Cluster-Randomized, Crossover Trial of Head Positioning in Acute Stroke.

PubMed

Anderson, Craig S; Arima, Hisatomi; Lavados, Pablo; Billot, Laurent; Hackett, Maree L; Olavarría, Verónica V; Muñoz Venturelli, Paula; Brunser, Alejandro; Peng, Bin; Cui, Liying; Song, Lily; Rogers, Kris; Middleton, Sandy; Lim, Joyce Y; Forshaw, Denise; Lightbody, C Elizabeth; Woodward, Mark; Pontes-Neto, Octavio; De Silva, H Asita; Lin, Ruey-Tay; Lee, Tsong-Hai; Pandian, Jeyaraj D; Mead, Gillian E; Robinson, Thompson; Watkins, Caroline

2017-06-22

The role of supine positioning after acute stroke in improving cerebral blood flow and the countervailing risk of aspiration pneumonia have led to variation in head positioning in clinical practice. We wanted to determine whether outcomes in patients with acute ischemic stroke could be improved by positioning the patient to be lying flat (i.e., fully supine with the back horizontal and the face upwards) during treatment to increase cerebral perfusion. In a pragmatic, cluster-randomized, crossover trial conducted in nine countries, we assigned 11,093 patients with acute stroke (85% of the strokes were ischemic) to receive care in either a lying-flat position or a sitting-up position with the head elevated to at least 30 degrees, according to the randomization assignment of the hospital to which they were admitted; the designated position was initiated soon after hospital admission and was maintained for 24 hours. The primary outcome was degree of disability at 90 days, as assessed with the use of the modified Rankin scale (scores range from 0 to 6, with higher scores indicating greater disability and a score of 6 indicating death). The median interval between the onset of stroke symptoms and the initiation of the assigned position was 14 hours (interquartile range, 5 to 35). Patients in the lying-flat group were less likely than patients in the sitting-up group to maintain the position for 24 hours (87% vs. 95%, P<0.001). In a proportional-odds model, there was no significant shift in the distribution of 90-day disability outcomes on the global modified Rankin scale between patients in the lying-flat group and patients in the sitting-up group (unadjusted odds ratio for a difference in the distribution of scores on the modified Rankin scale in the lying-flat group, 1.01; 95% confidence interval, 0.92 to 1.10; P=0.84). Mortality within 90 days was 7.3% among the patients in the lying-flat group and 7.4% among the patients in the sitting-up group (P=0.83). There were no significant between-group differences in the rates of serious adverse events, including pneumonia. Disability outcomes after acute stroke did not differ significantly between patients assigned to a lying-flat position for 24 hours and patients assigned to a sitting-up position with the head elevated to at least 30 degrees for 24 hours. (Funded by the National Health and Medical Research Council of Australia; HeadPoST ClinicalTrials.gov number, NCT02162017 .).

Film growth, adsorption and desorption kinetics of indigo on SiO2

PubMed Central

Scherwitzl, Boris; Resel, Roland; Winkler, Adolf

2015-01-01

Organic dyes have recently been discovered as promising semiconducting materials, attributable to the formation of hydrogen bonds. In this work, the adsorption and desorption behavior, as well as thin film growth was studied in detail for indigo molecules on silicon dioxide with different substrate treatments. The material was evaporated onto the substrate by means of physical vapor deposition under ultra-high vacuum conditions and was subsequently studied by Thermal Desorption Spectroscopy (TDS), Auger Electron Spectroscopy, X-Ray Diffraction, and Atomic Force Microscopy. TDS revealed initially adsorbed molecules to be strongly bonded on a sputter cleaned surface. After further deposition a formation of dimers is suggested, which de-stabilizes the bonding mechanism to the substrate and leads to a weakly bonded adsorbate. The dimers are highly mobile on the surface until they get incorporated into energetically favourable three-dimensional islands in a dewetting process. The stronger bonding of molecules within those islands could be shown by a higher desorption temperature. On a carbon contaminated surface no strongly bonded molecules appeared initially, weakly bonded monomers rather rearrange into islands at a surface coverage that is equivalent to one third of a monolayer of flat-lying molecules. The sticking coefficient was found to be unity on both substrates. The desorption energies from carbon covered silicon dioxide calculated to 1.67 ± 0.05 eV for multilayer desorption from the islands and 0.84 ± 0.05 eV for monolayer des orption. Corresponding values for desorption from a sputter cleaned surface are 1.53 ± 0.05 eV for multilayer and 0.83 ± 0.05 eV for monolayer desorption. PMID:24832297

Film growth, adsorption and desorption kinetics of indigo on SiO{sub 2}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Scherwitzl, Boris, E-mail: b.scherwitzl@tugraz.at; Resel, Roland; Winkler, Adolf

2014-05-14

Organic dyes have recently been discovered as promising semiconducting materials, attributable to the formation of hydrogen bonds. In this work, the adsorption and desorption behavior, as well as thin film growth was studied in detail for indigo molecules on silicon dioxide with different substrate treatments. The material was evaporated onto the substrate by means of physical vapor deposition under ultra-high vacuum conditions and was subsequently studied by Thermal Desorption Spectroscopy (TDS), Auger Electron Spectroscopy, X-Ray Diffraction, and Atomic Force Microscopy. TDS revealed initially adsorbed molecules to be strongly bonded on a sputter cleaned surface. After further deposition a formation ofmore » dimers is suggested, which de-stabilizes the bonding mechanism to the substrate and leads to a weakly bonded adsorbate. The dimers are highly mobile on the surface until they get incorporated into energetically favourable three-dimensional islands in a dewetting process. The stronger bonding of molecules within those islands could be shown by a higher desorption temperature. On a carbon contaminated surface no strongly bonded molecules appeared initially, weakly bonded monomers rather rearrange into islands at a surface coverage that is equivalent to one third of a monolayer of flat-lying molecules. The sticking coefficient was found to be unity on both substrates. The desorption energies from carbon covered silicon dioxide calculated to 1.67 ± 0.05 eV for multilayer desorption from the islands and 0.84 ± 0.05 eV for monolayer desorption. Corresponding values for desorption from a sputter cleaned surface are 1.53 ± 0.05 eV for multilayer and 0.83 ± 0.05 eV for monolayer desorption.« less

Film growth, adsorption and desorption kinetics of indigo on SiO2.

PubMed

Scherwitzl, Boris; Resel, Roland; Winkler, Adolf

2014-05-14

Organic dyes have recently been discovered as promising semiconducting materials, attributable to the formation of hydrogen bonds. In this work, the adsorption and desorption behavior, as well as thin film growth was studied in detail for indigo molecules on silicon dioxide with different substrate treatments. The material was evaporated onto the substrate by means of physical vapor deposition under ultra-high vacuum conditions and was subsequently studied by Thermal Desorption Spectroscopy (TDS), Auger Electron Spectroscopy, X-Ray Diffraction, and Atomic Force Microscopy. TDS revealed initially adsorbed molecules to be strongly bonded on a sputter cleaned surface. After further deposition a formation of dimers is suggested, which de-stabilizes the bonding mechanism to the substrate and leads to a weakly bonded adsorbate. The dimers are highly mobile on the surface until they get incorporated into energetically favourable three-dimensional islands in a dewetting process. The stronger bonding of molecules within those islands could be shown by a higher desorption temperature. On a carbon contaminated surface no strongly bonded molecules appeared initially, weakly bonded monomers rather rearrange into islands at a surface coverage that is equivalent to one third of a monolayer of flat-lying molecules. The sticking coefficient was found to be unity on both substrates. The desorption energies from carbon covered silicon dioxide calculated to 1.67 ± 0.05 eV for multilayer desorption from the islands and 0.84 ± 0.05 eV for monolayer desorption. Corresponding values for desorption from a sputter cleaned surface are 1.53 ± 0.05 eV for multilayer and 0.83 ± 0.05 eV for monolayer desorption.

Structural deformation at the Flynn Creek impact crater, Tennessee - A preliminary report on deep drilling

NASA Technical Reports Server (NTRS)

Roddy, D. J.

1979-01-01

The geologic and core drilling studies described in the present paper show that the Flynn Creek crater has such distinctive morphological features as a broad flat hummocky floor; large central peak; locally terraced crater walls; uplifted, as well as flat-lying rim segments; and a surrounding ejecta blanket. The major structural features include a shallow depth of total brecciation and excavation as compared with apparent crater diameter; a thin breccia lens underlain by a thin zone of disrupted strata; concentric ring fault zones in inner rim, beneath crater wall, and outer crater floor regions; a large central uplift underlain by a narrow dipping zone of deeply disrupted strata; faulted, folded, brecciated, and fractured rim strata; and uplifted rim strata, which dip away from the crater, and flat-lying rim strata, which terminate as inward dipping rocks.

Molecular adsorption and multilayer growth of pentacene on Cu(100):Layer structure and energetics

NASA Astrophysics Data System (ADS)

Satta, M.; Iacobucci, S.; Larciprete, R.

2007-04-01

We used the partial charge tight binding method to perform a full structure optimization to determine equilibrium adsorption geometries, energetics, and local charge redistribution for molecular adsorption and multilayer growth of pentacene on Cu(100). We found that single molecule adsorption induces only a localized perturbation of the metal lattice which is limited to the topmost layers. At saturation coverage four stable topologies (Brick, Wave, Lines and Zigzag) were identified, all based on pentacene molecules lying flat on the metal surface and with the central phenyl ring adsorbed in top position. Only two (Brick and Wave) out of the four structures are able to sustain multilayer growth. In both cases, assembling beyond the second layer corresponds to a transition from the flat to a tilted geometry, in which the pentacenes adopt a face-plane-face arrangement leading to a herringbone structure. The energetics of the different structure are reported as a function of the molecular number density of the pentacene multilayer by calculating cohesive, stress, and electrostatic energies. The dominant tilted molecular orientation in the pentacene multilayer is in agreement with the average tilt angle of 65° between the molecular plane and the Cu surface derived by near edge x-ray absorption spectroscopy of a four monolayer pentacene film deposited on Cu(100).

Active sites and states in the heterogeneous catalysis of carbon-hydrogen bonds.

PubMed

Somorjai, Gabor A; Marsh, Anderson L

2005-04-15

C-H bond activation for several alkenes (ethylene, propylene, isobutene, cyclohexene and 1-hexene) and alkanes (methane, ethane, n-hexane, 2-methylpentane and 3-methylpentane) has been studied on the (111) crystal face of platinum as a function of temperature at low (10(-6) Torr) and high (>/=1 Torr) pressures in the absence and presence of hydrogen pressures (>/=10 Torr). Sum frequency generation (SFG) vibrational spectroscopy has been used to characterize the adsorbate structures and high pressure scanning tunnelling microscopy (HP-STM) has been used to monitor their surface mobility under reaction conditions during hydrogenation, dehydrogenation and CO poisoning. C-H bond dissociation occurs at low temperatures, approximately 250 K, for all of these molecules, although only at high pressures for the weakly bound alkanes because of their low desorption temperatures. Bond dissociation is known to be surface structure sensitive and we find that it is also accompanied by the restructuring of the metal surface. The presence of hydrogen slows down dehydrogenation and for some of the molecules it influences the molecular rearrangement, thus altering reaction selectivity. Surface mobility of adsorbates is essential to produce catalytic activity. When surface diffusion is inhibited by CO adsorption, ordered surface structures form and the reaction is poisoned. Ethylene hydrogenation is surface structure insensitive, while cyclohexene hydrogenation and dehydrogenation are structure sensitive. n-Hexane and other C6 alkanes form either upright or flat-lying molecules on the platinum surface which react to produce branched isomers or benzene, respectively.

Face specificity and the role of metal adatoms in molecular reorientation at surfaces

NASA Astrophysics Data System (ADS)

Perry, C. C.; Haq, S.; Frederick, B. G.; Richardson, N. V.

1998-07-01

Using reflection absorption infrared spectroscopy (RAIRS), the coverage-dependent reorientation of the benzoate species on the (110) and (111) faces of copper is compared and contrasted. Whereas on Cu(110) benzoate reorients from a flat-lying to an upright orientation with increasing coverage, on Cu(111), at all coverages, benzoate is aligned normal to the surface. The formation of periodic, flat-lying copper-benzoate structures has been attributed to the availability of metal adatoms, which differs dramatically between the (111) and (110) faces. We discuss the face specificity of molecular orientation by comparing calculated formation energies of adatom vacancies from ledges and kink sites on (100), (110) and (111) faces. Further support for this model is given by the evaporation of sodium, either by pre- or post-dosing, onto low-coverage benzoate/Cu(111), which induces benzoate to convert from a perpendicular to a parallel orientation. Likewise, coevaporation of Cu while dosing benzoic acid onto the Cu(111) surface also results in a majority of flat-lying benzoate species. Finally, for adsorption on the p(2×1)O/Cu(110) reconstruction, benzoate occurs only as the upright species, which is consistent with reducing the copper mobility and availability on the (110) face. We therefore suggest the possible role of metal adatoms as a new mechanism in controlling adsorbate orientation and therefore face specificity in surface reactions.

Electronic structure at transition metal phthalocyanine-transition metal oxide interfaces: Cobalt phthalocyanine on epitaxial MnO films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Glaser, Mathias; Peisert, Heiko, E-mail: heiko.peisert@uni-tuebingen.de; Adler, Hilmar

2015-03-14

The electronic structure of the interface between cobalt phthalocyanine (CoPc) and epitaxially grown manganese oxide (MnO) thin films is studied by means of photoemission (PES) and X-ray absorption spectroscopy (XAS). Our results reveal a flat-lying adsorption geometry of the molecules on the oxide surface which allows a maximal interaction between the π-system and the substrate. A charge transfer from MnO, in particular, to the central metal atom of CoPc is observed by both PES and XAS. The change of the shape of N-K XAS spectra at the interface points, however, to the involvement of the Pc macrocycle in the chargemore » transfer process. As a consequence of the charge transfer, energetic shifts of MnO related core levels were observed, which are discussed in terms of a Fermi level shift in the semiconducting MnO films due to interface charge redistribution.« less

Well-ordered structure of methylene blue monolayers on Au(111) surface: electrochemical scanning tunneling microscopy studies.

PubMed

Song, Yonghai; Wang, Li

2009-02-01

Well-ordered structure of methylene blue (MB) monolayers on Au(111) surface has been successfully obtained by controlling the substrate potential. Electrochemical scanning tunneling microscopy (ECSTM) examined the monolayers of MB on Au(111) in 0.1 M HClO(4) and showed long-range ordered, interweaved arrays of MB with quadratic symmetry on the substrate in the potential range of double-layer charging. High-resolution ECSTM image further revealed the details of the MB monolayers structure of c(5 x 5 radical 3)rect and the flat-lying orientation of ad-molecules. The dependence of molecular organization on the substrate potential and the formation mechanism of well-ordered structure on Au(111) surface were investigated in detail. The obtained well-ordered structure at the interface between a metal and an aqueous electrolyte might possibly be used as high-density device for signal memory and templates for the advanced nanopatterning of surfaces. (c) 2008 Wiley-Liss, Inc.

Air Photo Analysis, Photo Interpretation Logic, and Feature Extraction,

DTIC Science & Technology

1984-06-01

and at times predict their composi- tion and texture. Such events as deposition, sedimentation , and volcanism constantly add new materials to the...established by depositing sediments in low areas, by large lava flows, by exposure of flat-lying intrusive masses, and * by grinding or eroding an irregular...lying area of sediments can be called a plain only so long. There comes a time when the forces of erosion have so ex- tended and deepened the valleys

Crystal structure and theoretical studies of derivative of imidazo-1,2,4-triazine

NASA Astrophysics Data System (ADS)

Dybała, Izabela; Sztanke, Krzysztof

2016-09-01

In this study, we present the result of X-ray structure analysis of methyl [8-(3-chlorophenyl)-4-oxo-2,3,4,6,7,8-heksahydroimidazo[2,1-c][1,2,4]triazin-3-yl]acetate (1). The molecule conformation is flat, with a chlorophenyl substituent and the ester moiety lying in the plain of the heterobicyclic scaffold. Its conformation is stabilized by an intramolecular Nsbnd H…O hydrogen bond. Within the crystalline structure of 1, molecules associate with one another by weak Csbnd H…O, Csbnd H…Cl and Csbnd H…π bonds. The molecular and crystal structure of 1 was compared with the previously described structurally similar compound possessing the same bicyclic rigid core and similar chemical nature of the functional ester moiety. Very interesting differences in molecules geometry and association were observed. Non-covalent bonds within the crystals are additionally visualized by determination of Hirshfeld surfaces. Moreover, the quantum chemical calculation for 1 in the gas phase were carried out. The DFT calculation methods was used to optimize of molecule geometry and obtain molecular energy profiles with respect to selected torsion angles. The quantum chemical conformational analysis that was carried out for compound 1 in the gas phase suggests that in the solid state the molecules adopt the minimum energy conformation.

Fabrication of ion bombardment induced rippled TiO₂ surfaces to influence subsequent organic thin film growth.

PubMed

Kratzer, Markus; Szajna, Konrad; Wrana, Domink; Belza, Wojciech; Krok, Franciszek; Teichert, Christian

2018-05-23

Control over organic thin film growth is a central issue in the development of organic electronics. The anisotropy and extended size of the molecular building blocks introduce a high degree of complexity within the formation of thin films. This complexity can be even increased for substrates with induced, sophisticated morphology and anisotropy. Thus, targeted structuring like ion beam mediated modification of substrates in order to create ripples, pyramids, or pit structures provides a further degree of freedom in manipulating the growth morphology of organic thin films. We provide a comprehensive review of recent work on para-hexaphenyl (C36H26, 6P) as a typical representative of the class of small, rod-like conjugated molecules and rutile TiO2(110) as an example for a transparent oxide electrode to demonstrate the effect of ion beam induced nanostructuring on organic thin film growth. Starting from molecular growth on smooth, atomically flat TiO2(110) (11) surfaces, we investigate the influence of the ripple size on the resulting 6P thin films. The achieved 6P morphologies are either crystalline nano-needles composed of flat lying molecules or islands consisting of upright standing 6P, which are elongated in ripple direction. The islands' length to width ratio can be controlled by tuning of the ripples' shape. © 2018 IOP Publishing Ltd.

The role of the van der Waals interactions in the adsorption of anthracene and pentacene on the Ag(111) surface

NASA Astrophysics Data System (ADS)

Morbec, Juliana M.; Kratzer, Peter

2017-01-01

Using first-principles calculations based on density-functional theory (DFT), we investigated the effects of the van der Waals (vdW) interactions on the structural and electronic properties of anthracene and pentacene adsorbed on the Ag(111) surface. We found that the inclusion of vdW corrections strongly affects the binding of both anthracene/Ag(111) and pentacene/Ag(111), yielding adsorption heights and energies more consistent with the experimental results than standard DFT calculations with generalized gradient approximation (GGA). For anthracene/Ag(111) the effect of the vdW interactions is even more dramatic: we found that "pure" DFT-GGA calculations (without including vdW corrections) result in preference for a tilted configuration, in contrast to the experimental observations of flat-lying adsorption; including vdW corrections, on the other hand, alters the binding geometry of anthracene/Ag(111), favoring the flat configuration. The electronic structure obtained using a self-consistent vdW scheme was found to be nearly indistinguishable from the conventional DFT electronic structure once the correct vdW geometry is employed for these physisorbed systems. Moreover, we show that a vdW correction scheme based on a hybrid functional DFT calculation (HSE) results in an improved description of the highest occupied molecular level of the adsorbed molecules.

The gas phase structure of transition metal dihydrides

NASA Astrophysics Data System (ADS)

Demuynck, Jean; Schaefer, Henry F.

1980-01-01

ESR and infrared spectroscopic measurements on matrix isolated MnH2 and CrH2 have recently suggested that these simple molecules may be bent. This result would be the opposite of that found experimentally for the transition metal dihalides MX2, known to be linear. Here the geometrical structure of MnH2 has been investigated by molecular electronic structure theory. A large contracted Gaussian basis set [Mn(14s11p6p/9s8p3d), H(5s1p/3s1p)] was used in conjunction with self-consistent field and configuration interaction methods. These suggest that the 6A1 ground state of MnH2 is linear. Further studies of the 3A1 state (one of several low-lying states) of TiH2 also favor linearity, although this potential energy surface is extremely flat with respect to bending. Thus it appears probable that most MH2 molecules, like the related MX2 family, are linear.

Structure formation in organic thin films observed in real time by energy dispersive near-edge x-ray absorption fine-structure spectroscopy

NASA Astrophysics Data System (ADS)

Scholz, M.; Sauer, C.; Wiessner, M.; Nguyen, N.; Schöll, A.; Reinert, F.

2013-08-01

We study the structure formation of 1,4,5,8-naphthalene-tetracarboxylicacid-dianhydride (NTCDA) multilayer films on Ag(111) surfaces by energy dispersive near-edge x-ray absorption fine-structure spectroscopy (NEXAFS) and photoelectron spectroscopy. The time resolution of seconds of the method allows us to identify several sub-processes, which occur during the post-growth three-dimensional structural ordering, as well as their characteristic time scales. After deposition at low temperature the NTCDA molecules are preferentially flat lying and the films exhibit no long-range order. Upon annealing the molecules flip into an upright orientation followed by an aggregation in a transient phase which exists for several minutes. Finally, three-dimensional islands are established with bulk-crystalline structure involving substantial mass transport on the surface and morphological roughening. By applying the Kolmogorov-Johnson-Mehl-Avrami model the activation energies of the temperature-driven sub-processes can be derived from the time evolution of the NEXAFS signal.

The Killing-Yano equation on Lie groups

NASA Astrophysics Data System (ADS)

Barberis, M. L.; Dotti, I. G.; Santillán, O.

2012-03-01

In this paper we study 2-forms which are solutions of the Killing-Yano equation on Lie groups endowed with a left invariant metric having various curvature properties. We prove a general result for 2-step nilpotent Lie groups and as a corollary we obtain a nondegenerate solution of the Killing-Yano equation on the Iwasawa manifold with its half-flat metric.

Effect of Solvent and Substrate on the Surface Binding Mode of Carboxylate-Functionalized Aromatic Molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Domenico, Janna; Foster, Michael E.; Spoerke, Erik D.

