS reflectivity is found to saturate above a threshold laser intensity at a level of reflectivity that depends on k{lambda}{sub D}: higher k{lambda}{sub D} leads to lower SRS and the reflectivity scales as {approx}(k{lambda}{sub D}){sup -4}. As k{lambda}{sub D} and Landau damping increase, speckle interaction via sidescattered light and side-loss hot electrons decreases and the occurrence of self-organized events becomes infrequent, leading to the reduction of time-averaged SRS reflectivity. It is found that the inclusion of a moderately strong magnetic field in the laser direction can effectively control SRS by suppressing transverse speckle interaction via hot electron transport.

70 PLASMA PHYSICS AND FUSION TECHNOLOGY↗

Continuous roll-to-roll fabrication of organic photovoltaic cells via interconnected high-vacuum and low-pressure organic vapor phase deposition systems

We demonstrate continuous roll-to-roll (R2R) fabrication of single junction and tandem organic photovoltaic (OPV) cells on flexible plastic substrates employing a system that integrates organic deposition by high vacuum thermal evaporation (VTE) and low pressure organic vapor phase deposition (OVPD). By moving the substrate from chamber to chamber and then depositing films on stationary substrates, we achieve power conversion efficiencies of PCE = 8.6 ± 0.3% and 8.9 ± 0.2% for the single junction and tandem cells, respectively. Single junction OPVs are also fabricated on a continuously translating substrate at 0.3 cm/s, to achieve PCE = 8.5 ± 0.2%. Thin films grown on translating substrates by OVPD show <3% thickness non-uniformity and 0.66 nm root mean square surface roughness, similar to that obtained by VTE. Our results suggest that R2R film deposition comprising multiple vapor deposition technologies is a promising method for rapid speed and continuous manufacturing of high quality, small molecular weight organic electronic materials.

42 ENGINEERING↗

Enabling enhanced emission and low-threshold lasing of organic molecules using special Fano resonances of macroscopic photonic crystals

The nature of light interaction with matter can be dramatically altered in optical cavities, often inducing nonclassical behavior. In solid-state systems, excitons need to be spatially incorporated within nanostructured cavities to achieve such behavior. Although fascinating phenomena have been observed with inorganic nanostructures, the incorporation of organic molecules into the typically inorganic cavity is more challenging. We present a unique optofluidic platform comprising organic molecules in solution suspended on a photonic crystal surface, which supports macroscopic Fano resonances and allows strong and tunable interactions with the molecules anywhere along the surface. We develop a theoretical framework of this system and present a rigorous comparison with experimental measurements, showing dramatic spectral and angular enhancement of emission. We then demonstrate that these enhancement mechanisms enable lasing of only a 100-nm thin layer of diluted solution of organic molecules with substantially reduced threshold intensity, which has important implications for organic light-emitting devices and molecular sensing.

74 ATOMIC AND MOLECULAR PHYSICS↗

Quenching measurements and modeling of a boron-loaded organic liquid scintillator

Organic liquid scintillators are used in a wide variety of applications in experimental nuclear and particle physics. Boron-loaded scintillators are particularly useful for detecting neutron captures, due to the high thermal neutron capture cross section of 10 B. These scintillators are commonly used in neutron detectors, including the DarkSide-50 neutron veto, where the neutron may produce a signal when it scatters o protons in the scintillator or when it captures on 10 B. Reconstructing the energy of these recoils is complicated by scintillation quenching. Understanding how nuclear recoils are quenched in these scintillators is an important and dicult problem. In this article, we present a set of measurements of neutron-induced proton recoils in a boron-loaded organic liquid scintillator at recoil energies ranging from 57-467 keV, and we compare these measurements to predictions from different quenching models. We and that a modified Birks' model whose denominator is quadratic in dE=dx best describes the measurements, with χ 2 /NDF = 1:6. This result will help model nuclear recoil scintillation in similar detectors and can be used to improve their neutron tagging efficiency.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

Toward optimal organ at risk sparing in complex volumetric modulated arc therapy: An exponential trade-off with target volume dose homogeneity