Here, the efficiency of dye-sensitized solar cells (DSSCs) is strongly influenced by dye molecule orientation and interactions with the substrate. Understanding the factors controlling the surface orientation of sensitizing organic molecules will aid in the improvement of both traditional DSSCs and other devices that integrate molecular linkers at interfaces. Here, we describe a general approach to understand relative dye–substrate orientation and provide analytical expressions predicting orientation. We consider the effects of substrate, solvent, and protonation state on dye molecule orientation. In the absence of solvent, our model predicts that most carboxylic acid-functionalized molecules prefer to lie flat (parallel) on themore » surface, due to van der Waals interactions, as opposed to a tilted orientation with respect to the surface that is favored by covalent bonding of the carboxylic acid group to the substrate. When solvation effects are considered, however, the molecules are predicted to orient perpendicular to the surface. We extend this approach to help understand and guide the orientation of metal–organic framework (MOF) thin-film growth on various metal–oxide substrates. A two-part analytical model is developed on the basis of the results of DFT calculations and ab initio MD simulations that predicts the binding energy of a molecule by chemical and dispersion forces on rutile and anatase TiO 2 surfaces, and quantifies the dye solvation energy for two solvents. The model is in good agreement with the DFT calculations and enables rapid prediction of dye molecule and MOF linker binding preference on the basis of the size of the adsorbing molecule, identity of the surface, and the solvent environment. We establish the threshold molecular size, governing dye molecule orientation, for each condition.« less

Effect of Solvent and Substrate on the Surface Binding Mode of Carboxylate-Functionalized Aromatic Molecules

DOE PAGES

Domenico, Janna; Foster, Michael E.; Spoerke, Erik D.; ...

2018-04-25

Here, the efficiency of dye-sensitized solar cells (DSSCs) is strongly influenced by dye molecule orientation and interactions with the substrate. Understanding the factors controlling the surface orientation of sensitizing organic molecules will aid in the improvement of both traditional DSSCs and other devices that integrate molecular linkers at interfaces. Here, we describe a general approach to understand relative dye–substrate orientation and provide analytical expressions predicting orientation. We consider the effects of substrate, solvent, and protonation state on dye molecule orientation. In the absence of solvent, our model predicts that most carboxylic acid-functionalized molecules prefer to lie flat (parallel) on themore » surface, due to van der Waals interactions, as opposed to a tilted orientation with respect to the surface that is favored by covalent bonding of the carboxylic acid group to the substrate. When solvation effects are considered, however, the molecules are predicted to orient perpendicular to the surface. We extend this approach to help understand and guide the orientation of metal–organic framework (MOF) thin-film growth on various metal–oxide substrates. A two-part analytical model is developed on the basis of the results of DFT calculations and ab initio MD simulations that predicts the binding energy of a molecule by chemical and dispersion forces on rutile and anatase TiO 2 surfaces, and quantifies the dye solvation energy for two solvents. The model is in good agreement with the DFT calculations and enables rapid prediction of dye molecule and MOF linker binding preference on the basis of the size of the adsorbing molecule, identity of the surface, and the solvent environment. We establish the threshold molecular size, governing dye molecule orientation, for each condition.« less

Invariant classification of second-order conformally flat superintegrable systems

NASA Astrophysics Data System (ADS)

Capel, J. J.; Kress, J. M.

2014-12-01

In this paper we continue the work of Kalnins et al in classifying all second-order conformally-superintegrable (Laplace-type) systems over conformally flat spaces, using tools from algebraic geometry and classical invariant theory. The results obtained show, through Stäckel equivalence, that the list of known nondegenerate superintegrable systems over three-dimensional conformally flat spaces is complete. In particular, a seven-dimensional manifold is determined such that each point corresponds to a conformal class of superintegrable systems. This manifold is foliated by the nonlinear action of the conformal group in three dimensions. Two systems lie in the same conformal class if and only if they lie in the same leaf of the foliation. This foliation is explicitly described using algebraic varieties formed from representations of the conformal group. The proof of these results rely heavily on Gröbner basis calculations using the computer algebra software packages Maple and Singular.

Resource targets for advanced underground coal extraction systems

NASA Technical Reports Server (NTRS)

Hoag, J. H.; Whipple, D. W.; Habib-Agahi, H.; Lavin, M. L.

1982-01-01

Resource targets appropriate for federal sponsorship of research and development of advanced underground coal mining systems are identified. A comprehensive examination of conventional and unconventional coals with particular attention to exceptionally thin and thick seams, steeply dipping beds, and multiple seam geometry was made. The results indicate that the resource of primary importance is flat lying bituminous coal of moderate thickness, under moderate cover, and located within the lower 48 states. Resources of secondary importance are the flat lying multiple seams and thin seams (especially those in Appalachia). Steeply dipping coals, abandoned pillars, and exceptionally thick western coals may be important in some regions of subregions, but the limited tonnage available places them in a position of tertiary importance.

Effect of gold nanoparticle on stability of the DNA molecule: A study of molecular dynamics simulation.

PubMed

Izanloo, Cobra

2017-09-02

An understanding of the mechanism of DNA interactions with gold nanoparticles is useful in today medicine applications. We have performed a molecular dynamics simulation on a B-DNA duplex (CCTCAGGCCTCC) in the vicinity of a gold nanoparticle with a truncated octahedron structure composed of 201 gold atoms (diameter ∼1.8 nm) to investigate gold nanoparticle (GNP) effects on the stability of DNA. During simulation, the nanoparticle is closed to DNA and phosphate groups direct the particles into the major grooves of the DNA molecule. Because of peeling and untwisting states that are occur at end of DNA, the nucleotide base lies flat on the surface of GNP. The configuration entropy is estimated using the covariance matrix of atom-positional fluctuations for different bases. The results show that when a gold nanoparticle has interaction with DNA, entropy increases. The results of conformational energy and the hydrogen bond numbers for DNA indicated that DNA becomes unstable in the vicinity of a gold nanoparticle. The radial distribution function was calculated for water hydrogen-phosphate oxygen pairs. Almost for all nucleotide, the presence of a nanoparticle around DNA caused water molecules to be released from the DNA duplex and cations were close to the DNA.

Imaging ultrafast dynamics of molecules with laser-induced electron diffraction.

PubMed

Lin, C D; Xu, Junliang

2012-10-14

We introduce a laser-induced electron diffraction method (LIED) for imaging ultrafast dynamics of small molecules with femtosecond mid-infrared lasers. When molecules are placed in an intense laser field, both low- and high-energy photoelectrons are generated. According to quantitative rescattering (QRS) theory, high-energy electrons are produced by a rescattering process where electrons born at the early phase of the laser pulse are driven back to rescatter with the parent ion. From the high-energy electron momentum spectra, field-free elastic electron-ion scattering differential cross sections (DCS), or diffraction images, can be extracted. With mid-infrared lasers as the driving pulses, it is further shown that the DCS can be used to extract atomic positions in a molecule with sub-angstrom spatial resolution, in close analogy to the standard electron diffraction method. Since infrared lasers with pulse duration of a few to several tens of femtoseconds are already available, LIED can be used for imaging dynamics of molecules with sub-angstrom spatial and a few-femtosecond temporal resolution. The first experiment with LIED has shown that the bond length of oxygen molecules shortens by 0.1 Å in five femtoseconds after single ionization. The principle behind LIED and its future outlook as a tool for dynamic imaging of molecules are presented.

Selective adsorption of a supramolecular structure on flat and stepped gold surfaces

NASA Astrophysics Data System (ADS)

Peköz, Rengin; Donadio, Davide

2018-04-01

Halogenated aromatic molecules assemble on surfaces forming both hydrogen and halogen bonds. Even though these systems have been intensively studied on flat metal surfaces, high-index vicinal surfaces remain challenging, as they may induce complex adsorbate structures. The adsorption of 2,6-dibromoanthraquinone (2,6-DBAQ) on flat and stepped gold surfaces is studied by means of van der Waals corrected density functional theory. Equilibrium geometries and corresponding adsorption energies are systematically investigated for various different adsorption configurations. It is shown that bridge sites and step edges are the preferred adsorption sites for single molecules on flat and stepped surfaces, respectively. The role of van der Waals interactions, halogen bonds and hydrogen bonds are explored for a monolayer coverage of 2,6-DBAQ molecules, revealing that molecular flexibility and intermolecular interactions stabilize two-dimensional networks on both flat and stepped surfaces. Our results provide a rationale for experimental observation of molecular carpeting on high-index vicinal surfaces of transition metals.

Properties of copper (fluoro-)phthalocyanine layers deposited on epitaxial graphene.

PubMed

Ren, Jun; Meng, Sheng; Wang, Yi-Lin; Ma, Xu-Cun; Xue, Qi-Kun; Kaxiras, Efthimios

2011-05-21

We investigate the atomic structure and electronic properties of monolayers of copper phthalocyanines (CuPc) deposited on epitaxial graphene substrate. We focus in particular on hexadecafluorophthalocyanine (F(16)CuPc), using both theoretical and experimental (scanning tunneling microscopy - STM) studies. For the individual CuPc and F(16)CuPc molecules, we calculated the electronic and optical properties using density functional theory (DFT) and time-dependent DFT and found a red-shift in the absorption peaks of F(16)CuPc relative to those of CuPc. In F(16)CuPc, the electronic wavefunctions are more polarized toward the electronegative fluorine atoms and away from the Cu atom at the center of the molecule. When adsorbed on graphene, the molecules lie flat and form closely packed patterns: F(16)CuPc forms a hexagonal pattern with two well-ordered alternating α and β stripes while CuPc arranges into a square lattice. The competition between molecule-substrate and intermolecular van der Waals interactions plays a crucial role in establishing the molecular patterns leading to tunable electron transfer from graphene to the molecules. This transfer is controlled by the layer thickness of, or the applied voltage on, epitaxial graphene resulting in selective F(16)CuPc adsorption, as observed in STM experiments. In addition, phthalocyanine adsorption modifies the electronic structure of the underlying graphene substrate introducing intensity smoothing in the range of 2-3 eV below the Dirac point (E(D)) and a small peak in the density of states at ∼0.4 eV above E(D). © 2011 American Institute of Physics.

Ultrafast direct electron transfer at organic semiconductor and metal interfaces.

PubMed

Xiang, Bo; Li, Yingmin; Pham, C Huy; Paesani, Francesco; Xiong, Wei

2017-11-01

The ability to control direct electron transfer can facilitate the development of new molecular electronics, light-harvesting materials, and photocatalysis. However, control of direct electron transfer has been rarely reported, and the molecular conformation-electron dynamics relationships remain unclear. We describe direct electron transfer at buried interfaces between an organic polymer semiconductor film and a gold substrate by observing the first dynamical electric field-induced vibrational sum frequency generation (VSFG). In transient electric field-induced VSFG measurements on this system, we observe dynamical responses (<150 fs) that depend on photon energy and polarization, demonstrating that electrons are directly transferred from the Fermi level of gold to the lowest unoccupied molecular orbital of organic semiconductor. Transient spectra further reveal that, although the interfaces are prepared without deliberate alignment control, a subensemble of surface molecules can adopt conformations for direct electron transfer. Density functional theory calculations support the experimental results and ascribe the observed electron transfer to a flat-lying polymer configuration in which electronic orbitals are found to be delocalized across the interface. The present observation of direct electron transfer at complex interfaces and the insights gained into the relationship between molecular conformations and electron dynamics will have implications for implementing novel direct electron transfer in energy materials.

An experimental study of furan adsorption and decomposition on vicinal palladium surfaces using scanning tunneling microscopy

NASA Astrophysics Data System (ADS)

Loui, A.; Chiang, S.

2018-04-01

The intact adsorption and decomposition of furan (C4H4O) on vicinal palladium surfaces with (111)-oriented terraces has been studied by scanning tunneling microscopy (STM) over a range of temperatures. STM images at 225 K show that furan molecules lie flat and prefer to adsorb at upper step edges. At 225 K, furan molecules adsorbed on "narrow" terraces of 20 to 45 Å in width appear to diffuse more readily than those adsorbed on "wide" terraces of 160 to 220 Å. A distinct population of smaller features appears in STM images on "narrow" terraces at 288 K and on "wide" terraces at 415 K and is identified with the C3H3 decomposition product, agreeing with prior studies which demonstrated that furan dissociates on Pd(111) to yield carbon monoxide (CO) and a C3H3 moiety in the 280 to 320 K range. Based on our direct visualization of this reaction using STM, we propose a spatial mechanism in which adsorption of furan at upper step edges allows catalysis of the dissociation, followed by diffusion of the product to lower step edges.

Chimpanzees know that others make inferences

PubMed Central

Schmelz, Martin; Call, Josep; Tomasello, Michael

2011-01-01

If chimpanzees are faced with two opaque boards on a table, in the context of searching for a single piece of food, they do not choose the board lying flat (because if food was under there it would not be lying flat) but, rather, they choose the slanted one— presumably inferring that some unperceived food underneath is causing the slant. Here we demonstrate that chimpanzees know that other chimpanzees in the same situation will make a similar inference. In a back-and-forth foraging game, when their competitor had chosen before them, chimpanzees tended to avoid the slanted board on the assumption that the competitor had already chosen it. Chimpanzees can determine the inferences that a conspecific is likely to make and then adjust their competitive strategies accordingly. PMID:21282649

An analysis of fracture trace patterns in areas of flat-lying sedimentary rocks for the detection of buried geologic structure. [Kansas and Texas

NASA Technical Reports Server (NTRS)

Podwysocki, M. H.

1974-01-01

Two study areas in a cratonic platform underlain by flat-lying sedimentary rocks were analyzed to determine if a quantitative relationship exists between fracture trace patterns and their frequency distributions and subsurface structural closures which might contain petroleum. Fracture trace lengths and frequency (number of fracture traces per unit area) were analyzed by trend surface analysis and length frequency distributions also were compared to a standard Gaussian distribution. Composite rose diagrams of fracture traces were analyzed using a multivariate analysis method which grouped or clustered the rose diagrams and their respective areas on the basis of the behavior of the rays of the rose diagram. Analysis indicates that the lengths of fracture traces are log-normally distributed according to the mapping technique used. Fracture trace frequency appeared higher on the flanks of active structures and lower around passive reef structures. Fracture trace log-mean lengths were shorter over several types of structures, perhaps due to increased fracturing and subsequent erosion. Analysis of rose diagrams using a multivariate technique indicated lithology as the primary control for the lower grouping levels. Groupings at higher levels indicated that areas overlying active structures may be isolated from their neighbors by this technique while passive structures showed no differences which could be isolated.

The Martian, Part 3: Meridiani Planum

NASA Image and Video Library

2015-10-14

All this week, the THEMIS Image of the Day is following on the real Mars the path taken by fictional astronaut Mark Watney, stranded on the Red Planet in the book and movie, The Martian. Today's image shows a part of the flat terrain of northern Meridiani Planum. This area lies about 300 kilometers (190 miles) north of where Mars rover Opportunity is currently exploring the rim rocks of Endeavour Crater. Meridiani is a large expanse of sedimentary rock, mostly flat-lying basalt sandstone with hematite nodules ("blueberries") embedded in it. Farther south from this scene, Opportunity has examined several craters like these that expose deeper rock layers. They show that the Meridiani sandstone is made of dune sands that were soaked in sulfur-rich water. Flat terrain may make for dull scenery, but the driving is easy. This area is where astronaut Mark Watney turns his vehicle east toward Schiaparelli Crater. Before arriving here, he was driving south to get out from under a dust storm that threatened to shut off power to the vehicle's solar cells. At this point he has journeyed about 2,300 kilometers (1,400 miles) from Acidalia. Orbit Number: 6304 Latitude: 2.51711 Longitude: 355.154 Instrument: VIS Captured: 2003-05-17 13:18 http://photojournal.jpl.nasa.gov/catalog/PIA19798

Shock

MedlinePlus

... skin Rapid but weak pulse Shallow breathing Unconsciousness First Aid Take the following steps if you think a ... harm, leave the person lying flat. Give appropriate first aid for any wounds, injuries, or illnesses. Keep the ...

Extracting conformational structure information of benzene molecules via laser-induced electron diffraction

DOE PAGES

Ito, Yuta; Wang, Chuncheng; Le, Anh-Thu; ...

2016-05-01

Here, we have measured the angular distributions of high energy photoelectrons of benzene molecules generated by intense infrared femtosecond laser pulses. These electrons arise from the elastic collisions between the benzene ions with the previously tunnel-ionized electrons that have been driven back by the laser field. Theory shows that laser-free elastic differential cross sections (DCSs) can be extracted from these photoelectrons, and the DCS can be used to retrieve the bond lengths of gas-phase molecules similar to the conventional electron diffraction method. From our experimental results, we have obtained the C-C and C-H bond lengths of benzene with a spatialmore » resolution of about 10 pm. Our results demonstrate that laser induced electron diffraction (LIED) experiments can be carried out with the present-day ultrafast intense lasers already. Looking ahead, with aligned or oriented molecules, more complete spatial information of the molecule can be obtained from LIED, and applying LIED to probe photo-excited molecules, a “molecular movie” of the dynamic system may be created with sub-A°ngstrom spatial and few-ten femtosecond temporal resolutions.« less

Critical bifurcation of shallow microtidal landforms in tidal flats and salt marshes

PubMed Central

Fagherazzi, Sergio; Carniello, Luca; D'Alpaos, Luigi; Defina, Andrea

2006-01-01

Shallow tidal basins are characterized by extensive tidal flats and salt marshes that lie within specific ranges of elevation, whereas intermediate elevations are less frequent in intertidal landscapes. Here we show that this bimodal distribution of elevations stems from the characteristics of wave-induced sediment resuspension and, in particular, from the reduction of maximum wave height caused by dissipative processes in shallow waters. The conceptual model presented herein is applied to the Venice Lagoon, Italy, and demonstrates that areas at intermediate elevations are inherently unstable and tend to become either tidal flats or salt marshes. PMID:16707583

Breathing Difficulties

MedlinePlus

... frequently during the night (insomnia) Difficulty lying flat ALS and your lungs Breathing in and out is ... improve effective coughing. Techniques are explained in The ALS Association’s Living with ALS manual #6 “Adapting to ...

OUT Success Stories: Solar Hot Water Technology

DOE R&D Accomplishments Database

Clyne, R.

2000-08-01

Solar hot water technology was made great strides in the past two decades. Every home, commercial building, and industrial facility requires hot water. DOE has helped to develop reliable and durable solar hot water systems. For industrial applications, the growth potential lies in large-scale systems, using flat-plate and trough-type collectors. Flat-plate collectors are commonly used in residential hot water systems and can be integrated into the architectural design of the building.

A Review of Land and Stream Classifications in Support of Developing a National Ordinary High Water Mark (OHWM) Classification

DTIC Science & Technology

2014-08-01

northern Minnesota, Wisconsin, and Michigan. This region is dominated by igneous and metamorphic rock , with some sedimentary units and a generally...faulted igneous and metamorphic rocks and folded sediments in the Appalachians and flat-lying sedimentary rocks in the Plateau and Catskills. Streams...mixture of igneous, metamorphic , and sedimentary rocks . High relief and coarse materials are typical. Riffle and pool development is largely

Rock Slope Design Criteria

DOT National Transportation Integrated Search

2010-06-01

Based on the stratigraphy and the type of slope stability problems, the flat lying, Paleozoic age, sedimentary : rocks of Ohio were divided into three design units: 1) competent rock design unit consisting of sandstones, limestones, : and siltstones ...

Incomplete Puzzle

NASA Technical Reports Server (NTRS)

2006-01-01

15 April 2006 This Mars Global Surveyor (MGS) Mars Orbiter Camera (MOC) image shows a mid-summer view of a portion of the south polar residual cap of Mars. The large, relatively flat-lying, puzzle-like pieces in this scene are mesas composed largely of solid carbon dioxide.

Location near: 85.5oS, 76.8oW Image width: 3 km (1.9 mi) Illumination from: upper left Season: Southern Summer

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ito, Yuta; Wang, Chuncheng; Le, Anh-Thu

Here, we have measured the angular distributions of high energy photoelectrons of benzene molecules generated by intense infrared femtosecond laser pulses. These electrons arise from the elastic collisions between the benzene ions with the previously tunnel-ionized electrons that have been driven back by the laser field. Theory shows that laser-free elastic differential cross sections (DCSs) can be extracted from these photoelectrons, and the DCS can be used to retrieve the bond lengths of gas-phase molecules similar to the conventional electron diffraction method. From our experimental results, we have obtained the C-C and C-H bond lengths of benzene with a spatialmore » resolution of about 10 pm. Our results demonstrate that laser induced electron diffraction (LIED) experiments can be carried out with the present-day ultrafast intense lasers already. Looking ahead, with aligned or oriented molecules, more complete spatial information of the molecule can be obtained from LIED, and applying LIED to probe photo-excited molecules, a “molecular movie” of the dynamic system may be created with sub-A°ngstrom spatial and few-ten femtosecond temporal resolutions.« less

Storage change in a flat-lying fracture during well tests

NASA Astrophysics Data System (ADS)

Murdoch, Lawrence C.; Germanovich, Leonid N.

2012-12-01

The volume of water released from storage per unit head drop per volume of an REV is a basic quantity in groundwater hydrology, but the details of the process of storage change in the vicinity of a well are commonly overlooked. We characterize storage change in a flat-lying fracture or thin sedimentary bed through the apparent hydraulic compliance,Cf, the change in aperture of the fracture or thickness of the layer per unit change in pressure. The results of theoretical analyses and field measurements show that Cf increases with time near the well during pumping, but it drops suddenly and may become negative at the beginning of recovery during a well test. Profiles of Cfincrease with radial distance from a well, but they are marked by a sharp increase and a sharp decrease at the edge of the region affected by the wellbore pressure transient. The conventional view in groundwater hydrology is that storage change at a point is proportional to the local change in pressure, which requires that the hydraulic compliance is uniform and constant. It appears that this conventional view is a simplification of a process that varies in both space and time and can even take on negative values. This simplification may be a source of uncertainty when interpreting well tests and extensometer records or predicting long-term well performance.

Rock Slope Design Criteria : Executive Summary Report

DOT National Transportation Integrated Search

2010-06-01

Based on the stratigraphy and the type of slope stability problems, the flat lying, Paleozoic age, sedimentary rocks of Ohio were divided into three design units: 1) competent rock design unit consisting of sandstones, limestones, and siltstones that...

An online detection system for aggregate sizes and shapes based on digital image processing

NASA Astrophysics Data System (ADS)

Yang, Jianhong; Chen, Sijia

2017-02-01

Traditional aggregate size measuring methods are time-consuming, taxing, and do not deliver online measurements. A new online detection system for determining aggregate size and shape based on a digital camera with a charge-coupled device, and subsequent digital image processing, have been developed to overcome these problems. The system captures images of aggregates while falling and flat lying. Using these data, the particle size and shape distribution can be obtained in real time. Here, we calibrate this method using standard globules. Our experiments show that the maximum particle size distribution error was only 3 wt%, while the maximum particle shape distribution error was only 2 wt% for data derived from falling aggregates, having good dispersion. In contrast, the data for flat-lying aggregates had a maximum particle size distribution error of 12 wt%, and a maximum particle shape distribution error of 10 wt%; their accuracy was clearly lower than for falling aggregates. However, they performed well for single-graded aggregates, and did not require a dispersion device. Our system is low-cost and easy to install. It can successfully achieve online detection of aggregate size and shape with good reliability, and it has great potential for aggregate quality assurance.

Adsorption study of copper phthalocyanine on Si(111)(√3 × √3)R30°Ag surface

NASA Astrophysics Data System (ADS)

Menzli, S.; Ben Hamada, B.; Arbi, I.; Souissi, A.; Laribi, A.; Akremi, A.; Chefi, C.

2016-04-01

The adsorption of copper phthalocyanine (CuPc) molecules on Si(111)(√3 × √3)R30°Ag surface is studied at room temperature under ultra high vacuum. Crystallographic, chemical and electronic properties of the interface are investigated by low energy electron diffraction (LEED), ultraviolet and X-ray photoemission spectroscopies (UPS, XPS) and X-ray photoemission diffraction (XPD). LEED and XPD results indicate that after one monolayer deposition the molecular layer is highly ordered with a flat lying adsorption configuration. The corresponding pattern reveals the coexistence of three symmetrically equivalent orientations of molecules with respect to the substrate. XPS core level spectra of the substrate reveal that there is no discernible chemical interaction between molecules and substrate; however there is evidence of Fermi level movement. During the growth, the work function was found to decrease from 4.90 eV for the clean substrate to 4.35 eV for the highest coverage (60 monolayers). Within a thickness of two monolayer deposition an interface dipole of 0.35 eV and a band bending of 0.2 eV have been found. UPS spectra indicate the existence of a band bending of the highest occupied molecular orbital (HOMO) of 0.55 eV. The changes in the work function, in the Fermi level position and in the HOMO state have been used to determine the energy level alignment at the interface.

Mineral resources of the Adobe Town Wilderness Study Area, Sweetwater County, Wyoming

DOE Office of Scientific and Technical Information (OSTI.GOV)

Van Loenen, R.E.; Hill, R.H.; Bankey, V.

1989-01-01

The Adobe Town Wilderness Study Area is in Southwest Wyoming about 60 miles southeast of Rock Springs. This study area consists of flat-lying sedimentary rock of Eocene age located near the center of the Washakie Basin. There are no identified resources. This study area has a high resource potential for undiscovered oil and gas, in over pressured Cretaceous and Tertiary sandstone reservoirs. This study area has a low resource potential for undiscovered oil shale, zeolites, uranium, coal, and metallic minerals.

Head Position in Stroke Trial (HeadPoST)--sitting-up vs lying-flat positioning of patients with acute stroke: study protocol for a cluster randomised controlled trial.

PubMed

Muñoz-Venturelli, Paula; Arima, Hisatomi; Lavados, Pablo; Brunser, Alejandro; Peng, Bin; Cui, Liying; Song, Lily; Billot, Laurent; Boaden, Elizabeth; Hackett, Maree L; Heritier, Stephane; Jan, Stephen; Middleton, Sandy; Olavarría, Verónica V; Lim, Joyce Y; Lindley, Richard I; Heeley, Emma; Robinson, Thompson; Pontes-Neto, Octavio; Natsagdorj, Lkhamtsoo; Lin, Ruey-Tay; Watkins, Caroline; Anderson, Craig S

2015-06-05

Positioning a patient lying-flat in the acute phase of ischaemic stroke may improve recovery and reduce disability, but such a possibility has not been formally tested in a randomised trial. We therefore initiated the Head Position in Stroke Trial (HeadPoST) to determine the effects of lying-flat (0°) compared with sitting-up (≥ 30°) head positioning in the first 24 hours of hospital admission for patients with acute stroke. We plan to conduct an international, cluster randomised, crossover, open, blinded outcome-assessed clinical trial involving 140 study hospitals (clusters) with established acute stroke care programs. Each hospital will be randomly assigned to sequential policies of lying-flat (0°) or sitting-up (≥ 30°) head position as a 'business as usual' stroke care policy during the first 24 hours of admittance. Each hospital is required to recruit 60 consecutive patients with acute ischaemic stroke (AIS), and all patients with acute intracerebral haemorrhage (ICH) (an estimated average of 10), in the first randomised head position policy before crossing over to the second head position policy with a similar recruitment target. After collection of in-hospital clinical and management data and 7-day outcomes, central trained blinded assessors will conduct a telephone disability assessment with the modified Rankin Scale at 90 days. The primary outcome for analysis is a shift (defined as improvement) in death or disability on this scale. For a cluster size of 60 patients with AIS per intervention and with various assumptions including an intracluster correlation coefficient of 0.03, a sample size of 16,800 patients at 140 centres will provide 90 % power (α 0.05) to detect at least a 16 % relative improvement (shift) in an ordinal logistic regression analysis of the primary outcome. The treatment effect will also be assessed in all patients with ICH who are recruited during each treatment study period. HeadPoST is a large international clinical trial in which we will rigorously evaluate the effects of different head positioning in patients with acute stroke. ClinicalTrials.gov identifier: NCT02162017 (date of registration: 27 April 2014); ANZCTR identifier: ACTRN12614000483651 (date of registration: 9 May 2014). Protocol version and date: version 2.2, 19 June 2014.

Projective flatness in the quantisation of bosons and fermions

NASA Astrophysics Data System (ADS)

Wu, Siye

2015-07-01

We compare the quantisation of linear systems of bosons and fermions. We recall the appearance of projectively flat connection and results on parallel transport in the quantisation of bosons. We then discuss pre-quantisation and quantisation of fermions using the calculus of fermionic variables. We define a natural connection on the bundle of Hilbert spaces and show that it is projectively flat. This identifies, up to a phase, equivalent spinor representations constructed by various polarisations. We introduce the concept of metaplectic correction for fermions and show that the bundle of corrected Hilbert spaces is naturally flat. We then show that the parallel transport in the bundle of Hilbert spaces along a geodesic is a rescaled projection provided that the geodesic lies within the complement of a cut locus. Finally, we study the bundle of Hilbert spaces when there is a symmetry.

Effect of Dispersion on Surface Interactions of Cobalt(II) Octaethylporphyrin Monolayer on Au(111) and HOPG(0001) Substrates: a Comparative First Principles Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chilukuri, Bhaskar; Mazur, Ursula; Hipps, Kerry W.

A density functional theory study of a cobalt(II) octaethylporphyrin (CoOEP) monolayer on Au(111) and HOPG(0001) surfaces was performed under periodic boundary conditions. Calculations with and without dispersion corrections are performed and the effect of van der Waals forces on the interface properties is analyzed. Calculations have determined that the CoOEP molecule tends to bind at the 3-fold and the 6-fold center sites on Au(111) and HOPG(0001), respectively. Geometric optimizations at the center binding sites have indicated that the porphyrin molecules (in the monolayer) lie flat on both substrates. Calculations also reveal that the CoOEP monolayer binds slightly more strongly tomore » Au(111) than to HOPG(0001). Charge density difference plots disclose that charge is redistributed mostly around the porphyrin plane and the first layer of the substrates. Dispersion interactions cause a larger substrate to molecule charge pushback on Au(111) than on HOPG. CoOEP adsorption tends to lower the work functions of either substrate, qualitatively agreeing with the experimental photoelectron spectroscopic data. Comparison of the density of states (DOS) of the isolated CoOEP molecule with that on gold and HOPG substrates showed significant band shifts around the Fermi energy due to intermolecular orbital hybridization. Simulated STM images were plotted with the Tersoff–Hamann approach using the local density of states, which also agree with the experimental results. This study elucidates the role of dispersion for better describing porphyrin–substrate interactions. A DFT based overview of geometric, adsorption and electronic properties of a porphyrin monolayer on conductive surfaces is presented.« less

Effect of dispersion on surface interactions of cobalt(II) octaethylporphyrin monolayer on Au(111) and HOPG(0001) substrates: a comparative first principles study.

PubMed

Chilukuri, Bhaskar; Mazur, Ursula; Hipps, K W

2014-07-21

A density functional theory study of a cobalt(II) octaethylporphyrin (CoOEP) monolayer on Au(111) and HOPG(0001) surfaces was performed under periodic boundary conditions. Calculations with and without dispersion corrections are performed and the effect of van der Waals forces on the interface properties is analyzed. Calculations have determined that the CoOEP molecule tends to bind at the 3-fold and the 6-fold center sites on Au(111) and HOPG(0001), respectively. Geometric optimizations at the center binding sites have indicated that the porphyrin molecules (in the monolayer) lie flat on both substrates. Calculations also reveal that the CoOEP monolayer binds slightly more strongly to Au(111) than to HOPG(0001). Charge density difference plots disclose that charge is redistributed mostly around the porphyrin plane and the first layer of the substrates. Dispersion interactions cause a larger substrate to molecule charge pushback on Au(111) than on HOPG. CoOEP adsorption tends to lower the work functions of either substrate, qualitatively agreeing with the experimental photoelectron spectroscopic data. Comparison of the density of states (DOS) of the isolated CoOEP molecule with that on gold and HOPG substrates showed significant band shifts around the Fermi energy due to intermolecular orbital hybridization. Simulated STM images were plotted with the Tersoff-Hamann approach using the local density of states, which also agree with the experimental results. This study elucidates the role of dispersion for better describing porphyrin-substrate interactions. A DFT based overview of geometric, adsorption and electronic properties of a porphyrin monolayer on conductive surfaces is presented.

Proper Conformal Killing Vectors in Kantowski-Sachs Metric

NASA Astrophysics Data System (ADS)

Hussain, Tahir; Farhan, Muhammad

2018-04-01

This paper deals with the existence of proper conformal Killing vectors (CKVs) in Kantowski-Sachs metric. Subject to some integrability conditions, the general form of vector filed generating CKVs and the conformal factor is presented. The integrability conditions are solved generally as well as in some particular cases to show that the non-conformally flat Kantowski-Sachs metric admits two proper CKVs, while it admits a 15-dimensional Lie algebra of CKVs in the case when it becomes conformally flat. The inheriting conformal Killing vectors (ICKVs), which map fluid lines conformally, are also investigated.

Topological properties of flat electroencephalography's state space

NASA Astrophysics Data System (ADS)

Ken, Tan Lit; Ahmad, Tahir bin; Mohd, Mohd Sham bin; Ngien, Su Kong; Suwa, Tohru; Meng, Ong Sie

2016-02-01

Neuroinverse problem are often associated with complex neuronal activity. It involves locating problematic cell which is highly challenging. While epileptic foci localization is possible with the aid of EEG signals, it relies greatly on the ability to extract hidden information or pattern within EEG signals. Flat EEG being an enhancement of EEG is a way of viewing electroencephalograph on the real plane. In the perspective of dynamical systems, Flat EEG is equivalent to epileptic seizure hence, making it a great platform to study epileptic seizure. Throughout the years, various mathematical tools have been applied on Flat EEG to extract hidden information that is hardly noticeable by traditional visual inspection. While these tools have given worthy results, the journey towards understanding seizure process completely is yet to be succeeded. Since the underlying structure of Flat EEG is dynamic and is deemed to contain wealthy information regarding brainstorm, it would certainly be appealing to explore in depth its structures. To better understand the complex seizure process, this paper studies the event of epileptic seizure via Flat EEG in a more general framework by means of topology, particularly, on the state space where the event of Flat EEG lies.

Monterrey, Mexico as seen from STS-60

NASA Image and Video Library

1994-02-09

STS060-83-041 (3-11 Feb 1994) --- The large city of Monterrey, in northeastern Mexico, was founded at the edge between the Sierra Madre Oriental and the Rio Grande Embayment portion of the Gulf Coastal Plain. This location is analogous to the Fall Line along the United States eastern seaboard, but instead of lying along a stream at the head of navigation, Monterrey lies at the boundary between a well-watered mountain range and a semi-arid plain where irrigation is often necessary for successful agriculture. The mountains themselves are formed from folded limestone and shale beds; to the south of the city, beds are crumpled into tight folds. Around and north of the city, more open folds gradually give way to nearly flat-lying beds of the coastal plain. Because of the water and other resources such as shale and limestone to quarry and burn for cement, Monterrey early became a thriving industrial center. It is now one of Mexico's largest cities with a population of approximately 5 million. According to NASA geologists, the STS-60 photography of this area is the best that has been acquired during the past 32 years of space photography by the United States. Monterrey remains an area of high interest for future photography in order to assess the impact of urbanization in this area.

A Lie based 4-dimensional higher Chern-Simons theory

NASA Astrophysics Data System (ADS)

Zucchini, Roberto

2016-05-01

We present and study a model of 4-dimensional higher Chern-Simons theory, special Chern-Simons (SCS) theory, instances of which have appeared in the string literature, whose symmetry is encoded in a skeletal semistrict Lie 2-algebra constructed from a compact Lie group with non discrete center. The field content of SCS theory consists of a Lie valued 2-connection coupled to a background closed 3-form. SCS theory enjoys a large gauge and gauge for gauge symmetry organized in an infinite dimensional strict Lie 2-group. The partition function of SCS theory is simply related to that of a topological gauge theory localizing on flat connections with degree 3 second characteristic class determined by the background 3-form. Finally, SCS theory is related to a 3-dimensional special gauge theory whose 2-connection space has a natural symplectic structure with respect to which the 1-gauge transformation action is Hamiltonian, the 2-curvature map acting as moment map.

Ten Ideas Worth Stealing from New Zealand.

ERIC Educational Resources Information Center

Jarchow, Elaine

1992-01-01

New Zealand educators have some ideas worth stealing, including morning tea-time, the lie-flat manifold duplicate book for recording classroom observation comments, school uniforms, collegial planning and grading of college assignments, good meeting etiquette, a whole-child orientation, portable primary architecture, group employment interviews…

Engineering Ni-Mo-S Nanoparticles for Hydrodesulfurization.

PubMed

Bodin, Anders; Christoffersen, Ann-Louise N; Elkjær, Christian F; Brorson, Michael; Kibsgaard, Jakob; Helveg, Stig; Chorkendorff, Ib

2018-06-13

Nanoparticle engineering for catalytic applications requires both a synthesis technique for the production of well-defined nanoparticles and measurements of their catalytic performance. In this paper, we present a new approach to rationally engineering highly active Ni-Mo-S nanoparticle catalysts for hydrodesulfurization (HDS), i.e., the removal of sulfur from fossil fuels. Nanoparticle catalysts are synthesized by the sputtering of a Mo 75 Ni 25 metal target in a reactive atmosphere of Ar and H 2 S followed by the gas aggregation of the sputtered material into nanoparticles. The nanoparticles are filtered by a quadrupole mass filter and subsequently deposited on a planar substrate, such as a grid for electron microscopy or a microreactor. By varying the mass of the deposited nanoparticles, it is demonstrated that the Ni-Mo-S nanoparticles can be tuned into fullerene-like particles, flat-lying platelets, and upright-oriented platelets. The nanoparticle morphologies provide different abundances of Ni-Mo-S edge sites, which are commonly considered the catalytically important sites. Using a microreactor system, we assess the catalytic activity of the Ni-Mo-S nanoparticles for the HDS of dibenzothiophene. The measurements show that platelets are twice as active as the fullerene-like particles, demonstrating that the Ni-Mo-S edges are more active than basal planes for the HDS. Furthermore, the upright-standing orientation of platelets show an activity that is six times higher than the fullerene-like particles, demonstrating the importance of the edge site number and accessibility to reducing, e.g., sterical hindrance for the reacting molecules.

Subduction zone evolution and low viscosity wedges and channels

NASA Astrophysics Data System (ADS)

Manea, Vlad; Gurnis, Michael

2007-12-01

Dehydration of subducting lithosphere likely transports fluid into the mantle wedge where the viscosity is decreased. Such a decrease in viscosity could form a low viscosity wedge (LVW) or a low viscosity channel (LVC) on top of the subducting slab. Using numerical models, we investigate the influence of low viscosity wedges and channels on subduction zone structure. Slab dip changes substantially with the viscosity reduction within the LVWs and LVCs. For models with or without trench rollback, overthickening of slabs is greatly reduced by LVWs or LVCs. Two divergent evolutionary pathways have been found depending on the maximum depth extent of the LVW and wedge viscosity. Assuming a viscosity contrast of 0.1 with background asthenosphere, models with a LVW that extends down to 400 km depth show a steeply dipping slab, while models with an LVW that extends to much shallower depth, such as 200 km, can produce slabs that are flat lying beneath the overriding plate. There is a narrow range of mantle viscosities that produces flat slabs (5 to10 × 10 19 Pa s) and the slab flattening process is enhanced by trench rollback. Slab can be decoupled from the overriding plate with a LVC if the thickness is at least a few 10 s of km, the viscosity reduction is at least a factor of two and the depth extent of the LVC is several hundred km. These models have important implications for the geochemical and spatial evolution of volcanic arcs and the state of stress within the overriding plate. The models explain the poor correlation between traditional geodynamic controls, subducting plate age and convergence rates, on slab dip. We predict that when volcanic arcs change their distance from the trench, they could be preceded by changes in arc chemistry. We predict that there could be a larger volatile input into the wedge when arcs migrate toward the trench and visa-versa. The transition of a subduction zone into the flat-lying regime could be preceded by changes in the volatile budget such that the dehydration front moves to shallower depths. Our flat-slab models shed some light on puzzling flat subduction systems, like in Central Mexico, where there is no deformation within the overriding plate above the flat segment. The lack of in-plane compression in Central Mexico suggests the presence of a low viscosity shear zone above the flat slab.

Refining Rodinia: New Paleomagnetic Results From Amazonia and Paleogeographic Implications For The Grenville Orogeny.

NASA Astrophysics Data System (ADS)

Tohver, E.; van der Pluijm, B. A.; van der Voo, R.

The Grenville province of eastern Laurentia is commonly considered to be the product of continental collision between ancestral North America and an as yet unidentified continent. New paleogeographic information for the Amazon craton in early Grenvil- lian times was determined from a new paleomagnetic pole based on the hypabyssal gabbros and flat-lying basalts of the Nova Floresta Fm. found in the western Brazil- ian state of Rondonia. Measurement of the anisotropy of magnetic susceptibility of the gabbros reveals a flat-lying fabric, suggesting an undeformed, igneous body. A paleomagnetic pole (n = 16 sites, Plat = 24.6N, Plon. = 164.6E, A95 = 5.5, Q = 5) is calculated from a steep, characteristic remanence (ChRM) that is inferred to be primary. This ChRM is isolated at applied field >30 mT and is probably carried by magnetite present in large, oxyexsolved titanomagnetites or igneous reaction rims. Emplacement of the body and acquisition of magnetization is dated by 40Ar/39Ar analysis of igneous biotite and plagioclase, both phases yielding ages of ca.1.2 Ga. Comparison of the position of Amazonia with that of ancestral North America deter- mined from the Laurentian APWP from 1.3 - 1.15 Ga suggests that Amazonia may have collided with the southernmost portion of Laurentia at ca.1.2 Ga. The timing of this collision is in agreement with geochronological constraints on the timing of de- formation in the Llano segment of Laurentia as well as observed deformation of the western Amazon craton.

Paleogeography of the Amazon craton at 1.2 Ga: early Grenvillian collision with the Llano segment of Laurentia

NASA Astrophysics Data System (ADS)

Tohver, Eric; van der Pluijm, B. A.; Van der Voo, R.; Rizzotto, G.; Scandolara, J. E.

2002-05-01

A paleomagnetic, geochronologic and petrographic study was undertaken on the flat-lying gabbros and basalts of the Nova Floresta Formation of Rondônia state, western Brazil in order to constrain the Mesoproterozoic paleogeography of the Amazon craton. Measurement of the anisotropy of magnetic susceptibility on the gabbroic samples reveals a flat-lying foliation with a radiating pattern of lineations, supporting the field evidence that the gabbros are part of a large, undeformed sill. Petrographic observations of oxides in the gabbros reveals two populations of magnetite grains produced during the original cooling of the sill: large, oxyexsolved titanomagnetite grains and fine-grained magnetite in igneous reaction rims. New 40Ar/39Ar age dating of biotite and plagioclase yield ages of ∼1.2 Ga, which represent the rapid cooling following emplacement of the mafic magma. Whole rock dating of basalt samples yields total gas ages of 1062±3 Ma, similar to the ∼1.0 Ga K/Ar ages reported by previous workers. However, the strong compositional dependence of the age spectrum renders this younger whole rock age unreliable except as a minimum constraint. A single magnetic component is found in the basalts, indistinguishable from the characteristic remanence found in the gabbros that is oriented WNW and steeply upward. This magnetization is considered to be primary and was acquired during the cooling of the sill and associated lavas. A paleomagnetic pole calculated from the Nova Floresta Formation (n=16 sites, Plat.=24.6°N, Plong.=164.6°E, A95=5.5°, Q=5), the first reported pole for the Amazon craton for the 1200-600 Ma Rodinia time period, constrains the paleogeographic position of Amazonia at ∼1.2 Ga. Juxtaposition of the western Amazon craton with the Llano segment of the Laurentia's Grenville margin causes the NF pole to lie on the 1.2 Ga portion of the combined APWP for Laurentia and Greenland, which indicates that a collision with the Amazon craton could have caused the Llano deformation in early Grenvillian times.

Janine Freeman | NREL

Science.gov Websites

investigator for the project. Her expertise lies in photovoltaic and wind power modeling, as well as Data Directly in Photovoltaic Modeling: Methodology and Validation. NREL/CP-6A20-66465, National . Dobos. 2014. Validation of Multiple Tools for Flat Plate Photovoltaic Modeling Against Measured Data

Spontaneous adsorption on a hydrophobic surface governed by hydrogen bonding.