Purpose: Conventional radiotherapy typically aims for homogenous dose in the planning target volume (PTV) while sparing organs at risk (OAR). The authors quantified and characterized the trade-off between PTV dose inhomogeneity (IH) and OAR sparing in complex head and neck volumetric modulated arc therapy plans. Methods: Thirteen simultaneous integrated boost plans were created per patient, for ten patients. PTV boost{sub (B)}/elective{sub (E)} optimization priorities were systematically increased. IH{sub B} and IH{sub E}, defined as (100% − V95%) + V107%, were evaluated against the average of the mean dose to the combined composite swallowing and combined salivary organs (D-OAR{sub comp}). To investigate the influence of OAR size and position with respect to PTV{sub B/E}, OAR dose was evaluated against a modified Euclidean distance (DM{sub B}/DM{sub E}) between OAR and PTV. Results: Although the achievable D-OAR{sub comp} for a given level of PTV IH differed between patients, excellent logarithmic fits described the D-OAR{sub comp}/IH{sub B} and IH{sub E} relationship in all patients (mean R{sup 2} of 0.98 and 0.97, respectively). Allowing an increase in average IH{sub B} and IH{sub E} over a clinically acceptable range, e.g., from 0.4% ± 0.5% to 2.0% ± 2.0% and 6.9% ± 2.8% to 14.8% ± 2.7%, respectively, corresponded to a decrease in average dose to the composite salivary and swallowing structures from 30.3 ± 6.5 to 23.6 ± 4.7 Gy and 32.5 ± 8.3 to 26.8 ± 9.3 Gy. The increase in PTV{sub E} IH was mainly accounted for by an increase in V107, by on average 5.9%, rather than a reduction in V95, which was on average only 2%. A linear correlation was found between the OAR dose to composite swallowing structures and contralateral parotid and submandibular gland, with DM{sub E} (R{sup 2} = 0.83, 0.88, 0.95). Only mean ipsilateral parotid dose correlated with DM{sub B} (R{sup 2} = 0.87). Conclusions: OAR sparing is highly dependent on the permitted PTV{sub B/E} IH. PTV{sub E} IH substantially influences OAR doses. These results are relevant for clinical practice and for future automated treatment-planning strategies.

62 RADIOLOGY AND NUCLEAR MEDICINE↗

Manipulating Light with Transition Metal Clusters, Organic Dyes, and Metal Organic Frameworks

The primary goals of our research program is to develop and apply state-of-the-art first-principles methods to predict electronic and optical properties of three systems of significant scientific and technological interest: transition metal clusters, organic dyes, and metal-organic frameworks. These systems offer great opportunities to manipulate light for a wide ranging list of energy-related scientific problems and applications. During this grant period, we focused our investigations on the development, implementation, and benchmarking of many-body Green’s function methods (GW approximation and the Bethe-Salpeter equation) to examine excited-state properties of transition metal/transition-metal-oxide clusters and organic molecules that comprise the building blocks of dyes and metal-organic frameworks.

36 MATERIALS SCIENCE↗

Dispersible Colloid Facilitated Release of Organic Carbon From Two Contrasting Riparian Sediments

In aqueous systems, including groundwater, nano-colloids (1–100 nm diameter) and small colloids (<450 nm diameter) provide a vast store of surfaces to which organic carbon (OC) can sorb, precluding its normal bioavailability. Because nanomaterials are ubiquitous and abundant throughout Earth systems, it is reasonable that they would play a significant role in biogeochemical cycles. As such, mineral nano-colloids (MNC) and small colloids, formed through mineral weathering and precipitation processes, are both an unaccounted-for reservoir and unquantified vector for transport of OC and nutrients and contaminants within watersheds. Water extractions and leaching experiments were conducted under (1) aerobic (ambient) and (2) anaerobic (environmental chamber) conditions for each of two contrasting riparian sediments from (1) Columbia River, Washington and (2) Tims Branch, South Carolina. Water dispersible colloid-adsorbed OC was as high as 48% of OC for Tims Branch anaerobic batch water extraction and as low as 0% for Columbia River aerobic batch water extractions. Anaerobic leaching from column experiments yielded higher colloid and OC release rates. Transmission electron microscopy with electron dispersive spectroscopy mapping revealed organic carbon associated with aggregations of nano-particulate silicate minerals and Mossbauer identified nano-particulate goethite. This exploratory study demonstrates that mineral facilitated release of OC in riparian sediments is both significant and variable between locations.

Rod, Kenton A.↗

Volatility and lifetime against OH heterogeneous reaction of ambient isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA)