PubMed

Dang, Fuquan; Hasegawa, Takeshi; Biju, Vasudevanpillai; Ishikawa, Mitsuru; Kaji, Noritada; Yasui, Takao; Baba, Yoshinobu

2009-08-18

Spontaneous adsorption from solution onto solid surface is a common phenomenon in nature, but the force that governs adsorption is still a matter of considerable debate. (1, 2) We found that surfactants and cellulose adsorb from solution onto a poly(methyl methacrylate) (PMMA) surface in an ordered and cooperative way governed by hydrogen bonding. The glucose rings of n-dodecyl-beta-D-maltoside (DDM) and hydroxyethylcellulose (HEC) stand perpendicular to the surface, H-bond to the surface COOMe groups with their C=O and Me-O bonds parallel to the surface, and form a tight monolayer. The non-H-bonded COOMe groups orient their C=O bonds perpendicular to the surface. In contrast, the glucose rings of hydrophobically modified hydroxyethylcellulose (HMHEC) lie flat with the side chains perpendicular to the surface and H-bond to the perpendicular-oriented C=O groups. The non-H-bonded COOMe groups orient their C=O bonds parallel but Me-O bonds near-perpendicular to the surface for stabilizing HMHEC. The current work provides a detailed picture of how surface-active molecules interact with a solid surface and self-assemble into greatly different architectures.

Step-by-step growth of epitaxially aligned polythiophene by surface-confined reaction

PubMed Central

Lipton-Duffin, J. A.; Miwa, J. A.; Kondratenko, M.; Cicoira, F.; Sumpter, B. G.; Meunier, V.; Perepichka, D. F.; Rosei, F.

2010-01-01

One of the great challenges in surface chemistry is to assemble aromatic building blocks into ordered structures that are mechanically robust and electronically interlinked—i.e., are held together by covalent bonds. We demonstrate the surface-confined growth of ordered arrays of poly(3,4-ethylenedioxythiophene) (PEDOT) chains, by using the substrate (the 110 facet of copper) simultaneously as template and catalyst for polymerization. Copper acts as promoter for the Ullmann coupling reaction, whereas the inherent anisotropy of the fcc 110 facet confines growth to a single dimension. High resolution scanning tunneling microscopy performed under ultrahigh vacuum conditions allows us to simultaneously image PEDOT oligomers and the copper lattice with atomic resolution. Density functional theory calculations confirm an unexpected adsorption geometry of the PEDOT oligomers, which stand on the sulfur atom of the thiophene ring rather than lying flat. This polymerization approach can be extended to many other halogen-terminated molecules to produce epitaxially aligned conjugated polymers. Such systems might be of central importance to develop future electronic and optoelectronic devices with high quality active materials, besides representing model systems for basic science investigations. PMID:20534511

Growth of the flat bones of the membranous neurocranium: a computational model.

PubMed

Garzón-Alvarado, Diego A; González, Andres; Gutiérrez, Maria Lucia

2013-12-01

This article assumes two stages in the formation of the bones in the calvaria, the first one takes into account the formation of the primary centers of ossification. This step counts on the differentiation from mesenchymal cells into osteoblasts. A molecular mechanism is used based on a system of reaction-diffusion between two antagonistic molecules, which are BMP2 and Noggin. To this effect we used equations whose behavior allows finding Turing patterns that determine the location of the primary centers. In the second step of the model we used a molecule that is expressed by osteoblasts, called Dxl5 and that is expressed from the osteoblasts of each flat bone. This molecule allows bone growth through its borders through cell differentiation adjacent to each bone of the skull. The model has been implemented numerically using the finite element method. The results allow us to observe a good approximation of the formation of flat bones of the membranous skull as well as the formation of fontanelles and sutures. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

A Lie-theoretic Description of the Solution Space of the tt*-Toda Equations

NASA Astrophysics Data System (ADS)

Guest, Martin A.; Ho, Nan-Kuo

2017-12-01

We give a Lie-theoretic explanation for the convex polytope which parametrizes the globally smooth solutions of the topological-antitopological fusion equations of Toda type (tt ∗-Toda equations) which were introduced by Cecotti and Vafa. It is known from Guest and Lin (J. Reine Angew. Math. 689, 1-32 2014) Guest et al. (It. Math. Res. Notices 2015, 11745-11784 2015) and Mochizuki (2013, 2014) that these solutions can be parametrized by monodromy data of a certain flat S L n+ 1 ℝ-connection. Using Boalch's Lie-theoretic description of Stokes data, and Steinberg's description of regular conjugacy classes of a linear algebraic group, we express this monodromy data as a convex subset of a Weyl alcove of S U n+ 1.

BMS3 invariant fluid dynamics at null infinity

NASA Astrophysics Data System (ADS)

Penna, Robert F.

2018-02-01

We revisit the boundary dynamics of asymptotically flat, three dimensional gravity. The boundary is governed by a momentum conservation equation and an energy conservation equation, which we interpret as fluid equations, following the membrane paradigm. We reformulate the boundary’s equations of motion as Hamiltonian flow on the dual of an infinite-dimensional, semi-direct product Lie algebra equipped with a Lie–Poisson bracket. This gives the analogue for boundary fluid dynamics of the Marsden–Ratiu–Weinstein formulation of the compressible Euler equations on a manifold, M, as Hamiltonian flow on the dual of the Lie algebra of \

5,10-Methylene-5,6,7,8-tetrahydrofolate conformational transitions upon binding to thymidylate synthase: molecular mechanics and continuum solvent studies

NASA Astrophysics Data System (ADS)

Jarmuła, Adam; Cieplak, Piotr; Montfort, William R.

2005-02-01

We applied the molecular mechanics Poisson-Boltzmann surface area (MM-PBSA) approach to evaluate relative stability of the extended (flat) and C-shaped (bent) solution conformational forms of the 5,10-methylene-5,6,7,8-tetrahydrofolate (mTHF) molecule in aqueous solution. Calculations indicated that both forms have similar free energies in aqueous solution but detailed energy components are different. The bent solution form has lower intramolecular electrostatic and van der Waals interaction energies. The flat form has more favorable solvation free energy and lower contribution from the bond, angle and torsion angle molecular mechanical internal energies. We exploit these results and combine them with known crystallographic data to provide a model for the progressive binding of the mTHF molecule, a natural cofactor of thymidylate synthase (TS), to the complex forming in the TS-catalyzed reaction. We propose that at the time of initial weak binding in the open enzyme the cofactor molecule remains in a close balance between the flat and bent solution conformations, with neither form clearly favored. Later, thymidylate synthase undergoes conformational change leading to the closure of the active site and the mTHF molecule is withdrawn from the solvent. That effect shifts the thermodynamic equilibrium of the mTHF molecule toward the bent solution form. At the same time, burying the cofactor molecule in the closed active site produces numerous contacts between mTHF and protein that render change in the shape of the mTHF molecule. As a result, the bent solution conformer is converted to more strained L-shaped bent enzyme conformer of the mTHF molecule. The strain in the bent enzyme conformation allows for the tight binding of the cofactor molecule to the productive ternary complex that forms in the closed active site, and facilitates the protonation of the imidazolidine N10 atom, which promotes further reaction.

Closed-form solutions of the Wheeler-DeWitt equation in a scalar-vector field cosmological model by Lie symmetries

NASA Astrophysics Data System (ADS)

Paliathanasis, Andronikos; Vakili, Babak

2016-01-01

We apply as selection rule to determine the unknown functions of a cosmological model the existence of Lie point symmetries for the Wheeler-DeWitt equation of quantum gravity. Our cosmological setting consists of a flat Friedmann-Robertson-Walker metric having the scale factor a( t), a scalar field with potential function V(φ ) minimally coupled to gravity and a vector field of its kinetic energy is coupled with the scalar field by a coupling function f(φ ). Then, the Lie symmetries of this dynamical system are investigated by utilizing the behavior of the corresponding minisuperspace under the infinitesimal generator of the desired symmetries. It is shown that by applying the Lie symmetry condition the form of the coupling function and also the scalar field potential function may be explicitly determined so that we are able to solve the Wheeler-DeWitt equation. Finally, we show how we can use the Lie symmetries in order to construct conservation laws and exact solutions for the field equations.

First principles studies of the dependence of magnetism on the crystal phase in 4d and 5d late transition metals

NASA Astrophysics Data System (ADS)

Hüger, E.; Osuch, K.

2005-03-01

We investigate the possibility of inducing ferromagnetic order in 4d and 5d late transition metals through crystal symmetry change. First principles, self-consistent density functional theory calculations, with spin-orbit coupling included, performed at 0 K show that ferromagnetism occurs in the bulk of Rh and Pd at the optimum lattice constant if Rh is in the bcc and Pd in the hcp/dhcp phase. The ferromagnetic order originates in the d-band occupancy of Rh or Pd which locates the Fermi energy at the top of the highest peak of the respective (paramagnetic) density of states induced by the bcc or hcp/dhcp structure. This peak in the density of states is caused by flat bands which lie at the surface of the respective Brillouin zone. For a bcc crystal these flat bands have the eg character and are positioned at the surface of the bcc Brillouin zone along the N-P line. The origin of the flatness of the bands was found to be the translation symmetry of the cubic lattice which causes the bands with the eg character to be narrow along the k-lines whose k-vector directions are furthest off the directions to which the orbitals of the eg symmetry point. Due to the d-band occupancy of Rh these flat bands lie in the paramagnetic state at the Fermi energy, whereas in the ferromagnetic state they exhibit the largest energetic split. This indicates that a smaller degree of orbital overlap narrows electronic bands enhancing the tendency of the system for ferromagnetic band split. For the hcp/dhcp structure the states contributing to the high density of para-magnetic states at the Fermi level of Pd lie in the vicinity of the M-L line of the hcp Brillouin zone boundary, which possesses a high number of symmetry (M and L) points. Moreover, the M-L line is aligned with the stacking sequence direction ([0001]) which is furthest off the densest-packed atomic chain direction of an hcp-crystal and, consequently, the weakest-bond direction in the crystal. This makes the narrow bands along the M-L line flat. The instability of the bcc and the meta-stability of the hcp crystal phase modifications for metals with native close-packed crystal structures is subsequently analysed in order to find whether they can be grown as films on suitable substrates.

Geology of the Brick Flat massive sulfide body, Iron Mountain cluster, West Shasta district, California ( USA).

USGS Publications Warehouse

Albers, J.P.

1985-01-01

The Brick Flat massive sulfide body is one of a group of 8 individual bodies that constitute the Iron Mountain cluster in the S part of the West Shasta district. Before they were separated by postmineral faulting, 5 of the 8 sulfide bodies formed a single large deposit about 1375 m long with a mass of some 23 million metric tons. The pyritic Brick Flat sulfide body is one of the 5 faulted segements of this deposit. The Brick Flat massive sulfide lies within medium phenocryst rhyolite that is characteristic of the ore-bearing middle unit of the Balaklala Rhyolite. It is interpreted to be downfaulted a vertical distance of 75 to 85 m from the Old Mine sulfide-gossan orebody along the N-dipping Camden South fault. It is bounded in turn on its N side by another parallel fault, the Camden North, which drops the orebody down another 75 m to the level of the Richmond orebody. -from Author

Quasi-3-D Seismic Reflection Imaging and Wide-Angle Velocity Structure of Nearly Amagmatic Oceanic Lithosphere at the Ultraslow-Spreading Southwest Indian Ridge

NASA Astrophysics Data System (ADS)

Momoh, Ekeabino; Cannat, Mathilde; Watremez, Louise; Leroy, Sylvie; Singh, Satish C.

2017-12-01

We present results from 3-D processing of 2-D seismic data shot along 100 m spaced profiles in a 1.8 km wide by 24 km long box during the SISMOSMOOTH 2014 cruise. The study is aimed at understanding the oceanic crust formed at an end-member mid-ocean ridge environment of nearly zero melt supply. Three distinct packages of reflectors are imaged: (1) south facing reflectors, which we propose correspond to the damage zone induced by the active axial detachment fault: reflectors in the damage zone have dips up to 60° and are visible down to 5 km below the seafloor; (2) series of north dipping reflectors in the hanging wall of the detachment fault: these reflectors may correspond to damage zone inherited from a previous, north dipping detachment fault, or small offset recent faults, conjugate from the active detachment fault, that served as conduits for isolated magmatic dykes; and (3) discontinuous but coherent flat-lying reflectors at shallow depths (<1.5 km below the seafloor), and at depths between 4 and 5 km below the seafloor. Comparing these deeper flat-lying reflectors with the wide-angle velocity model obtained from ocean-bottom seismometers data next to the 3-D box shows that they correspond to parts of the model with P wave velocity of 6.5-8 km/s, suggesting that they occur in the transition between lower crust and upper mantle. The 4-5 km layer with crustal P wave velocities is interpreted as primarily due to serpentinization and fracturation of the exhumed mantle-derived peridotites in the footwall of active and past detachment faults.

77 FR 39561 - Advanced Braking Technologies That Rely on Forward-Looking Sensors; Request for Comments

Federal Register 2010, 2011, 2012, 2013, 2014

2012-07-03

... test scenarios: driving over a 1-inch thick steel plate lying flat on the pavement (a plate often used... provide specific recommendations for other surrogate vehicle design considerations that should be... perform as designed (e.g., driving in the dark or in adverse weather)? What information should be...

Effect of Nonionic Surfactants on the Stability of Hydrophobic Colloids.

DTIC Science & Technology

1987-07-30

as a point of referen e for the data with the polyoxyethlated alkylphenols . The surfactant selected was the C12E12. The reason for the selection was...ccnsequently in the stability of disper- sion. One may expect that the adsorption of polyoxyethylated alkylphenols , with the aromatic ring lying flat on

Predicting one repetition maximum equations accuracy in paralympic rowers with motor disabilities.

PubMed

Schwingel, Paulo A; Porto, Yuri C; Dias, Marcelo C M; Moreira, Mônica M; Zoppi, Cláudio C

2009-05-01

Predicting one repetition maximum equations accuracy in paralympic rowers Resistance training intensity is prescribed using percentiles of the maximum strength, defined as the maximum tension generated for a muscle or muscular group. This value is found through the application of the one maximal repetition (1RM) test. One maximal repetition test demands time and still is not appropriate for some populations because of the risk it offers. In recent years, the prediction of maximal strength, through predicting equations, has been used to prevent the inconveniences of the 1RM test. The purpose of this study was to verify the accuracy of 12 1RM predicting equations for disabled rowers. Nine male paralympic rowers (7 one-leg amputated rowers and 2 cerebral paralyzed rowers; age, 30 +/- 7.9 years; height, 175.1 +/- 5.9 cm; weight, 69 +/- 13.6 kg) performed 1RM test for lying T-bar row and flat barbell bench press exercises to determine upper-body strength and leg press exercise to determine lower-body strength. One maximal repetition test was performed, and based on submaximal repetitions loads, several linear and exponential equations models were tested with regard of their accuracy. We did not find statistical differences for lying T-bar row and bench press exercises between measured and predicted 1RM values (p = 0.84 and 0.23 for lying T-bar row and flat barbell bench press, respectively); however, leg press exercise reached a high significant difference between measured and predicted values (p < 0.01). In conclusion, rowers with motor disabilities tolerate 1RM testing procedures, and predicting 1RM equations are accurate for bench press and lying T-bar row, but not for leg press, in this kind of athlete.

The Togo-Benin-Nigeria Shield: evidence of crustal aggregation in the Pan-African belt

NASA Astrophysics Data System (ADS)

Ajibade, A. C.; Wright, J. B.

1989-08-01

The importance of "suspect" or "exotic" (i.e. allochthonous) terranes as a major element in collisional orogenic belts is becoming well established. We propose that the southern Pan-African domain in West Africa is an aggregation or " mosaic" of island arcs, interarc (ensimatic) basins and continental fragments. A fracture zone in northwestern Nigeria, already identified as a possible crustal suture, is shown to separate two contrasted basement terranes. Elsewhere in the shield are flat-lying structures characteristic of those associated with crustal convergence, lying within or near to major fractures. Many small ultramafic/mafic bodies occur in the shield and some of them may be remnants of ophiolites caught up in suture zones. An aggregation of allochthonous terranes (island arcs, sedimentary basins and continental blocks) would help to explain: (a) the great width of the Pan-African belt; (b) the spread of ages within the "Pan-African" range (c. 750-450 Ma), also the relict Liberian and Eburnian ages (c. 2700 and 2000 Ma respectively); and the enigmatic Kibaran "event" (c. 1100 Ma); (c) the contrasted volcano-sedimentary characteristics of the different supracrustal belts.

Polymeric and Lipid Membranes—From Spheres to Flat Membranes and vice versa

PubMed Central

Saveleva, Mariia S.; Gorin, Dmitry A.; Skirtach, Andre G.

2017-01-01

Membranes are important components in a number of systems, where separation and control of the flow of molecules is desirable. Controllable membranes represent an even more coveted and desirable entity and their development is considered to be the next step of development. Typically, membranes are considered on flat surfaces, but spherical capsules possess a perfect “infinite” or fully suspended membranes. Similarities and transitions between spherical and flat membranes are discussed, while applications of membranes are also emphasized. PMID:28809796

Polymeric and Lipid Membranes-From Spheres to Flat Membranes and vice versa.

PubMed

Saveleva, Mariia S; Lengert, Ekaterina V; Gorin, Dmitry A; Parakhonskiy, Bogdan V; Skirtach, Andre G

2017-08-15

Membranes are important components in a number of systems, where separation and control of the flow of molecules is desirable. Controllable membranes represent an even more coveted and desirable entity and their development is considered to be the next step of development. Typically, membranes are considered on flat surfaces, but spherical capsules possess a perfect "infinite" or fully suspended membranes. Similarities and transitions between spherical and flat membranes are discussed, while applications of membranes are also emphasized.

Preliminary bedrock and surficial geologic map of the west half of the Sanders 30' x 60' quadrangle, Navajo and Apache Counties, northern Arizona

USGS Publications Warehouse

Amoroso, Lee; Priest, Susan S.; Hiza-Redsteer, Margaret

2014-01-01

The bedrock and surficial geologic map of the west half of the Sanders 30' x 60' quadrangle was completed in a cooperative effort of the U.S. Geological Survey (USGS) and the Navajo Nation to provide regional geologic information for management and planning officials. This report provides baseline geologic information that will be useful in future studies of groundwater and surface water resources, geologic hazards, and the distribution of soils and plants. The west half of the Sanders quadrangle encompasses approximately 2,509 km2 (980 mi2) within Navajo and Apache Counties of northern Arizona and is bounded by lat 35°30' to 35° N., long 109°30' to 110° W. The majority of the land within the map area lies within the Navajo Nation. South of the Navajo Nation, private and State lands form a checkerboard pattern east and west of Petrified Forest National Park. In the west half of the Sanders quadrangle, Mesozoic bedrock is nearly flat lying except near folds. A shallow Cenozoic erosional basin that developed about 20 Ma in the western part of the map area cut across late Paleozoic and Mesozoic rocks that were subsequently filled with flat-lying Miocene and Pliocene mudstone and argillaceous sandstone and fluvial sediments of the Bidahochi Formation and associated volcanic rocks of the Hopi Buttes volcanic field. The Bidahochi rocks are capped by Pliocene(?) and Pleistocene fluvial sediments and Quaternary eolian and alluvial deposits. Erosion along northeast-southwest-oriented drainages have exposed elongated ridges of Bidahochi Formation and basin-fill deposits that are exposed through shallow eolian cover of similarly oriented longitudinal dunes. Stokes (1964) concluded that the accumulation of longitudinal sand bodies and the development of confined parallel drainages are simultaneous processes resulting in parallel sets of drainages and ridges oriented along the prevailing southwest wind direction on the southern Colorado Plateau.

Space configuration as an explanation for lithology-related cross-polarized radar image anomalies

NASA Technical Reports Server (NTRS)

Mccauley, J. R.

1972-01-01

Three rock types are described that produce dark cross-polarized images on Ka-band imagery: lava flows dating from Pleistocene and Holocene, some Tertiary volcanics, and certain massive sandstones. Their planar surfaces are large with respect to the wavelength of the Ka-band system, yet are small in comparison to the resolution. It is found that only outcrops with proper faceted surface orientations produce significant radar returns showing the dominance of specular reflectors. The omnidirectional attitude of the facets and their wide distribution on the outcrops explains the independence of look-direction that the flat-lying anomalous outcrops exhibit in production of darker cross-polarized images.

High sensitivity flat SiO2 fibres for medical dosimetry

NASA Astrophysics Data System (ADS)

Abdul Sani, Siti. F.; Alalawi, Amani I.; Azhar, Hairul A. R.; Amouzad Mahdiraji, Ghafour; Tamchek, Nizam; Nisbet, A.; Maah, M. J.; Bradley, D. A.

2014-11-01

We describe investigation of a novel undoped flat fibre fabricated for medical radiation dosimetry. Using high energy X-ray beams generated at a potential of 6 MV, comparison has been made of the TL yield of silica flat fibres, TLD-100 chips and Ge-doped silica fibres. The flat fibres provide competitive TL yield to that of TLD-100 chips, being some 100 times that of the Ge-doped fibres. Pt-coated flat fibres have then been used to increase photoelectron production and hence local dose deposition, obtaining significant increase in dose sensitivity over that of undoped flat fibres. Using 250 kVp X-ray beams, the TL yield reveals a progressive linear increase in dose for Pt thicknesses from 20 nm up to 80 nm. The dose enhancement factor (DEF) of (0.0150±0.0003) nm-1 Pt is comparable to that obtained using gold, agreeing at the 1% level with the value expected on the basis of photoelectron generation. Finally, X-ray photoelectron spectroscopy (XPS) has been employed to characterize the surface oxidation state of the fibre medium. The charge state of Si2p was found to lie on 103.86 eV of binding energy and the atomic percentage obtained from the XPS analysis is 22.41%.

Theoretical aerodynamic characteristics of a family of slender wing-tail-body combinations

NASA Technical Reports Server (NTRS)

Lomax, Harvard; Byrd, Paul F

1951-01-01

The aerodynamic characteristics of an airplane configuration composed of a swept-back, nearly constant chord wing and a triangular tail mounted on a cylindrical body are presented. The analysis is based on the assumption that the free-stream Mach number is near unity or that the configuration is slender. The calculations for the tail are made on the assumption that the vortex system trailing back from the wing is either a sheet lying entirely in the plane of the flat tail surface or has completely "rolled up" into two point vortices that lie either in, above, or below the plane of the tail surface.

Ocean Drilling Program Leg 178 (Antarctic Peninsula): Sedimentology of glacially influenced continental margin topsets and foresets

USGS Publications Warehouse

Eyles, N.; Daniels, J.; Osterman, L.E.; Januszczak, N.

2001-01-01

Ocean Drilling Program Leg 178 (February-April 1998) drilled two sites (Sites 1097 and 1103) on the outer Antarctic Peninsula Pacific continental shelf. Recovered strata are no older than late Miocene or early Pliocene (<4.6 Ma). Recovery at shallow depths in loosely consolidated and iceberg-turbated bouldery sediment was poor but improved with increasing depth and consolidation to allow description of lithofacies and biofacies and interpretation of depositional environment. Site 1097 lies on the outer shelf within Marguerite Trough which is a major outlet for ice expanding seaward from the Antarctic Peninsula and reached a maximum depth drilled of 436.6 m below the sea floor (mbsf). Seismic stratigraphic data show flat-lying upper strata resting on strata that dip gently seaward. Uppermost strata, to a depth of 150 mbsf, were poorly recovered, but data suggest they consist of diamictites containing reworked and abraded marine microfauna. This interval is interpreted as having been deposited largely as till produced by subglacial cannibalization of marine sediments (deformation till) recording ice sheet expansion across the shelf. Underlying gently dipping strata show massive, stratified and graded diamictite facies with common bioturbation and slump stuctures that are interbedded with laminated and massive mudstones with dropstones. The succession contains a well-preserved in situ marine microfauna typical of open marine and proglacial marine environments. The lower gently dipping succession at Site 1097 is interpreted as a complex of sediment gravity flows formed of poorly sorted glacial debris. Site 1103 was drilled in that part of the continental margin that shows uppermost flat-lying continental shelf topsets overlying steeper dipping slope foresets seaward of a structural mid-shelf high. Drilling reached a depth of 363 mbsf with good recovery in steeply dipping continental slope foreset strata. Foreset strata are dominated by massive and chaotically stratified diamictites interbedded with massive and graded sandstones and mudstones. The sedimentary record and seismic stratigraphy is consistent with deposition on a continental slope from debris flows and turbidity currents released from a glacial source. Data from Sites 1097 and 1103 suggest the importance of aggradation of the Antarctic Peninsula continental shelf by tilt deposition and progradation of the slope by mass flow. This may provide a model for the interpretation of Palaeozoic and Proterozoic glacial successions that accumulated on glacially influenced continental margins.

Mixing of MnPc electronic states at the MnPc/Au(110) interface

NASA Astrophysics Data System (ADS)

Gargiani, Pierluigi; Lisi, Simone; Avvisati, Giulia; Mondelli, Pierluigi; Fatale, Sara; Betti, Maria Grazia

2017-10-01

Manganese-phthalocyanines form assembled chains with a variety of ordered super-structures, flat lying along the Au(110) reconstructed channels. The chains first give rise to a ×5 symmetry reconstruction, while further deposition of MnPc leads to a ×7 periodicity at the completion of the first single layer. A net polarization with the formation of an interface dipole is mainly due to the molecular π-states located on the macrocycles pyrrole rings, while the central metal ion induces a reduction in the polarization, whose amount is related to the Mn-Au interaction. The adsorption-induced interface polarization is compared to other 3d-metal phthalocyanines, to unravel the role of the central metal atom configuration in the interaction process of the d-states. The MnPc adsorption on Au(110) induces the re-hybridization of the electronic states localized on the central metal atom, promoting a charge redistribution of the molecular orbitals of the MnPc molecules. The molecule-substrate interaction is controlled by a symmetry-determined mixing between the electronic states, involving also the molecular empty orbitals with d character hybridized with the nitrogen atoms of the pyrrole ring, as deduced by photoemission and X-ray absorption spectroscopy exploiting light polarization. The symmetry-determined mixing between the electronic states of the Mn metal center and of the Au substrate induces a density of states close to the Fermi level for the ×5 phase.

Flat band in disorder-driven non-Hermitian Weyl semimetals

NASA Astrophysics Data System (ADS)

Zyuzin, A. A.; Zyuzin, A. Yu.

2018-01-01

We study the interplay of disorder and band-structure topology in a Weyl semimetal with a tilted conical spectrum around the Weyl points. The spectrum of particles is given by the eigenvalues of a non-Hermitian matrix, which contains contributions from a Weyl Hamiltonian and complex self-energy due to electron elastic scattering on disorder. We find that the tilt-induced matrix structure of the self-energy gives rise to either a flat band or a nodal line segment at the interface of the electron and hole pockets in the bulk band structure of type-II Weyl semimetals depending on the Weyl cone inclination. For the tilt in a single direction in momentum space, each Weyl point expands into a flat band lying on the plane, which is transverse to the direction of the tilt. The spectrum of the flat band is fully imaginary and is separated from the in-plane dispersive part of the spectrum by the "exceptional nodal ring" where the matrix of the Green's function in momentum-frequency space is defective. The tilt in two directions might shrink a flat band into a nodal line segment with "exceptional edge points." We discuss the connection to the non-Hermitian topological theory.

A Writer's Reference. Third Edition.

ERIC Educational Resources Information Center

Hacker, Diana

Designed to save the user time and packaged in a compact size which lies flat, this book is easy to consult while revising and editing a written draft. The book's "main menu," just inside the front cover, displays the contents as briefly and simply as possible. Each of the 12 sections in the book's main menu leads the user to a tabbed…

Charge loss (or the lack thereof) for AdS black holes

NASA Astrophysics Data System (ADS)

Ong, Yen Chin; Chen, Pisin

2014-06-01

The evolution of evaporating charged black holes is complicated to model in general, but is nevertheless important since the hints to the Information Loss Paradox and its recent firewall incarnation may lie in understanding more generic geometries than that of Schwarzschild spacetime. Fortunately, for sufficiently large asymptotically flat Reissner-Nordström black holes, the evaporation process can be modeled via a system of coupled linear ordinary differential equations, with charge loss rate governed by Schwinger pair-production process. The same model can be generalized to study the evaporation of AdS Reissner-Nordström black holes with flat horizon. It was recently found that such black holes always evolve towards extremality since charge loss is inefficient. This property is completely opposite to the asymptotically flat case in which the black hole eventually loses its charges and tends towards Schwarzschild limit. We clarify the underlying reason for this different behavior.

Pair Formation of Hard Core Bosons in Flat Band Systems

NASA Astrophysics Data System (ADS)

Mielke, Andreas

2018-05-01

Hard core bosons in a large class of one or two dimensional flat band systems have an upper critical density, below which the ground states can be described completely. At the critical density, the ground states are Wigner crystals. If one adds a particle to the system at the critical density, the ground state and the low lying multi particle states of the system can be described as a Wigner crystal with an additional pair of particles. The energy band for the pair is separated from the rest of the multi-particle spectrum. The proofs use a Gerschgorin type of argument for block diagonally dominant matrices. In certain one-dimensional or tree-like structures one can show that the pair is localised, for example in the chequerboard chain. For this one-dimensional system with periodic boundary condition the energy band for the pair is flat, the pair is localised.

Energy and Spectroscopic Characterization of the Isomers of C4H3-, C6H3-, and C6H5-

NASA Technical Reports Server (NTRS)

Wright, Danielle; Bera, Partha P.; Lee, Timothy J.

2015-01-01

Organic and inorganic molecules, neutral and ions have been observed in the interstellar medium. A few anions of organic molecules have also been observed recently. The Cassini spacecraft in the upper atmosphere of Titan has observed anions of large organic molecules. In this project we have studied the physical and spectroscopic properties of C4H3-, C6H3-, and C6H5-. We have optimized the geometrical structures of all low-lying isomers of the anions, calculated rotational, and harmonic vibrational frequencies of the anions mentioned above using the B3LYP density functional along with the augmented correlation consistent polar valence triple zeta (aug-cc-pVTZ) basis set. We have found many low-lying isomers on the potential energy surface of these anions.

Epitaxially Grown Films of Standing and Lying Pentacene Molecules on Cu(110) Surfaces

PubMed Central

2011-01-01

Here, it is shown that pentacene thin films (30 nm) with distinctively different crystallographic structures and molecular orientations can be grown under essentially identical growth conditions in UHV on clean Cu(110) surfaces. By X-ray diffraction, we show that the epitaxially oriented pentacene films crystallize either in the “thin film” phase with standing molecules or in the “single crystal” structure with molecules lying with their long axes parallel to the substrate. The morphology of the samples observed by atomic force microscopy shows an epitaxial alignment of pentacene crystallites, which corroborates the molecular orientation observed by X-ray diffraction pole figures. Low energy electron diffraction measurements reveal that these dissimilar growth behaviors are induced by subtle differences in the monolayer structures formed by slightly different preparation procedures. PMID:21479111

Gravity-induced stresses near a vertical cliff

USGS Publications Warehouse

Savage, W.Z.

1993-01-01

The exact solution for gravity-induced stresses beneath a vertical cliff presented here has application to the design of cut slopes in rock, compares favorably with published photoelastic and finite-element results for this problem, and satisfies the condition that shear and normal stresses vanish on the ground surface, except at the bottom corner where stress concentrations exist. The solution predicts that horizontal stresses are tensile away from the bottom of the cliff-effects caused by movement below the cliff in response to the gravity loading of the cliff. Also, it is shown that along the top of the cliff normal stresses reduce to those predicted for laterally constrained flat-lying topography. ?? 1993.

Paved Path for Opportunity

NASA Technical Reports Server (NTRS)

2006-01-01

As NASA's Mars Exploration Rover Opportunity continues a southward trek from 'Erebus Crater' toward 'Victoria Crater,' the terrain consists of large sand ripples and patches of flat-lying rock outcrops, as shown in this image. Whenever possible, rover planners keep Opportunity on the 'pavement' for best mobility.

This false-color image mosaic was assembled using images acquired by the panoramic camera on Opportunity's 784th sol (April 8, 2006) at about 11:45 a.m. local solar time. The camera used its 753-nanometer, 535-nanometer and 432-nanometer filters. This view shows a portion of the outcrop named 'Bosque,' including rover wheel tracks, fractured and finely-layered outcrop rocks and smaller, dark cobbles littered across the surface.

Nanowire electron scattering spectroscopy

NASA Technical Reports Server (NTRS)

Hunt, Brian D. (Inventor); Bronikowski, Michael (Inventor); Wong, Eric W. (Inventor); von Allmen, Paul (Inventor); Oyafuso, Fabiano A. (Inventor)

2009-01-01

Methods and devices for spectroscopic identification of molecules using nanoscale wires are disclosed. According to one of the methods, nanoscale wires are provided, electrons are injected into the nanoscale wire; and inelastic electron scattering is measured via excitation of low-lying vibrational energy levels of molecules bound to the nanoscale wire.

Pyramidal-Reflector Solar Heater

NASA Technical Reports Server (NTRS)

1982-01-01

Motor-driven reflector compensates for seasonal changes in Sun's altitude. System has flat-plate absorbers mounted on north side of attic interior. Skylight window on south-facing roof admits Sunlight into attic, lined with mirrors that reflect light to absorbers. Reflectors are inner surfaces of a pyramid lying on its side with window at its base and absorber plates in a cross-sectional plane near its apex.

The Earth Is Flat when Personally Significant Experiences with the Sphericity of the Earth Are Absent

ERIC Educational Resources Information Center

Carbon, Claus-Christian

2010-01-01

Participants with personal and without personal experiences with the Earth as a sphere estimated large-scale distances between six cities located on different continents. Cognitive distances were submitted to a specific multidimensional scaling algorithm in the 3D Euclidean space with the constraint that all cities had to lie on the same sphere. A…

20 CFR 404.1529 - How we evaluate symptoms, including pain.

Code of Federal Regulations, 2012 CFR

2012-04-01

... kinds of evidence described in §§ 404.1512(b)(2) through (8) and 404.1513(b)(1), (4), and (5), and (d.... Your symptoms, such as pain, fatigue, shortness of breath, weakness, or nervousness, will not be found... to relieve your pain or other symptoms (e.g., lying flat on your back, standing for 15 to 20 minutes...

20 CFR 404.1529 - How we evaluate symptoms, including pain.

Code of Federal Regulations, 2014 CFR

2014-04-01

... kinds of evidence described in §§ 404.1512(b)(2) through (8) and 404.1513(b)(1), (4), and (5), and (d.... Your symptoms, such as pain, fatigue, shortness of breath, weakness, or nervousness, will not be found... to relieve your pain or other symptoms (e.g., lying flat on your back, standing for 15 to 20 minutes...

20 CFR 404.1529 - How we evaluate symptoms, including pain.

Code of Federal Regulations, 2013 CFR

2013-04-01

... kinds of evidence described in §§ 404.1512(b)(2) through (8) and 404.1513(b)(1), (4), and (5), and (d.... Your symptoms, such as pain, fatigue, shortness of breath, weakness, or nervousness, will not be found... to relieve your pain or other symptoms (e.g., lying flat on your back, standing for 15 to 20 minutes...

T-duality, non-geometry and Lie algebroids in heterotic double field theory

NASA Astrophysics Data System (ADS)

Blumenhagen, Ralph; Sun, Rui

2015-02-01

A number of issues in heterotic double field theory are studied. This includes the analysis of the T-dual configurations of a flat constant gauge flux background, which turn out to be non-geometric. Performing a field redefinition to a non-geometric frame, these T-duals take a very simple form reminiscent of the constant Q- and R-flux backgrounds. In addition, it is shown how the analysis of arXiv:1304.2784 generalizes to heterotic generalized geometry. For every field redefinition specified by an O( D, D + n) transformation, the structure of the resulting supergravity action is governed by the differential geometry of a corresponding Lie algebroid.

Sediment drifts and contourites on the continental margin off northwest Britain

NASA Astrophysics Data System (ADS)

Stoker, M. S.; Akhurst, M. C.; Howe, J. A.; Stow, D. A. V.

1998-01-01

Seismic reflection profiles and short cores from the continental margin off northwest Britain have revealed a variety of sediment-drift styles and contourite deposits preserved in the northeast Rockall Trough and Faeroe-Shetland Channel. The sediment drifts include: (1) distinctly mounded elongate drifts, both single- and multi-crested; (2) broad sheeted drift forms, varying from gently domed to flat-lying; and (3) isolated patch drifts, including moat-related drifts. Fields of sediment waves are locally developed in association with the elongate and gently domed, broad sheeted drifts. The contrasting styles of the sediment drifts most probably reflect the interaction between a variable bottom-current regime and the complex bathymetry of the continental margin. The bulk of the mounded/gently domed drifts occur in the northeast Rockall Trough, whereas the flat-lying, sheet-form deposits occur in the Faeroe-Shetland Channel, a much narrower basin which appears to have been an area more of sediment export than drift accumulation. Patch drifts are present in both basins. In the northeast Rockall Trough, the along-strike variation from single- to multi-crested elongate drifts may be a response to bottom-current changes influenced by developing drift topography. Muddy, silty muddy and sandy contourites have been recovered in sediment cores from the uppermost parts of the drift sequences. On the basis of their glaciomarine origin, these mid- to high-latitude contourites can be referred to, collectively, as glacigenic contourites. Both partial and complete contourite sequences are preserved; the former consist largely of sandy (mid-only) and top-only contourites. Sandy contourites, by their coarse-grained nature and their formation under strongest bottom-current flows, are the most likely to be preserved in the rock record. However, the very large scale of sediment drifts should be borne in mind with regard to the recognition of fossil contourites in ancient successions.

Ash Shutbah: A possible impact structure in Saudi Arabia

NASA Astrophysics Data System (ADS)

Gnos, Edwin; Hofmann, Beda A.; Schmieder, Martin; Al-Wagdani, Khalid; Mahjoub, Ayman; Al-Solami, Abdulaziz A.; Habibullah, Siddiq N.; Matter, Albert; Alwmark, Carl

2014-10-01

We have investigated the Ash Shutbah circular structure in central Saudi Arabia (21°37'N 45°39'E) using satellite imagery, field mapping, thin-section petrography, and X-ray diffraction of collected samples. The approximately 2.1 km sized structure located in flat-lying Jurassic Tuwaiq Mountain Limestone has been nearly peneplained by erosional processes. Satellite and structural data show a central area consisting of Dhruma Formation sandstones with steep bedding and tight folds plunging radially outward. Open folding occurs in displaced, younger Tuwaiq Mountain Limestone Formation blocks surrounding the central area, but is absent outside the circular structure. An approximately 60 cm thick, unique folded and disrupted orthoquartzitic sandstone marker bed occurring in the central area of the structure is found 140 m deeper in undisturbed escarpment outcrops located a few hundred meters west of the structure. With exception of a possible concave shatter cone found in the orthoquartzite of the central area, other diagnostic shock features are lacking. Some quartz-rich sandstones from the central area show pervasive fracturing of quartz grains with common concussion fractures. This deformation was followed by an event of quartz dissolution and calcite precipitation consistent with local sea- or groundwater heating. The combination of central stratigraphic uplift of 140 m, concussion features in discolored sandstone, outward-dipping concentric folds in the central area, deformation restricted to the rocks of the ring structure, a complex circular structure of 2.1 km diameter that appears broadly consistent with what one would expect from an impact structure in sedimentary targets, and a possible shatter cone all point to an impact origin of the Ash Shutbah structure. In fact, the Ash Shutbah structure appears to be a textbook example of an eroded, complex impact crater located in flat-lying sedimentary rocks, where the undisturbed stratigraphic section can be studied in escarpment outcrops in the vicinity of the structure.

Reconstructing Rodinia: the view from Amazonia

NASA Astrophysics Data System (ADS)

Tohver, E.; van der Pluijm, B.; Van der Voo, R.; Scandolara, J.; Rizzotto, G.

2001-05-01

Many Rodinia reconstructions propose that the North American Grenville orogeny at c.1.1 Ga was due to collision between Laurentia and the western Amazon craton, the position of which is presently unrestricted by paleomagnetic data. New paleomagnetic data was collected from the flat-lying basalts and gabbros of the Nova Floresta Formation (K-Ar whole rock, 982 +/-10 Ma, 1038 +/-14 Ma) of Rondonia, western Brazil to constrain the paleogeography of the proposed Laurentia-Amazonia link. Measurement of the anisotropy of magnetic susceptibility (AMS) on the gabbroic samples reveals a flat-lying foliation with a radiating pattern of lineations, demonstrating that the gabbros are part of a large, undeformed sill. Thermal and alternating field (AF) demagnetization of the basalt samples reveals a single component that is oriented WNW and steeply upward. For the gabbro samples, AF demagnetization is more successful than thermal demagnetization at resolving individual components. A characteristic remanence isolated in fields commonly above 40 mT is identical to the single component recorded in the basalts, suggesting that this magnetization was acquired at the same time. A paleomagnetic N-pole calculated from the Nova Floresta Formation (n = 16 sites, Plat. = 26.1N, PLon. = 163.4E, A95 = 5.9) can be matched to the Laurentia APWP for the 1150-750 Ma interval and permits geographic proximity of the two cratons during Grenvillian times. However, the orientation of the Aguapee-Sunsas belt based on this pole suggests a N-S oriented belt, in contrast with the E-W orientation of the Grenville belt on the Laurentian margin. It is proposed that the Amazon craton was rotated 90 degrees counterclockwise from the orientation required by the Laurentia-Amazonia connection. This N-S orientation of the Sunsas-Aguapei belt suggests that the western margin of the Amazon craton was juxtaposed with the Namaqua belt of the western Kalahari craton. This configuration is supported by a common Neoproterozoic rift stratigraphy between Namibia and Mato Grosso.

Geologic map of the Winslow 30’ × 60’ quadrangle, Coconino and Navajo Counties, northern Arizona

USGS Publications Warehouse

Billingsley, George H.; Block, Debra L.; Redsteer, Margaret Hiza

2013-01-01

The Winslow 30’ × 60’ quadrangle encompasses approximately 5,018 km2 (1,960 mi2) within Coconino and Navajo Counties of northern Arizona. It is characterized by gently dipping Paleozoic and Mesozoic strata that dip 1° to 2° northeastward in the southwestern part of the quadrangle and become nearly flat-lying in the northeastern part of the quadrangle. In the northeastern part, a shallow Cenozoic erosional basin developed about 20 million years ago, which subsequently was filled with flat-lying Miocene and Pliocene lacustrine sediments of the Bidahochi Formation, as well as associated volcanic rocks of the Hopi Buttes Volcanic Field. The lacustrine sediments and volcanic rocks unconformably overlie Triassic, Jurassic, and Cretaceous strata. Beginning about early Pliocene time, the Little Colorado River and its tributaries began to remove large volumes of Paleozoic and Mesozoic bedrock from the map area. This erosional development has continued through Pleistocene and Holocene time. Fluvial sediments accumulated episodically throughout this erosional cycle, as indicated by isolated Pliocene(?) and Pleistocene Little Colorado River terrace-gravel deposits on Tucker Mesa and Toltec Divide west of Winslow and younger terrace-gravel deposits along the margins of the Little Colorado River Valley. These gravel deposits suggest that the ancestral Little Colorado River and its valley has eroded and migrated northeastward toward its present location and largely parallels the strike of the Chinle Formation. Today, the Little Colorado River meanders within a 5-km (3-mi) wide valley between Winslow and Leupp, where soft strata of the Chinle Formation is mostly covered by an unknown thickness of Holocene flood-plain deposits. In modern times, the Little Colorado River channel has changed its position as much as a 1.5 km (1 mi) during flood events, but for much of the year the channel is a dry river bed. Surficial alluvial and eolian deposits cover extensive parts of the bedrock outcrops over the entire Winslow quadrangle.

Low-lying π∗ resonances associated with cyano groups: A CAP/SAC-CI study

NASA Astrophysics Data System (ADS)

Ehara, Masahiro; Kanazawa, Yuki; Sommerfeld, Thomas

2017-01-01

The complex absorbing potential (CAP)/symmetry-adapted cluster-configuration interaction (SAC-CI) method is applied to low-lying π∗ resonance states of molecules containing one or two cyano (CN) groups. Benchmark calculations are carried out comparing the non-variational and approximate variational approach of SAC-CI and studying the selection threshold of operators. Experimental resonance positions from electron transmission spectroscopy (ETS) are reproduced provided the anticipated deviations due to vibronic effects are taken into account. Moreover, the calculated positions and widths agree well with those obtained in previous electron scattering calculations for HCN, CH3CN and their isonitriles. Based on our results, we suggest a reassignment of the experimental ETS of fumaronitrile and malononitrile. Our present results demonstrate again that the CAP/SAC-CI method reliably predicts low-lying π∗ resonances, and regarding the total numbers of molecules and resonances investigated, it is fair to say that it is presently the most extensively used high-level method in the temporary anion field.