Abstract. Isoprene-epoxydiols-derived secondary organic aerosol (IEPOX-SOA) can contribute substantially to organic aerosol (OA) concentrations in forested areas under low NO conditions, hence significantly influencing the regional and global OA budgets, accounting, for example, for 16–36 % of the submicron OA in the southeastern United States (SE US) summer. Particle evaporation measurements from a thermodenuder show that the volatility of ambient IEPOX-SOA is lower than that of bulk OA and also much lower than that of known monomer IEPOX-SOA tracer species, indicating that IEPOX-SOA likely exists mostly as oligomers in the aerosol phase. The OH aging process of ambient IEPOX-SOA was investigated with an oxidation flow reactor (OFR). New IEPOX-SOA formation in the reactor was negligible, as the OFR does not accelerate processes such as aerosol uptake and reactions that do not scale with OH. Simulation results indicate that adding ∼ 100 µg m−3 of pure H2SO4 to the ambient air allows IEPOX-SOA to be efficiently formed in the reactor. The heterogeneous reaction rate coefficient of ambient IEPOX-SOA with OH radical (kOH) was estimated as 4.0 ± 2.0 × 10−13 cm3 molec−1 s−1, which is equivalent to more than a 2-week lifetime. A similar kOH was found for measurements of OH oxidation of ambient Amazon forest air in an OFR. At higher OH exposures in the reactor (> 1 × 1012 molec cm−3 s), the mass loss of IEPOX-SOA due to heterogeneous reaction was mainly due to revolatilization of fragmented reaction products. We report, for the first time, OH reactive uptake coefficients (γOH = 0.59 ± 0.33 in SE US and γOH = 0.68 ± 0.38 in Amazon) for SOA under ambient conditions. A relative humidity dependence of kOH and γOH was observed, consistent with surface-area-limited OH uptake. No decrease of kOH was observed as OH concentrations increased. These observations of physicochemical properties of IEPOX-SOA can help to constrain OA impact on air quality and climate.

Hu, Weiwei↗

The effects of ultraviolet light on the degradation of organic compounds - A possible explanation for the absence of organic matter on Mars

The analysis of the top layer of the Martian regolith at the two Viking landing sites did not reveal any indigenous organic compounds. However, the existence of such compounds at deeper layers cannot be ruled out. Cosmochemical considerations indicate various potential sources for organic matter on Mars, such as comets and meteorites. The study tested the stability of a sample of the Murchison meteorite and various organic substances which have been detected in carbonaceous chondrites, such as glycine, adenine and naphthalene, to the action of ultraviolet light. The compounds were adsorbed on powdered quartz and on California desert soil and were irradiated in the presence or absence of oxygen. The organic content, before and after irradiation, was measured by carbon elementary analysis, UV-absorption, amino acid analysis or pyrolysis-gas chromatography-mass spectrometry. In the absence of oxygen, adenine and glycine appear to be stable over the given part of irradiation. A definite degradation was noticed in the case of naphtalene and the Murchison meteorite. In the presence of oxygen in amounts comparable to those on Mars all compounds were degraded. The degree of degradation was influenced by the irradiation time, temperature and oxygen content.

Oro, J.↗

The fate or organic matter during planetary accretion - Preliminary studies of the organic chemistry of experimentally shocked Murchison meteorite

The fate of organic matter in carbonaceous meteorites during hypervelocity (1-2 km/sec) impacts is investigated using results of experiments in which three samples of the Murchison (CM2) carbonaceous chondrite were shocked to 19, 20, and 36 GPa and analyzed by highly sensitive thermal-desorption photoionization mass spectrometry (SALI). The thermal-desorptive SALI mass spectra of unshocked CM2 material revealed presence of indigenous aliphatic, aromatic, sulfur, and organosulfur compounds, and samples shocked to about 20 GPa showed little or no loss of organic matter. On the other hand, samples shocked to 36 GPa exhibited about 70 percent loss of organic material and a lower alkene/alkane ratio than did the starting material. The results suggest that it is unlikely that the indigenous organic matter in carbonaceous chondritelike planetesimals could have survived the impact on the earth in the later stages of earth's accretion.

Tingle, Tracy N.↗

Interstellar/Precometary Organic Material and the Photochemical Evolution of Complex Organics