Observation of pendular butterfly Rydberg molecules

PubMed Central

Niederprüm, Thomas; Thomas, Oliver; Eichert, Tanita; Lippe, Carsten; Pérez-Ríos, Jesús; Greene, Chris H.; Ott, Herwig

2016-01-01

Engineering molecules with a tunable bond length and defined quantum states lies at the heart of quantum chemistry. The unconventional binding mechanism of Rydberg molecules makes them a promising candidate to implement such tunable molecules. A very peculiar type of Rydberg molecules are the so-called butterfly molecules, which are bound by a shape resonance in the electron–perturber scattering. Here we report the observation of these exotic molecules and employ their exceptional properties to engineer their bond length, vibrational state, angular momentum and orientation in a small electric field. Combining the variable bond length with their giant dipole moment of several hundred Debye, we observe counter-intuitive molecules which locate the average electron position beyond the internuclear distance. PMID:27703143

Heterogeneous nucleation of polymorphs on polymer surfaces: polymer-molecule interactions using a Coulomb and van der Waals model.

PubMed

Wahlberg, Nanna; Madsen, Anders Ø; Mikkelsen, Kurt V

2018-06-09

The nucleation processes of acetaminophen on poly(methyl methacrylate) and poly(vinyl acetate) have been investigated and the mechanisms of the processes are studied. This is achieved by a combination of theoretical models and computational investigations within the framework of a modified QM/MM method; a Coulomb-van der Waals model. We have combined quantum mechanical computations and electrostatic models at the atomistic level for investigating the stability of different orientations of acetaminophen on the polymer surfaces. Based on the Coulomb-van der Waals model, we have determined the most stable orientation to be a flat orientation, and the strongest interaction is seen between poly(vinyl acetate) and the molecule in a flat orientation in vacuum.

Tabular comparisons of the Flynn Creek impact crater, United States, Steinheim impact crater, Germany and Snowball explosion crater, Canada

NASA Technical Reports Server (NTRS)

Roddy, D. J.

1977-01-01

A tabular outline of comparative data is presented for 340 basic dimensional, morphological, and structural parameters and related aspects for three craters of the flat-floored, central uplift type, two of which are natural terrestrial impact craters and one is a large-scale experimental explosion crater. The three craters are part of a general class, in terms of their morphology and structural deformation that is represented on each of the terrestrial planets including the moon. One of the considered craters, the Flynn Creek Crater, was formed by a hypervelocity impact event approximately 360 m.y. ago in what is now north central Tennessee. The impacting body appears to have been a carbonaceous chondrite or a cometary mass. The second crater, the Steinheim Crater, was formed by an impact event approximately 14.7 m.y. ago in what is now southwestern Germany. The Snowball Crater was formed by the detonation of a 500-ton TNT hemisphere on flat-lying, unconsolidated alluvium in Alberta, Canada.

Designing an Early Childhood Environment: A Community-Built Playscape on Matakana Island, New Zealand

ERIC Educational Resources Information Center

Christie, Toni; Christie, Robin

2011-01-01

Across the mouth of the Tauranga Harbour lies a piece of paradise, Te Moutere o Matakana--Matakana Island. It is blessed with an ocean beach with white sand and a mean surf break, tidal flats, wetlands, fertile pasture, and a native and exotic forest. It is home to a maori language nest for the local children--Te Kohanga Reo o te Moutere o…

Carter separable electromagnetic fields

NASA Astrophysics Data System (ADS)

Lynden-Bell, D.

2000-02-01

The purely electromagnetic analogue in flat space of Kerr's metric in general relativity is only rarely considered. Here we carry out in flat space a programme similar to Carter's investigation of metrics in general relativity in which the motion of a charged particle is separable. We concentrate on the separability of the motion (be it classical, relativistic or quantum) of a charged particle in electromagnetic fields that lie in planes through an axis of symmetry. In cylindrical polar coordinates (t,R,φ,z) the four-vector potential takes the form [formmu2] is the unit toroidal vector. The forms of the functions Φ(R,z) and A(R,z) are sought that allow separable motion. This occurs for relativistic motion only when AR,Φ and A2-Φ2 are all of the separable form ζ(λ)-η(μ)]/(λ-μ), where ζ and η are arbitrary functions, and λ and μ are spheroidal coordinates or degenerations thereof. The special forms of A and Φ that allow this are deduced. They include the Kerr metric analogue, with E+iB=-∇{q[(r-ia).(r-ia)]-1/2}. Rather more general electromagnetic fields allow separation when the motion is non-relativistic. The investigation is extended to fields that lie in parallel planes. Connections to Larmor's theorem are remarked upon.

Excited State Energetics and Dynamics of Large Molecules, Complexes and Clusters

DTIC Science & Technology

1988-07-01

tetracene. Ar (n=l-5) complexes, providing central information on microscopic solvent shifts. These studies were extended to M-metal atom com - plexes...corresponding to the bare molecule. At higher 2. Experimental stagnation pressures of Ar (p = 80-150 Toff) the contributions of van der Waals DPB. Ar, com - Our...gas aromatic-molecule complexes were docu- So - S1 transition of the trans-stilbene (TS)-Ar com - mented experimentally to lie in the rango - 30- plex

Probable Mid-Miocene Caldera in the Modoc Plateau, Northeast California

NASA Astrophysics Data System (ADS)

Bowens, T. E.; Grose, T. L.

2001-12-01

Regional geologic mapping within the Modoc Plateau has resulted in the discovery of a large volcanotectonic anomaly some 21-km in diameter approximately 50-km WSW of the city of Alturas in Modoc County, California. Centrally located within this anomaly lies a structural depression some 11-km in diameter which, based on structural, lithologic, and geophysical characteristics, is believed to represent a deeply eroded mid-Miocene caldera. The region extending outward some 5-km from the proposed caldera displays a sharp, localized structural deflection from a NNW to a WNW structural grain. Lying inboard of this deflection, a series of regionally discordant E-W to NE trending, generally down to the north, normal faults were discovered which are believed to represent rim faults to an ancient caldera. Bedding within the hanging wall of these discordant structures displays highly contorted and regionally anomalous dips. By stereographic removal of the regional northeast dip overprinting the area, the anomalous dips were found to display a radial, steeply inward dipping pattern in close proximity to the proposed rim structures while dips located further inboard are generally flat-lying. Lithologies within the proposed caldera are regionally anomalous and include abundant tuffaceous and flow dominated breccias, closed basin organic sedimentary facies, and an anomalous concentration of volcanic centers of both mafic and felsic compositions. One of these intrusives was age dated at 12.9 Ma indicating the anomaly formed during mid-Miocene time. The location of the proposed caldera is associated with a +20 mgal gravity high, which stands in contrast to a lesser high of +10 mgal associated with the Medicine Lake Caldera some 50-km to the northwest. This combination of structural, lithologic, and geophysical evidence leads to the interpretation of a caldera at this location, herein termed the Stone Coal Valley Caldera.

Electronic spectra from TDDFT and machine learning in chemical space

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ramakrishnan, Raghunathan; Hartmann, Mia; Tapavicza, Enrico

Due to its favorable computational efficiency, time-dependent (TD) density functional theory (DFT) enables the prediction of electronic spectra in a high-throughput manner across chemical space. Its predictions, however, can be quite inaccurate. We resolve this issue with machine learning models trained on deviations of reference second-order approximate coupled-cluster (CC2) singles and doubles spectra from TDDFT counterparts, or even from DFT gap. We applied this approach to low-lying singlet-singlet vertical electronic spectra of over 20 000 synthetically feasible small organic molecules with up to eight CONF atoms. The prediction errors decay monotonously as a function of training set size. For amore » training set of 10 000 molecules, CC2 excitation energies can be reproduced to within +/- 0.1 eV for the remaining molecules. Analysis of our spectral database via chromophore counting suggests that even higher accuracies can be achieved. Based on the evidence collected, we discuss open challenges associated with data-driven modeling of high-lying spectra and transition intensities.« less

Earth observations during STS-58

NASA Image and Video Library

1993-10-22

STS058-88-017 (18 Oct-1 Nov 1993) --- The eye-catching "bullseye" of the Richat Structure adds interest to the barren Gres de Chinguetti Plateau in central Mauretania, northwest Africa. It represents domally uplifted, layered (sedimentary) rocks that have been eroded by water and wind into the present shape. Desert sands have invaded the feature from the south. The origin of the structure is unknown. It is not an impact structure, because field work showed that strata are undisturbed and flat-lying in the middle of the feature, and no shock-altered rock could be found. There is no evidence for a salt dome or shale diapir, nor is there any geophysical evidence for an underlying dome of dense igneous rock having about the same density as the sedimentary layers.

On superintegrable monopole systems

NASA Astrophysics Data System (ADS)

Fazlul Hoque, Md; Marquette, Ian; Zhang, Yao-Zhong

2018-02-01

Superintegrable systems with monopole interactions in flat and curved spaces have attracted much attention. For example, models in spaces with a Taub-NUT metric are well-known to admit the Kepler-type symmetries and provide non-trivial generalizations of the usual Kepler problems. In this paper, we overview new families of superintegrable Kepler, MIC-harmonic oscillator and deformed Kepler systems interacting with Yang-Coulomb monopoles in the flat and curved Taub-NUT spaces. We present their higher-order, algebraically independent integrals of motion via the direct and constructive approaches which prove the superintegrability of the models. The integrals form symmetry polynomial algebras of the systems with structure constants involving Casimir operators of certain Lie algebras. Such algebraic approaches provide a deeper understanding to the degeneracies of the energy spectra and connection between wave functions and differential equations and geometry.

Solving the flatness problem with an anisotropic instanton in Hořava-Lifshitz gravity

NASA Astrophysics Data System (ADS)

Bramberger, Sebastian F.; Coates, Andrew; Magueijo, João; Mukohyama, Shinji; Namba, Ryo; Watanabe, Yota

2018-02-01

In Hořava-Lifshitz gravity a scaling isotropic in space but anisotropic in spacetime, often called "anisotropic scaling," with the dynamical critical exponent z =3 , lies at the base of its renormalizability. This scaling also leads to a novel mechanism of generating scale-invariant cosmological perturbations, solving the horizon problem without inflation. In this paper we propose a possible solution to the flatness problem, in which we assume that the initial condition of the Universe is set by a small instanton respecting the same scaling. We argue that the mechanism may be more general than the concrete model presented here. We rely simply on the deformed dispersion relations of the theory, and on equipartition of the various forms of energy at the starting point.

Differential characters and cohomology of the moduli of flat connections

NASA Astrophysics Data System (ADS)

Castrillón López, Marco; Ferreiro Pérez, Roberto

2018-05-01

Let π {:} P→ M be a principal bundle and p an invariant polynomial of degree r on the Lie algebra of the structure group. The theory of Chern-Simons differential characters is exploited to define a homology map χ k {:} H_{2r-k-1}(M)× Hk(F/G)→ R/Z , for k

Deep and shallow forms of the sulcus for extensor carpi ulnaris.

PubMed

Nakashima, T; Hojo, T; Furukawa, H

1993-12-01

Anatomical variations in the sulcus for the tendon of extensor carpi ulnaris were studied in 240 upper limbs. The sulcus lies between the head and the styloid process on the dorsal surface of the distal end of the ulna. This groove has deep and shallow forms and, rarely, a flat form. The sulcus was classified into 4 grades according to its depth. Grade I, a deep sulcus, was found in 51.3%. Grades II and III are shallow, but the styloid process in grade II is more prominent than in grade III. The former was found in 28.8%, the latter in 14.2%. Grade IV is a flat form. This was rare and found only in 1.3%. This variation was not age-related, but was a congenital feature.

Electron Transport through Porphyrin Molecular Junctions

NASA Astrophysics Data System (ADS)

Zhou, Qi

The goal of this work is to study the properties that would affect the electron transport through a porphyrin molecular junction. This work contributes to the field of electron transport in molecular junctions in the following 3 aspects. First of all, by carrying out experiments comparing the conductance of the iron (III) porphyrin (protected) and the free base porphyrin (protected), it is confirmed that the molecular energy level broadening and shifting occurs for porphyrin molecules when coupled with the metal electrodes, and this level broadening and shifting plays an important role in the electron transport through molecular junctions. Secondly, by carrying out an in-situ deprotection of the acetyl-protected free base porphyrin molecules, it is found out that the presence of acetyl groups reduces the conductance. Thirdly, by incorporating the Matrix-assisted laser desorption/ionization (MALDI) spectrum and the in-situ deprotection prior to formation of molecular junctions, it allows a more precise understanding of the molecules involved in the formation of molecular junctions, and therefore allows an accurate analysis of the conductance histogram. The molecules are prepared by self-assembly and the junctions are formed using a Scanning Tunneling Microscopy (STM) molecular break junction technique. The porphyrin molecules are characterized by MALDI in solution before self-assembly to a gold/mica substrate. The self-assembled monolayers (SAMs) of porphyrins on gold are characterized by Ultraviolet-visible (UV-Vis) reflection spectroscopy to confirm that the molecules are attached to the substrate. The SAMs are then characterized by Angle-Resolved X-ray photoelectron spectroscopy (ARXPS) to determine the thickness and the average molecular orientation of the molecular layer. The electron transport is measured by conductance-displacement (G-S) experiments under a given bias (-0.4V). The conductance value of a single molecule is identified by a statistical analysis over a large set of measurements. In this thesis, I focus on two factors that would affect the electron transport through the porphyrin molecules, namely, the metal ion center, and the deprotection of the end groups. The effect of metal ion center is studied by comparing the conductance of an iron (III) porphyrin (protected) to that of a free base porphyrin (protected). The in-situ deprotection of the molecules before forming the junctions is completed to study the effect of the molecular-electrode interaction. The first factor studied, that is, the metal ion center in the porphyrin molecule, show that the conductance for iron (III) porphyrin (protected) is 3.74 x10-5 G0, and the conductance for the free base porphyrin (protected) is 4.73x10-5 G0 , where G0 = e2 / pih = (25.8kO)-1 is the quantized unit of electrical conductance. Through our collaborative efforts, first principles calculations carried out by our collaborators for the molecular levels of an isolated molecule (without electrodes) show that the energy levels of an iron (III) porphyrin molecule are slightly shifted compared to that of the free base porphyrin. For the free base porphyrin, the highest occupied molecular orbital (HOMO) level (-4.952 eV) lies between the chemical potentials of the substrate (-4.7 eV) and the STM tip (-5.1 eV). This level serves as a channel for electron transport. For the iron (III) porphyrin, the HOMO is at -5.306 eV, which is not in between the chemical potentials of the substrate. Therefore, a significantly smaller conductance is expected for the iron (III) porphyrin compared to the conductance of a free base porphyrin, because of the lack of the electron transport channel. However, the conductance measured from G-S experiments is comparable, i.e. 3.74 x10-5 G0 for iron (III) porphyrin and 4.73x10-5 G0 for free base porphyrin. This suggests that the molecular energy level broadening and shifting occurs for porphyrin molecules when coupled with the metal electrodes, and this level broadening and shifting may significantly affect the electron transport through molecular junctions. The second factor studied, that is, the deprotection of the porphyrin end groups (acetylthio, -SCOCH3), was completed in-situ for the free base porphyrin through the reaction of the acetylthio with sulfuric acid at 35° Celsius for 3 hours. MALDI spectroscopy confirms that two additional deprotected porphyrin species are formed by deprotection, with protonated (MH+) molecular masses of 721 and 679, corresponding to a partially deprotected porphyrin (i.e. only one of the two end groups deprotected), and a fully deprotected porphyrin molecule. Along with the un-reacted acetyl protected porphyrin, a total of 3 porphyrin species are in the solution. This solution is used for self-assembly on a gold/mica surface. The thickness of the in-situ deprotected SAM is determined to be ˜1.7 nm, confirming a relatively upright molecular orientation (54.0°-63.5° between the substrate surface and the molecule), compared to a thickness of ˜1.5 nm for the protected SAM that has a more flat-lying molecular orientation (˜45.6° between the substrate surface and the molecule). From G-S measurements on SAMs prepared by in-situ deprotection, junctions with lower conductance steps at mid 10-5 G0 and junctions with higher conductance steps around 10-4 G 0 are observed. Supported by computational modeling from our collaborating research group, we associate the lower conductance steps to junctions based on the protected form of thiols at the tip-molecule interface, and the higher conductance steps to the deprotected form of the thiol contacts. We suggest that the reduced conductance in the protected porphyrin originates from the presence of the acetyl end groups (-COCH3), rather than from the elongation of the sulfur-gold (S-Au) bonds at the tip-molecule interface. By studying these two factors, I expect this work to provide insights into electron transport through molecules or metal-molecule-metal junctions, and in applications related to integrating molecules as functional units in electronic devices. Future work related to this thesis may include the molecular conductance based on reduction-oxidation (redox) properties of iron ligated porphyrins for the application of molecular switches and molecular memory elements.

Fullerene-free small molecule organic solar cells with a high open circuit voltage of 1.15 V.

PubMed

Ni, Wang; Li, Miaomiao; Kan, Bin; Liu, Feng; Wan, Xiangjian; Zhang, Qian; Zhang, Hongtao; Russell, Thomas P; Chen, Yongsheng

2016-01-11

A new small molecule named DTBTF with thiobarbituric acid as a terminal group was designed and synthesized as an acceptor for organic photovoltaic applications. DTBTF exhibits strong absorption in the visible region, and a relatively high lying LUMO energy level (-3.62 eV). All-small-molecule organic solar cells based on DR3TSBDT:DTBTF blend films show a considerable PCE of 3.84% with a high V(oc) of 1.15 V.

High-temperature partition functions, specific heats and spectral radiative properties of diatomic molecules with an improved calculation of energy levels

NASA Astrophysics Data System (ADS)

Qin, Z.; Zhao, J. M.; Liu, L. H.

2018-05-01

The level energies of diatomic molecules calculated by the frequently used Dunham expansion will become less accurate for high-lying vibrational and rotational levels. In this paper, the potential curves for the lower-lying electronic states with accurate spectroscopic constants are reconstructed using the Rydberg-Klein-Rees (RKR) method, which are extrapolated to the dissociation limits by fitting of the theoretical potentials, and the rest of the potential curves are obtained from the ab-initio results in the literature. Solving the rotational dependence of the radial Schrödinger equation over the obtained potential curves, we determine the rovibrational level energies, which are then used to calculate the equilibrium and non-equilibrium thermodynamic properties of N2, N2+, NO, O2, CN, C2, CO and CO+. The partition functions and the specific heats are systematically validated by available data in the literature. Finally, we calculate the radiative source strengths of diatomic molecules in thermodynamic equilibrium, which agree well with the available values in the literature. The spectral radiative intensities for some diatomic molecules in thermodynamic non-equilibrium are calculated and validated by available experimental data.

Structural features of small benzene clusters (C6H6)n (n ≤ 30) as investigated with the all-atom OPLS potential.

PubMed

Takeuchi, Hiroshi

2012-10-18

The structures of the simplest aromatic clusters, benzene clusters (C(6)H(6))(n), are not well elucidated. In the present study, benzene clusters (C(6)H(6))(n) (n ≤ 30) were investigated with the all-atom optimized parameters for liquid simulation (OPLS) potential. The global minima and low-lying minima of the benzene clusters were searched with the heuristic method combined with geometrical perturbations. The structural features and growth sequence of the clusters were examined by carrying out local structure analyses and structural similarity evaluation with rotational constants. Because of the anisotropic interaction between the benzene molecules, the local structures consisting of 13 molecules are considerably deviated from regular icosahedron, and the geometries of some of the clusters are inconsistent with the shapes constructed by the interior molecules. The distribution of the angle between the lines normal to two neighboring benzene rings is anisotropic in the clusters, whereas that in the liquid benzene is nearly isotropic. The geometries and energies of the low-lying configurations and the saddle points between them suggest that most of the configurations previously detected in supersonic expansions take different orientations for one to four neighboring molecules.

Generalizations of the Toda molecule

NASA Astrophysics Data System (ADS)

Van Velthoven, W. P. G.; Bais, F. A.

1986-12-01

Finite-energy monopole solutions are constructed for the self-dual equations with spherical symmetry in an arbitrary integer graded Lie algebra. The constraint of spherical symmetry in a complex noncoordinate basis leads to a dimensional reduction. The resulting two-dimensional ( r, t) equations are of second order and furnish new generalizations of the Toda molecule equations. These are then solved by a technique which is due to Leznov and Saveliev. For time-independent solutions a further reduction is made, leading to an ansatz for all SU(2) embeddings of the Lie algebra. The regularity condition at the origin for the solutions, needed to ensure finite energy, is also solved for a special class of nonmaximal embeddings. Explicit solutions are given for the groups SU(2), SO(4), Sp(4) and SU(4).

Dimer formation of perylene: An ultracold spectroscopic and computational study

NASA Astrophysics Data System (ADS)

Birer, Ö.; Yurtsever, E.

2015-10-01

The electronic spectra of perylene inside helium nanodroplets recorded by the depletion method are presented. The results show two broad peaks in addition to sharp monomer vibronic transitions due to dimer formation. In order to understand the details of the spectra, first the dimer formation is studied by DFT and SCS-MP2 calculations and then the electronic spectra are calculated at the minima of the potential energy surface (PES). Theoretical calculations show that there are two low-lying energetically degenerate dimer structures; namely a parallel displaced one and a rotated stacked one. PES around these minima is very flat with a number of local minima at higher energies which at the experimental temperatures cannot be populated. Even though thermodynamically these two structures are equally populated, dynamical considerations point out that in helium droplet the parallel displaced geometry is encouraged by the natural alignment of the molecules due to the acquired angular momentum following the pick-up process. The calculated spectrum of the parallel displaced geometry predicts the positions of the dimer transitions within 30 nm of the experimental spectrum. Furthermore, the difference between the two dimer transitions is accurately predicted to be about 25 nm while the experimental difference was about 20 nm. Such a small difference could only be detected due to the ultracold conditions helium nanodroplets provided.

A SERS-based pH sensor utilizing 3-amino-5-mercapto-1,2,4-triazole functionalized Ag nanoparticles.

PubMed

Piotrowski, Piotr; Wrzosek, Beata; Królikowska, Agata; Bukowska, Jolanta

2014-03-07

We report the first use of 3-amino-5-mercapto-1,2,4-triazole (AMT) to construct a surface-enhanced Raman scattering (SERS) based pH nano- and microsensor, utilizing silver nanoparticles. We optimize the procedure of homogenous attachment of colloidal silver to micrometer-sized silica beads via an aminosilane linker. Such micro-carriers are potential optically trappable SERS microprobes. It is demonstrated that the SERS spectrum of AMT is strongly dependent on the pH of the surroundings, as the transformation between two different adsorption modes, upright (A form) and lying flat (B form) orientation, is provoked by pH variation. The possibility of tuning the nanosensor working range by changing the concentration of AMT in the surrounding solution is demonstrated. A strong correlation between the pH response of the nanosensor and the AMT concentration in solution is found to be controlled by the interactions between the surface and solution molecules. In the absence of the AMT monomer, the performance of both the nano- and microsensor is shifted substantially to the strongly acidic pH range, from 1.5 to 2.5 and from 1.0 to 2.0, respectively, which is quite unique even for SERS-based sensors.

Microfluidic Extraction of Biomarkers using Water as Solvent

NASA Technical Reports Server (NTRS)

Amashukeli, Xenia; Manohara, Harish; Chattopadhyay, Goutam; Mehdi, Imran

2009-01-01

A proposed device, denoted a miniature microfluidic biomarker extractor (mu-EX), would extract trace amounts of chemicals of interest from samples, such as soils and rocks. Traditionally, such extractions are performed on a large scale with hazardous organic solvents; each solvent capable of dissolving only those molecules lying within narrow ranges of specific chemical and physical characteristics that notably include volatility, electric charge, and polarity. In contrast, in the mu-EX, extractions could be performed by use of small amounts (typically between 0.1 and 100 L) of water as a universal solvent. As a rule of thumb, in order to enable solvation and extraction of molecules, it is necessary to use solvents that have polarity sufficiently close to the polarity of the target molecules. The mu-EX would make selection of specific organic solvents unnecessary, because mu-EX would exploit a unique property of liquid water: the possibility of tuning its polarity to match the polarity of organic solvents appropriate for extraction of molecules of interest. The change of the permittivity of water would be achieved by exploiting interactions between the translational states of water molecules and an imposed electromagnetic field in the frequency range of 300 to 600 GHz. On a molecular level, these interactions would result in disruption of the three-dimensional hydrogen-bonding network among liquid-water molecules and subsequent solvation and hydrolysis of target molecules. The mu-EX is expected to be an efficient means of hydrolyzing chemical bonds in complex macromolecules as well and, thus, enabling analysis of the building blocks of these complex chemical systems. The mu-EX device would include a microfluidic channel, part of which would lie within a waveguide coupled to an electronically tuned source of broad-band electromagnetic radiation in the frequency range from 300 to 600 GHz (see figure). The part of the microfluidic channel lying in the waveguide would constitute an interaction volume. The dimensions of the interaction volume would be chosen in accordance with the anticipated amount of solid sample material needed to ensure extraction of sufficient amount of target molecules for detection and analysis. By means that were not specified at the time of reporting the information for this article, the solid sample material would be placed in the interaction volume. Then the electromagnetic field would be imposed within the waveguide and water would be pumped through the interaction volume to effect the extraction.

Physical mechanism for flat-to-lenticular lens conversion in homogeneous liquid crystal cell with periodically undulated electrode.

PubMed

Na, Jun-Hee; Park, Seung Chul; Kim, Se-Um; Choi, Yoonseuk; Lee, Sin-Doo

2012-01-16

A convertible lenticular liquid crystal (LC) lens architecture is demonstrated using an index-matched planarization layer on a periodically undulated electrode for the homogeneous alignment of an LC. It is found that the in-plane component of the electric field by the undulated electrode plays a primary role in the flat-to-lens effect while the out-of-plane component contributes to the anchoring enhancement of the LC molecules in the surface layer. Our LC device having an index-matched planarization layer on the undulated electrode is capable of achieving the electrical tunability from the flat surface to the lenticular lens suitable for 2D/3D convertible displays.

Exploring biology with small organic molecules

PubMed Central

Stockwell, Brent R.

2011-01-01

Small organic molecules have proven to be invaluable tools for investigating biological systems, but there is still much to learn from their use. To discover and to use more effectively new chemical tools to understand biology, strategies are needed that allow us to systematically explore ‘biological-activity space’. Such strategies involve analysing both protein binding of, and phenotypic responses to, small organic molecules. The mapping of biological-activity space using small molecules is akin to mapping the stars — uncharted territory is explored using a system of coordinates that describes where each new feature lies. PMID:15602550

The binding energies of one and two water molecules to the first transition-row metal positive ions. II

NASA Technical Reports Server (NTRS)

Rosi, Marzio; Bauschlicher, Charles W., Jr.

1990-01-01

The present investigation of H2O's binding energy to transition-metal ions proceeds from the D(2h) structure and bends the two water molecules out of plane. The molecule is constrained to have C(2v) symmetry, so that each water molecule and metal ion lies on a plane. The ground states are bent only for Mn(H2O)2(+) and Zn(H2O)2(+), where only 4s4p hybridization is energetically favorable; 4s4p hybridization reduces repulsion.

The xyloglucan-cellulose assembly at the atomic scale.

PubMed

Hanus, Jaroslav; Mazeau, Karim

2006-05-01

The assembly of cell wall components, cellulose and xyloglucan (XG), was investigated at the atomistic scale using molecular dynamics simulations. A molecular model of a cellulose crystal corresponding to the allomorph Ibeta and exhibiting a flexible complex external morphology was employed to mimic the cellulose microfibril. The xyloglucan molecules considered were the three typical basic repeat units, differing only in the size of one of the lateral chain. All the investigated XG fragments adsorb nonspecifically onto cellulose fiber; multiple arrangements are equally probable, and every cellulose surface was capable of binding the short XG molecules. The following structural effects emerged: XG molecules that do not have any long side chains tended to adapt themselves nicely to the topology of the microfibril, forming a flat, outstretched conformation with all the sugar residues interacting with the surface. In contrast, the XG molecules, which have long side chains, were not able to adopt a flat conformation that would enable the interaction of all the XG residues with the surface. In addition to revealing the fundamental atomistic details of the XG adsorption on cellulose, the present calculations give a comprehensive understanding of the way the XG molecules can unsorb from cellulose to create a network that forms the cell wall. Our revisited view of the adsorption features of XG on cellulose microfibrils is consistent with experimental data, and a model of the network is proposed. Copyright (c) 2006 Wiley Periodicals, Inc.

Recent faulting and microearthquakes at the intersection of the Vema Fracture Zone and the Mid-Atlantic Ridge

NASA Astrophysics Data System (ADS)

Rowlett, Hugh; Forsyth, Donald W.

1984-07-01

New air gun reflection profiles, 3.5-kHz reflection profiles, and microearthquake data recorded by an array of ocean bottom seismographs form the basis for this study of the transition from a spreading center to a major transform fault. Disturbances of the thick, normally flat-lying, turbidite deposits provide indications of recent vertical motions. At the western intersection of the fracture zone with the median valley there is a depression in the sediments that represents the southerly extension of the median valley into the fracture zone valley. The depression is terminated abruptly on the south by the active transform fault, which acts as a locus for vertical as well as horizontal displacement. Flat-lying, undisturbed sediments terminate abruptly at the fault. The western boundary of the depression is much broader and is characterized by a series of slumplike steps. To the west, there is little or no evidence for uplift or tilting of sediments which might indicate vertical recovery of the crust as it spreads away from the depression. This suggests that uplift and recovery out of the depression is episodic in nature and has been inactive over the last million years along the western boundary. To the east there is clear evidence of uplift and tilting of sedimentary layers. A basement ridge emerging from the sediments is currently being uplifted and rotated in a manner analogous to processes responsible for the creation and cancellation of median valley relief. The transition between the spreading center and the transform fault appears to take place within 1-2 km. The width of the transform fault just east of the depression is less than a kilometer. Microearthquakes were located and displayed by new methods that directly account for nonlinearities associated with small arrays. Microearthquakes located by three or more ocean bottom seismometers show that the greatest seismic activity occurs along the eastern walls of the median valley, at the basement ridge, in the eastern portion of the depression and in the crestal mountains. Very little activity is associated with the western edge of the transform depression and the trace of the transform fault.

Structures and lithofacies of inferred silicic conduits in the Paraná-Etendeka LIP, southernmost Brazil

NASA Astrophysics Data System (ADS)

Simões, M. S.; Lima, E. F.; Sommer, C. A.; Rossetti, L. M. M.

2018-04-01

Extensive silicic units in the Paraná-Etendeka LIP have been long interpreted as pyroclastic density currents (rheomorphic ignimbrites) derived from the Messum Complex in Namibia. In recent literature, however, they have been characterized as effusive lava flows and domes. In this paper we describe structures and lithofacies related to postulated silicic lava feeder conduits at Mato Perso, São Marcos and Jaquirana-Cambará do Sul areas in southern Brazil. Inferred conduits are at least 15-25 m in width and the lithofacies include variably vesicular monomictic welded and non-welded breccias in the margins to poorly vesicular, banded, spherulitic and microfractured vitrophyres in the central parts. Flat-lying coherent vitrophyres and massive obsidian are considered to be the subaerial equivalents of the conduits. Large-scale, regional tectonic structures in southern Brazil include the NE-SW aligned Porto Alegre Suture, Leão and Açotea faults besides the Antas Lineament, a curved tectonic feature accompanying the bed of Antas river. South of the Antas Lineament smaller-scale, NW-SE lineaments limit the exposure areas of the inferred conduits. NE-SW and subordinate NW-SE structures within this smaller-scale lineaments are represented by the main postulated conduit outcrops and are parallel to the dominant sub-vertical banding in the widespread banded vitrophyre lithofacies. Upper lava flows display flat-lying foliation, pipe-like and spherical vesicles and have better developed microlites. Petrographic characteristics of the silicic vitrophyres indicate that crystal-poor magmas underwent distinct cooling paths for each inferred conduit area. The vitrophyre chemical composition is defined by the evolution of trachydacitic/dacitic vitrophyres with 62-65 wt% SiO2 to rhyodacite and rhyolite with 66-68 wt% SiO2. The more evolved rocks are assigned to the latest intrusive grey vitrophyre outcropping in the center of the conduits. Degassing pathways formed during fragmentation and fracturing episodes within the conduits may have helped to inhibit the explosivity of the eruptions. Based on the documented lithofacies architecture, we attribute the source of the silicic lava flows in the studied localities to tectonic-controlled, local conduits, rather than pyroclastic density currents from distant vent areas.

ORIENTATION AND LOCUS OF TROPIC PHOTORECEPTOR MOLECULES IN SPORES OF BOTRYTIS AND OSMUNDA

PubMed Central

Jaffe, Lionel; Etzold, Helmut

1962-01-01

Study of the tropic responses of Botrytis cinerea and Osmunda cinnamomea spores to blue light shows the photoreceptor molecules to be highly dichroic and oriented: in Botrytis their axes of maximum absorption lie perpendicular to the nearby cell surface; in Osmunda, parallel. The chief evidence lies in a comparison of their responses to plane polarized light—both germinate parallel to the vibration planes (defined by the axis of vibration of the electric vector and the axis of light propagation)—with those to partial illumination with unpolarized light: Botrytis grows from its brighter part; Osmunda, from its darker. The degree of orientation produced by polarized light corresponds, at high intensities, to that produced by the imposition of such large (about 100 per cent) intensity differences across a cell as to preclude all alternatives to oriented dichroic receptors. The photoreceptors of the Botrytis spore lie within the cell wall's inner half. The chief evidence lies in the component of its tropic responses to polarized light within the vibration plane: germination peaks about 10° off the vibration axis. This deviation arises from focusing which is effective only in the wall's inner half. At high intensities, anomalies appear in Botrytis which are interpreted as "centering," i.e., a tendency toward growth from the center of two or more equally illuminated points of a cell rather than from one of them. PMID:14450869

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhai, Liangjun; Zheng, Yujun, E-mail: yzheng@sdu.edu.cn

In the present study, the dynamical behaviors of tripartite entanglement of vibrations in triatomic molecules are studied based on the Lie algebraic models of molecules. The dynamical behaviors of tripartite entanglement of the local mode molecule H{sub 2}O and normal mode molecule NO{sub 2} are comparatively studied for different initial states by employing the general concurrence. Our results show that the dynamics of tripartite entanglement are relied on the dynamics of intramolecular energy distribution. The local mode molecule is more suitable to construct the tripartite entangled states. Also, the greater degree of tripartite entanglement can be obtained if the stretchingmore » vibration is first excited. These results shed new light on the understanding of quantum multipartite entanglement of vibrations in the polyatomic molecules.« less

Core molecule dependence of energy migration in phenylacetylene nanostar dendrimers: Ab initio molecular orbital-configuration interaction based quantum master equation study

NASA Astrophysics Data System (ADS)

Kishi, Ryohei; Minami, Takuya; Fukui, Hitoshi; Takahashi, Hideaki; Nakano, Masayoshi

2008-06-01

The core molecule dependence of energy (exciton) migration in phenylacetylene nanostar dendrimers is investigated using the ab initio molecular orbital (MO)-configuration interaction based quantum master equation approach. We examine three kinds of core molecular species, i.e., benzene, anthracene, and pentacene, with different highest occupied MO-lowest unoccupied MO (HOMO-LUMO) gaps, which lead to different orbital interactions between the dendron parts and the core molecule. The nanostars bearing anthracene and pentacene cores are characterized by multistep exciton states with spatially well-segmented distributions: The exciton distributions of high-lying exciton states are spatially localized well in the periphery region, whereas those of low-lying exciton states are done in the core region. On the other hand, for the nanostar bearing benzene core, which also has multistep exciton states, the spatial exciton distributions of low-lying exciton states are delocalized over the dendron and the core regions. It is found that the former nanostars exhibit nearly complete exciton migration from the periphery to the core molecule in contrast to the latter one, in which significant exciton distribution remains in the dendron parts attached to the core after the exciton relaxation, although all these dendrimers exhibit fast exciton relaxation from the initially populated states. It is predicted from the analysis based on the MO correlation diagrams and the relative relaxation factor that the complete exciton migration to the core occurs not only when the HOMO-LUMO gap of the core molecule is nearly equal to that of the dendron parts attached to the core (anthracene case) but also when fairly smaller than that (pentacene case), whereas the complete migration is not achieved when the HOMO-LUMO gap of the core is larger than that of the dendron parts (benzene case). These results suggest that the fast and complete exciton migration of real dendrimers could be realized by adjusting the HOMO-LUMO gap of the core molecule to be smaller than that of dendron parts, although there exist more complicated relaxation processes as compared to simple dendritic aggregate models studied so far.

Upper mantle seismic anisotropy beneath Northern Peru from shear wave splitting analysis.

NASA Astrophysics Data System (ADS)

Franca, G. S.; Condori, C.; Tavera, H.; Eakin, C. M.; Beck, S. L.

2017-12-01

Beneath much of Peru lies the largest region of flat-slab subduction in the world today. The origins and dynamics of the Peruvian flat-slab however remain elusive, particularly in the north away from the Nazca Ridge. Studies of seismic anisotropy can potentially provide us with insight into the dynamics of recent and past deformational processes in the upper mantle. In this study, we conduct shear wave splitting to investigate seismic anisotropy across the northern extent of the Peruvian flat-slab for the first time. For the analysis, we used arrivals of SKS, SKKS and PKS phases from teleseismic events (88° > Δ < 150°) recorded at 30 broadband seismic stations from the Peruvian permanent and portable seismic networks, and international networks (CTBTO and RSBR-Brazil). The preliminary results reveal a complex anisotropy pattern with variations along strike. In the northernmost region, the average delay times range between 1.0 s and 1.2 s, with fast directions predominantly ENE-WSW oriented in a direction approximately perpendicular to the trench, parallel with subduction of the Nazca plate. Meanwhile towards the central region of Peru, the predominant fast direction changes to SE-NW oblique with the trench, but consistent with the pattern seen previously over the southern extent of the flat-slab by Eakin et al. (2013, 2015). These characteristics suggest a fundamental difference between the anisotropic structures, and therefore underlying mantle processes, beneath the northern and central portions of the Peruvian flat-slab.

A closed form, physical optics expression for the radar cross section of a perfectly conducting flat plate over a dielectric half-space

NASA Astrophysics Data System (ADS)

Anastassiu, Hristos T.

2003-04-01

The physical optics approximation is employed in the derivation of a closed form expression for the radar cross section (RCS) of a flat, perfectly conducting plate of various shapes, located over a dielectric, possibly lossy half-space. The half-space is assumed to lie in the far field region of the plate. The well-known "four-path model" is invoked in a first-order approximation of the half-space contribution to the scattering mechanisms. Numerical results are compared to a reference, Moment Method solution, and the agreement is investigated, to assess the accuracy of the approximations used. The analytical expressions derived can facilitate very fast RCS calculations for realistic scatterers, such as ships in a sea environment, or aircraft flying low over the ground.

Nested granites in question: Contrasted emplacement kinematics of independent magmas in the Zaër pluton, Morocco

NASA Astrophysics Data System (ADS)

Bouchez, Jean Luc; Diot, Herve

1990-10-01

The concentrically zoned Zaër pluton (Variscan Meseta of Morocco), previously modeled as the nesting of two magmas forming a ballooning pluton, is here subjected to a study of its internal magmatic and solid-state structures. The magmatic flow patterns, derived mainly from anisotropy of magnetic susceptibility measurements, together with structural observations down to thin-section scale, indicate that these two magmas have undergone totally independent kinematics of emplacement. This supports recent isotope geochemistry and geochronology data indicating independent origin of the magmas and diachronism of emplacement, respectively. Thus, we propose that a magma diapir, probably emplaced within a crustal fracture zone, cooled down to brittle conditions, before a likely flat-lying fracture was opened within the fracture zone and was filled with a new and compositionally different pulse of magma.

Electron-impact excitation of the low-lying electronic states of HCN

NASA Technical Reports Server (NTRS)

Chutjian, A.; Tanaka, H.; Srivastava, S. K.; Wicke, B. G.

1977-01-01

The first study of the low-energy electron-impact excitation of low-lying electronic transitions in the HCN molecule is reported. Measurements were made at incident electron energies of 11.6 and 21.6 eV in the energy-loss range of 3-10 eV, and at scattering angles of 20-130 deg. Inelastic scattering spectra were placed on the absolute cross-section scale by determining first the ratio of inelastic-to-elastic scattering cross sections, and then separately measuring the absolute elastic scattering cross section. Several new electronic transitions are observed which are intrinsically overlapped in the molecule itself. Assignments of these electronic transitions are suggested. These assignments are based on present spectroscopic and cross-sections measurements, high-energy electron scattering spectra, optical absorption spectra, and ab initio molecular orbital calculations.

Orientation-dependent energy level alignment and film growth of 2,7-diocty[1]benzothieno[3,2-b]benzothiophene (C8-BTBT) on HOPG

NASA Astrophysics Data System (ADS)

Lyu, Lu; Niu, Dongmei; Xie, Haipeng; Cao, Ningtong; Zhang, Hong; Zhang, Yuhe; Liu, Peng; Gao, Yongli

2016-01-01

Combining ultraviolet photoemission spectroscopy, X-ray photoemission spectroscopy, atomic force microscopy, and X-ray diffraction measurements, we performed a systematic investigation on the correlation of energy level alignment, film growth, and molecular orientation of 2,7-diocty[1]benzothieno[3,2-b]benzothiophene (C8-BTBT) on highly oriented pyrolytic graphite. The molecules lie down in the first layer and then stand up from the second layer. The ionization potential shows a sharp decrease from the lying down region to the standing up region. When C8-BTBT molecules start standing up, unconventional energy level band-bending-like shifts are observed as the film thickness increases. These shifts are ascribed to gradual decreasing of the molecular tilt angle about the substrate normal with the increasing film thickness.

Orientation-dependent energy level alignment and film growth of 2,7-diocty[1]benzothieno[3,2-b]benzothiophene (C8-BTBT) on HOPG.

PubMed

Lyu, Lu; Niu, Dongmei; Xie, Haipeng; Cao, Ningtong; Zhang, Hong; Zhang, Yuhe; Liu, Peng; Gao, Yongli

2016-01-21

Combining ultraviolet photoemission spectroscopy, X-ray photoemission spectroscopy, atomic force microscopy, and X-ray diffraction measurements, we performed a systematic investigation on the correlation of energy level alignment, film growth, and molecular orientation of 2,7-diocty[1]benzothieno[3,2-b]benzothiophene (C8-BTBT) on highly oriented pyrolytic graphite. The molecules lie down in the first layer and then stand up from the second layer. The ionization potential shows a sharp decrease from the lying down region to the standing up region. When C8-BTBT molecules start standing up, unconventional energy level band-bending-like shifts are observed as the film thickness increases. These shifts are ascribed to gradual decreasing of the molecular tilt angle about the substrate normal with the increasing film thickness.

Use of Laboratory Data to Model Interstellar Chemistry

NASA Technical Reports Server (NTRS)

Vidali, Gianfranco; Roser, J. E.; Manico, G.; Pirronello, V.

2006-01-01

Our laboratory research program is about the formation of molecules on dust grains analogues in conditions mimicking interstellar medium environments. Using surface science techniques, in the last ten years we have investigated the formation of molecular hydrogen and other molecules on different types of dust grain analogues. We analyzed the results to extract quantitative information on the processes of molecule formation on and ejection from dust grain analogues. The usefulness of these data lies in the fact that these results have been employed by theoreticians in models of the chemical evolution of ISM environments.

N‐Heterocyclic Carbene Self‐assembled Monolayers on Copper and Gold: Dramatic Effect of Wingtip Groups on Binding, Orientation and Assembly

PubMed Central

Larrea, Christian R.; Narouz, Mina R.; Mosey, Nicholas J.; Horton, J. Hugh; Crudden, Cathleen M.