During the past two decades ground-, air-, and space-based infrared spectroscopic observations, combined with realistic laboratory simulations, have revolutionized our understanding of interstellar ice and dust, the raw materials from which planets, comets and stars form. Most interstellar material is concentrated in Large molecular clouds where simple molecules are formed by dust grain and gas phase reactions. Gaseous species striking the cold (10 K) dust will stick, forming an icy grain mantle. This accretion, coupled with energetic particle bombardment and UV photolysis, will produce a complex chemical mixture containing volatile, non-volatile, and isotopically fractionated species. Ices in molecular clouds contain the very simple molecules H2O, CH3OH, CO, CO2, H2, and perhaps some NH3 and H2CO, as well as more complex species including nitriles and ketones or esters. The evidence for these compounds as well as carbon rich materials such as polycyclic aromatic hydrocarbons (PAHs), microdiamonds, and amorphous carbon will be reviewed and the possible connections with comets and meteorites will be presented in the first part of the talk. The second part of the presentation will focus on interstellar/precometary ice photochemical evolution. The chemical composition and photochemical evolution of realistic interstellar/pre-cometary ice analogs containing methanol will be discussed. ultraviolet photolysis of these ices produces H2, H2CO, CO2, CO, CH4, HCO, and more complex molecules. Infrared spectroscopy, H-1 and C-13 nuclear magnetic resonance (NMR) spectroscopy, and gas chromatography-mass spectrometry demonstrate that when ices representative of interstellar grains and comets are exposed to UV radiation at low temperature a series of moderately complex organic molecules are formed in the ice including: CH3CH2OH (ethanol), HC(=O)NH2 (formamide), CH3C(=O)NH2 (acetamide), and R-C(integral)N (nitriles). Several of these are already known to be in the interstellar medium, and their presence indicates the importance of grain processing. After warming to room temperature what remains is an organic residue composed primarily of Hexamethylenetetramine (HMT, C6H12N4), with lesser amounts of polyoxymethylene related species (POMs), amides, and ketones. This is in sharp contrast to the organic residues produced by irradiating ices which do not contain methanol (unrealistic interstellar ice analogs) or thermally promoted polymerization-type reactions in unirradiated realistic ice mixtures. Here HMT is only a minor product in a residue dominated by a mixture of polyoxymethylene related species. The implications, for infrared astronomy and astrochemistry, of high concentrations of HMT in interstellar and cometary ices may be profound. The ultraviolet photolysis of HMT frozen in H20 ice produces the "XCN" band observed in the spectra of protostellar objects and laboratory ices, as well as carbon oxides and other nitriles. Thus, HMT may be a precursor of XCN in protostellar objects and a source of CN and CO in the tail of comets. Also, HMT is known to hydrolyze under acidic conditions to yield ammonia and formaldehyde as well as amino acids. Thus, HMT may have been a source of organic material delivered to the early earth by comets.

Allamandola, Lou J.↗

The strength of a calcified tissue depends in part on the molecular structure and organization of its constituent mineral crystals in their organic matrix

High-voltage electron-microscopic tomographic (3D) studies of the ultrastructural interaction between mineral and organic matrix in a variety of calcified tissues reveal different crystal structural and organizational features in association with their respective organic matrices. In brittle or weak pathologic or ectopic calcifications, including examples of osteogenesis imperfecta, calciphylaxis, calcergy, and dermatomyositis, hydroxyapatite crystals occur in various sizes and shapes and are oriented and aligned with respect to collagen in a manner which is distinct from that found in normal calcified tissues. A model of collagen-mineral interaction is proposed which may account for the observed crystal structures and organization. The results indicate that the ultimate strength, support, and other mechanical properties provided by a calcified tissue are dependent in part upon the molecular structure and arrangement of its constituent mineral crystals within their organic matrix.

Non-NASA Center↗

Formation of Complex Organic Molecules (COMs) from Polycyclic Aromatic Hydrocarbons (PAHs): Top-Down Synthesis of organics in planetary systems

Complex, organic molecules have been found in many solar system objects (i.e., dust, comets, meteorites, moons, etc.); however, their origins and formation remain a mystery. Two chemical evolutionary pathways have been proposed to explain the organic inventory of our solar system. The first pathway, the top-down approach, suggests an interstellar (ISM) heritage whereby the organic material found in the solar system formed from the erosion and functionalization of large pre-solar carbon-bearing species (mainly large Polycyclic Aromatic Hydrocarbons or PAHs). The second pathway suggests that the origin of the Solar System prebiotic matter is the result of bottom-up synthesis from small reactive molecules (e.g., formaldehyde – H2CO, acetylene – H2C2, and similar species). In this second scenario, it is supposed that very few, if any, pre-solar large molecules could have survived due to the proto - solar nebula radiation environment. Polycyclic Aromatic Hydrocarbons or PAHs comprise ~20-30% of all available carbon in the Universe. The PAHs found within our Solar System tend to be smaller than those suspected to be in the ISM, comprised of only 14 to 18 carbon atoms in size whereas ISM PAHs are typically 50 to 100 carbon atoms. The disparity in PAH sizes between the ISM and Solar System environments is not understood, but may point to conversion of large ISM PAHs to Solar System Organics. This presentation details recent experiments regarding the stability of large PAHs to the various types of radiation found within a proto - solar disk and the production of smaller, complex, molecules from the degradation of the larger PAHs. The presentation will highlight differences and similarities in degradation products based on experimental conditions (e.g., radiation type) and discuss future work with a new experimental setup known as ICEE (Institute for Carbon Evolution Experiments).

molecukes↗

Methods for associating or dissociating guest materials with a metal organic framework, systems for associating or dissociating guest materials within a series of metal organic frameworks, thermal energy transfer assemblies, and methods for transferring thermal energy

Methods for releasing associated guest materials from a metal organic framework are provided. Methods for associating guest materials with a metal organic framework are also provided. Methods are provided for selectively associating or dissociating guest materials with a metal organic framework. Systems for associating or dissociating guest materials within a series of metal organic frameworks are provided. Thermal energy transfer assemblies are provided. Methods for transferring thermal energy are also provided.

42 ENGINEERING↗