2017-01-01

Abstract Self‐assembled monolayers of N‐heterocyclic carbenes (NHCs) on copper are reported. The monolayer structure is highly dependent on the N,N‐substituents on the NHC. On both Cu(111) and Au(111), bulky isopropyl substituents force the NHC to bind perpendicular to the metal surface while methyl‐ or ethyl‐substituted NHCs lie flat. Temperature‐programmed desorption studies show that the NHC binds to Cu(111) with a desorption energy of E des=152±10 kJ mol−1. NHCs that bind upright desorb cleanly, while flat‐lying NHCs decompose leaving adsorbed organic residues. Scanning tunneling microscopy of methylated NHCs reveals arrays of covalently linked dimers which transform into adsorbed (NHC)2Cu species by extraction of a copper atom from the surface after annealing. PMID:28960768

Photoresponsive Polymer Surfaces

NASA Astrophysics Data System (ADS)

Anastasiadis, Spiros H.; Lygeraki, M. I.; Lakiotaki, K.; Varda, M.; Athanassiou, A.; Farsari, M.; Fotakis, C.

2007-03-01

Photochromic spiropyran molecules are utilized as additives for the development of polymer surfaces whose wetting characteristics can reversibly respond to irradiation with laser beams of properly chosen photon energy. The hydrophilicity is enhanced upon UV laser irradiation since the embedded non-polar spiropyran molecules convert to their polar merocyanine isomers, which is reversed upon green laser irradiation. Micropatterning of the photochromic-polymer films using soft lithography or photo-polymerization techniques affects their wettability towards a more hydrophobic or more hydrophilic behavior depending on the dimensions of the patterned features and on the hydrophilicity-hydrophobicity of the flat surface. The light-induced wettability variations of the structured surfaces are enhanced by up to a factor of three as compared to those on the flat surfaces. This enhancement is attributed to the photoinduced reversible volume changes to the imprinted gratings, which additionally contribute to the wettability changes due to the light-induced photochromic interconversions.

In silico analysis and in vitro evaluation of immunogenic and immunomodulatory properties of promiscuous peptides derived from Leishmania infantum eukaryotic initiation factor.

PubMed

Koutsoni, Olga S; Routsias, John G; Kyriazis, Ioannis D; Barhoumi, Mourad; Guizani, Ikram; Tsakris, Athanassios; Dotsika, Eleni

2017-11-01

It is generally considered as imperative the ability to control leishmaniasis through the development of a protective vaccine capable of inducing long-lasting and protective cell-mediated immune responses. In this current study, we demonstrated potential epitopes that bind to H2 MHC class I and II molecules by conducting the in silico analysis of Leishmania infantum eukaryotic Initiation Factor (LieIF) protein, using online available algorithms. Moreover, we synthesized five peptides (16-18 amino acids long) which are part of the N-terminal portion of LieIF and contain promising MHC class I and II-restricted epitopes and afterwards, their predicted immunogenicity was evaluated in vitro by monitoring peptide-specific T-cell responses. Additionally, the immunomodulatory properties of these peptides were investigated in vitro by exploring their potential of inducing phenotypic maturation and functional differentiation of murine Bone-Marrow derived Dendritic Cells (BM-DCs). It was revealed by our data that all the synthetic peptides predicted for H2 alleles; present the property of immunogenicity. Among the synthetic peptides which contained T-cell epitopes, the peptide 52-68 aa (LieIF_2) exhibited immunomodulatory properties with the larger potential. LieIF_2-pulsed BM-DCs up-regulated the expression of the co-stimulatory surface molecules CD80 and CD86, as well as the production of the proinflammatory cytokine TNF-α and of the Th1-polarizing cytokines IL-12 and IFN-γ. The aforementioned data suggest that selected parts of LieIF could be used to develop innovative subunit protective vaccines able to induce effective immunity mediated by MHC class I-restricted as well as class II-restricted T-cell responses. Copyright © 2017 The Authors. Published by Elsevier Ltd.. All rights reserved.

Nonperturbative Renormalization Group Approach to Polymerized Membranes

NASA Astrophysics Data System (ADS)

Essafi, Karim; Kownacki, Jean-Philippe; Mouhanna, Dominique

2014-03-01

Membranes or membrane-like materials play an important role in many fields ranging from biology to physics. These systems form a very rich domain in statistical physics. The interplay between geometry and thermal fluctuations lead to exciting phases such flat, tubular and disordered flat phases. Roughly speaking, membranes can be divided into two group: fluid membranes in which the molecules are free to diffuse and thus no shear modulus. On the other hand, in polymerized membranes the connectivity is fixed which leads to elastic forces. This difference between fluid and polymerized membranes leads to a difference in their critical behaviour. For instance, fluid membranes are always crumpled, whereas polymerized membranes exhibit a phase transition between a crumpled phase and a flat phase. In this talk, I will focus only on polymerized phantom, i.e. non-self-avoiding, membranes. The critical behaviour of both isotropic and anisotropic polymerized membranes are studied using a nonperturbative renormalization group approach (NPRG). This allows for the investigation of the phase transitions and the low temperature flat phase in any internal dimension D and embedding d. Interestingly, graphene behaves just as a polymerized membrane in its flat phase.

Super-Laplacians and their symmetries

NASA Astrophysics Data System (ADS)

Howe, P. S.; Lindström, U.

2017-05-01

A super-Laplacian is a set of differential operators in superspace whose highestdimensional component is given by the spacetime Laplacian. Symmetries of super-Laplacians are given by linear differential operators of arbitrary finite degree and are determined by superconformal Killing tensors. We investigate these in flat superspaces. The differential operators determining the symmetries give rise to algebras which can be identified in many cases with the tensor algebras of the relevant superconformal Lie algebras modulo certain ideals. They have applications to Higher Spin theories.

Hydrogen Assisted Cracking and Corrosion of Some Highly Corrosion Resistant Alloys

DTIC Science & Technology

1990-01-01

Stainless Steel", June 1985, and "On the Roles of Corrosion Products in Local Cell Processes", January 1986. Research on the latter has occurred in the...concern. In closed systems. howevter, such as nuclear reactor cooling pipes. acid container systems, fuel cells, and so on. the production of ti, gas and...mernhra lie is also imiportant. fihe stirf.ice should he flat. m-e1I-polished and free of filims. (Whde or other corrosion product film-. :Are easil% formed

Earthshots: Satellite images of environmental change – Inland Delta of the Niger River, Mali

USGS Publications Warehouse

Adamson, Thomas

2016-01-01

This delta floods seasonally from September to December, as rainfall from the river’s headwaters in the Guinea Highlands reaches the delta’s vast flat floodplain. The southern part of the delta is low-lying floodplain with expanses of wetland grasses and reeds. The northern part has sand ridges that emerge from the water during the flood season. The seasonal flooding supports fisheries, pasture, and rice farming. Over 1 million people depend on resources in the delta.

PANDA2: Program for Minimum Weight Design of Stiffened, Composite, Locally Buckled Panels

DTIC Science & Technology

1986-09-01

a flat panel or a panel that spans less than about 45 degrees of circumference. However, in PANDA2 complete cylindrical shells can be treated by the...compression and that corresponding to maximum in-plane shear. It is usually best to treat complete cylindrical shells in this way rather than try to set up a...to treat panels, not complete cylindrical shells. Therefore, it is best applied to panels. In PANDA2 the curved edges of a cylindrical panel lie in

Prototype Superconducting Planar Transformers Using High-Tc Thin and Thick Films

DTIC Science & Technology

1992-01-01

AUG27 0%2 and Thick FilmsS A D W. C. McGinnis J. S. Briggs T. E . Jones L. J. Johnson 92-23707 Approved for public release; distribution Is unlimited. 92...platelet-like crystals, given the opportunity, will lie flat against each other. Reasonably good alignment can be produced by simply pressing the...these latter films, only the step-cooled sample (FCS-75) produced a reasonably smooth, uniform-looking film, and therefore only that film was

Lake Michigan Bluff Dewatering and Stabilization Study - Allegan County, Michigan

DTIC Science & Technology

2012-09-01

laminated to cross- bedded sand interbedded with reddish brown, often laminated clay; and reddish-brown to gray to blue-gray diamicton (till) containing...Till also is extremely variable in thickness and may be a thin gravel lens, or up to 44 ft of graded sand beds , planar and trough cross- beds , thin...lies lacustrine clay to below lake level. The in-place layers are nominally flat , behind the slumped bluff face. ERDC TR-12-11 12 Figure 8

Photogeologic maps of the Iris SE and Doyleville SW quadrangles, Saguache County, Colorado

USGS Publications Warehouse

McQueen, Kathleen

1957-01-01

The Iris SE and Doyleville SW quadrangles, Saguache County, Colorado include part ot the Cochetopa mining district. Photogeologic maps of these quadrangles show the distribution of sedimentary rocks of Jurassic and Cretaceous age; precambrian granite, schist, and gneiss; and igneous rocks of Tertiary age. Sedimentary rocks lie on an essentially flat erosion surface on Precambrian rocks. Folds appear to be absent but faults present an extremely complex structural terrane. Uraniferous deposits occur at fault intersections in Precambriam and Mesozoic rocks.

Orientation-dependent energy level alignment and film growth of 2,7-diocty[1]benzothieno[3,2-b]benzothiophene (C8-BTBT) on HOPG

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lyu, Lu; Niu, Dongmei, E-mail: mayee@csu.edu.cnmailto; Xie, Haipeng

Combining ultraviolet photoemission spectroscopy, X-ray photoemission spectroscopy, atomic force microscopy, and X-ray diffraction measurements, we performed a systematic investigation on the correlation of energy level alignment, film growth, and molecular orientation of 2,7-diocty[1]benzothieno[3,2-b]benzothiophene (C8-BTBT) on highly oriented pyrolytic graphite. The molecules lie down in the first layer and then stand up from the second layer. The ionization potential shows a sharp decrease from the lying down region to the standing up region. When C8-BTBT molecules start standing up, unconventional energy level band-bending-like shifts are observed as the film thickness increases. These shifts are ascribed to gradual decreasing of the molecularmore » tilt angle about the substrate normal with the increasing film thickness.« less

An Andean-type retro-arc foreland system beneath northwest South China revealed by SINOPROBE profiling

NASA Astrophysics Data System (ADS)

Li, Jianhua; Dong, Shuwen; Cawood, Peter A.; Zhao, Guochun; Johnston, Stephen T.; Zhang, Yueqiao; Xin, Yujia

2018-05-01

In the Mesozoic, South China was situated along the convergent margin between the Asian and Pacific plates, providing an excellent laboratory to understand the interactions between deformation, sedimentation and magmatism in a retroarc environment. The crustal architecture of northwest South China is displayed along the ∼600-km-long SINOPROBE deep seismic reflection profiles and reveals from east to west: (1) highly folded and truncated reflectors in the upper crust of the Yangtze Fold Zone, which correspond to thin- and thick-skinned thrust systems, and document large-scale intraplate structural imbrication and shortening; (2) a crustal-scale flat-ramp-flat structure, termed the Main Yangtze decollement, which forms a weak, viscous layer to accommodate strain decoupling and material transport in the thin- and thick-skinned systems; and (3) nearly flat-lying reflectors in the Sichuan Basin, which support interpretation of the basin as a weakly deformed depocentre. The Yangtze Fold Zone and the Sichuan Basin represent a retro-arc foreland basin system that is >800 km away from the continental-margin magmatic arc. We suggest that tectonic processes across the arc and retro-arc systems, including arc magma flare-up, basin sedimentation, retroarc thrust propagation, lithosphere underthrusting, root foundering, and extension-related magmatism were interrelated and governed mass transfer. Age data and geological relations link the tectonic processes to evolving geodynamics of the subducting Paleo-Pacific plate.

Plasmonic tunnel junctions for single-molecule redox chemistry.

PubMed

de Nijs, Bart; Benz, Felix; Barrow, Steven J; Sigle, Daniel O; Chikkaraddy, Rohit; Palma, Aniello; Carnegie, Cloudy; Kamp, Marlous; Sundararaman, Ravishankar; Narang, Prineha; Scherman, Oren A; Baumberg, Jeremy J

2017-10-20

Nanoparticles attached just above a flat metallic surface can trap optical fields in the nanoscale gap. This enables local spectroscopy of a few molecules within each coupled plasmonic hotspot, with near thousand-fold enhancement of the incident fields. As a result of non-radiative relaxation pathways, the plasmons in such sub-nanometre cavities generate hot charge carriers, which can catalyse chemical reactions or induce redox processes in molecules located within the plasmonic hotspots. Here, surface-enhanced Raman spectroscopy allows us to track these hot-electron-induced chemical reduction processes in a series of different aromatic molecules. We demonstrate that by increasing the tunnelling barrier height and the dephasing strength, a transition from coherent to hopping electron transport occurs, enabling observation of redox processes in real time at the single-molecule level.

Adsorbed states of chlorophenol on Cu(110) and controlled switching of single-molecule junctions

DOE Office of Scientific and Technical Information (OSTI.GOV)

Okuyama, H., E-mail: hokuyama@kuchem.kyoto-u.ac.jp; Kitaguchi, Y.; Hattori, T.

A molecular junction of substituted benzene (chlorophenol) is fabricated and controlled by using a scanning tunneling microscope (STM). Prior to the junction formation, the bonding geometry of the molecule on the surface is characterized by STM and electron energy loss spectroscopy (EELS). EELS shows that the OH group of chlorophenol is dissociated on Cu(110) and that the molecule is bonded nearly flat to the surface via an O atom, with the Cl group intact. We demonstrate controlled contact of an STM tip to the “available” Cl group and lift-up of the molecule while it is anchored to the surface viamore » an O atom. The asymmetric bonding motifs of the molecule to the electrodes allow for reversible control of the junction.« less

Using Fluorescent Viruses for Detecting Bacteria in Water

NASA Technical Reports Server (NTRS)

Tabacco, Mary Beth; Qian, Xiaohua; Russo, Jaimie A.

2009-01-01

A method of detecting water-borne pathogenic bacteria is based partly on established molecular-recognition and fluorescent-labeling concepts, according to which bacteria of a species of interest are labeled with fluorescent reporter molecules and the bacteria can then be detected by fluorescence spectroscopy. The novelty of the present method lies in the use of bacteriophages (viruses that infect bacteria) to deliver the fluorescent reporter molecules to the bacteria of the species of interest.

The Opportunity Rover's Athena science investigation at Meridiani Planum, Mars

NASA Technical Reports Server (NTRS)

Squyres, S. W.; Arvidson, R. E.; Bell, J. F., III; Bruckner, J.; Cabrol, N. A.; Calvin, W.; Carr, M. H.; Christensen, P. R.; Clark, B. C.; Crumpler, L.;

Observations of infragravity motions for reef fringed islands and atolls

NASA Astrophysics Data System (ADS)

Becker, J. M.; Merrifield, M. A.; Ford, M.

2012-12-01

The frequency of flooding events that affect low lying islands and atolls in the Pacific is expected to increase under current sea level rise projections. Infragravity (IG) motions, with periods ranging from approximately 25 to 400 seconds, are an important component of wave driven flooding events for reef fringed islands and atolls. The IG variability during wave events is analyzed and interpreted dynamically from pressure and current observations at four cross-reef transects in the North Pacific Ocean that include sites in the Republic of the Marshall Islands and Guam. The IG motions are shown to depend upon the spectral properties of the incident wave forcing and reef flat characteristics that include reef flat length (ranging from 100m to 450m at the four sites) and total water level due to setup and tides. A small inundation event at one of the sites is shown to occur due to large shoreline infragravity energy.

Bedrock Erosion Surfaces Record Former East Antarctic Ice Sheet Extent

NASA Astrophysics Data System (ADS)

Paxman, Guy J. G.; Jamieson, Stewart S. R.; Ferraccioli, Fausto; Bentley, Michael J.; Ross, Neil; Armadillo, Egidio; Gasson, Edward G. W.; Leitchenkov, German; DeConto, Robert M.

2018-05-01

East Antarctica hosts large subglacial basins into which the East Antarctic Ice Sheet (EAIS) likely retreated during past warmer climates. However, the extent of retreat remains poorly constrained, making quantifying past and predicted future contributions to global sea level rise from these marine basins challenging. Geomorphological analysis and flexural modeling within the Wilkes Subglacial Basin are used to reconstruct the ice margin during warm intervals of the Oligocene-Miocene. Flat-lying bedrock plateaus are indicative of an ice sheet margin positioned >400-500 km inland of the modern grounding zone for extended periods of the Oligocene-Miocene, equivalent to a 2-m rise in global sea level. Our findings imply that if major EAIS retreat occurs in the future, isostatic rebound will enable the plateau surfaces to act as seeding points for extensive ice rises, thus limiting extensive ice margin retreat of the scale seen during the early EAIS.

The opportunity Rover's athena science investigation at Meridiani Planum, Mars

USGS Publications Warehouse

Squyres, S. W.; Arvidson, R. E.; Bell, J.F.; Brückner, J.; Cabrol, N.A.; Calvin, W.; Carr, M.H.; Christensen, P.R.; Clark, B. C.; Crumpler, L.; Des Marais, D.J.; D'Uston, C.; Economou, T.; Farmer, J.; Farrand, W.; Folkner, W.; Golombek, M.; Gorevan, S.; Grant, J. A.; Greeley, R.; Grotzinger, J.; Haskin, L.; Herkenhoff, K. E.; Hviid, S.; Johnson, J.; Klingelhofer, G.; Knoll, A.H.; Landis, G.; Lemmon, M.; Li, R.; Madsen, M.B.; Malin, M.C.; McLennan, S.M.; McSween, H.Y.; Ming, D. W.; Moersch, J.; Morris, R.V.; Parker, T.; Rice, J. W.; Richter, L.; Rieder, R.; Sims, M.; Smith, M.; Smith, P.; Soderblom, L.A.; Sullivan, R.; Wanke, H.; Wdowiak, T.; Wolff, M.; Yen, A.

2004-01-01

The Mars Exploration Rover Opportunity has investigated the landing site in Eagle crater and the nearby plains within Meridiani Planum. The soils consist of fine-grained basaltic sand and a surface lag of hematite-rich spherules, spherule fragments, and other granules. Wind ripples are common. Underlying the thin soil layer, and exposed within small impact craters and troughs, are flat-lying sedimentary rocks. These rocks are finely laminated, are rich in sulfur, and contain abundant sulfate salts. Small-scale cross-lamination in some locations provides evidence for deposition in flowing liquid water. We interpret the rocks to be a mixture of chemical and siliciclastic sediments formed by episodic inundation by shallow surface water, followed by evaporation, exposure, and desiccation. Hematite-rich spherules are embedded in the rock and eroding from them. We interpret these spherules to be concretions formed by postdepositional diagenesis, again involving liquid water.

Note: Is it symmetric or not?

PubMed

Stanton, John F

2013-07-28

The reasons by which a molecule might distort from an idealized high symmetry configuration (for example, D3h for the nitrate radical) in a quantum-chemical computation are well-known, but briefly reviewed here in light of considerable recent debate on the BNB molecule. The role of the pseudo-Jahn-Teller effect in such cases is emphasized, as is the ultimate relevance and proper interpretation of the title question in cases where the adiabatic potential energy surface is extremely flat.

Structural framework and hydrocarbon potential of Ross Sea, Antarctica

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cooper, A.K.; Davey, F.J.

The 400 to 1100-m deep continental shelf of the Ross Sea is underlain by three major sedimentary basins (Eastern basin, Central trough, and Victoria Land basin), which contain 5 to 6 km of sedimentary rock of Late Cretaceous(.) and younger age. An addition 6 to 7 km of older sedimentary and volcanic rocks lie within the Victoria Land basin. Eroded basement ridges of early Paleozoic(.) and older rocks similar to those of onshore Victoria Land separate the basins. The three basins formed initially in late Mesozoic time during an early period of rifting between East and West Antarctica. The Easternmore » basin is a 300-km wide, asymmetric basement trough that structurally opens into the Southern Ocean. A seaward-prograding sequence of late Oligocene and younger glacial deposits covers a deeper, layered sequence of Paleogene(.) and older age. The Central trough, a 100-km wide depression, is bounded by basement block faults and is filled with a nearly flat-lying sedimentary section. A prominent positive gravity anomaly, possibly caused by rift-related basement rocks, lies along the axis of the basin. The Victoria Land basin, unlike the other two basins, additionally contains a Paleogene(.) to Holocene rift zone, the Terror Rift. Rocks in the rift, near the axis of the 150-km wide basement half-graben, show extensive shallow faulting and magmatic intrusion of the sedimentary section. The active Terror rift and older basin structures extend at least 300 km along the base of the Transantarctic Mountains. Petroleum hydrocarbons have not been reported in the Ross Sea region, with possible exception of ethane gas found in Deep Sea Drilling Project cores from the Eastern basin. Model studies indicate that hydrocarbons could be generated at depths of 3.5 to 6 km within the sedimentary section. The best structures for hydrocarbon entrapment occur in the Victoria Land basin and associated Terror Rift.« less

Charged Vaidya solution satisfies weak energy condition

NASA Astrophysics Data System (ADS)

Chatterjee, Soumyabrata; Ganguli, Suman; Virmani, Amitabh

2016-07-01

The external matter stress-tensor supporting charged Vaidya solution appears to violate weak energy condition in certain region of the spacetime. Motivated by this, a new interpretation of charged Vaidya solution was proposed by Ori (Class Quant Grav 8:1559, 1991) in which the energy condition continues to be satisfied. In this construction, one glues an outgoing Vaidya solution to the original ingoing Vaidya solution provided the surface where the external stress-tensor vanishes is spacelike. We revisit this study and extend it to higher-dimensions, to AdS settings, and to higher-derivative f( R) theories. In asymptotically flat space context, we explore in detail the case when the mass function m( v) is proportional to the charge function q( v). When the proportionality constant ν = q(v)/m(v) lies in between zero and one, we show that the surface where the external stress-tensor vanishes is spacelike and lies in between the inner and outer apparent horizons.

Storm-generated bedforms and relict dissolution pits and channels on the Yucatan carbonate platform

NASA Astrophysics Data System (ADS)

Gulick, S. P.; Goff, J. A.; Stewart, H. A.; Perez-Cruz, L. L.; Davis, M. B.; Duncan, D.; Saustrup, S.; Sanford, J. C.; Fucugauchi, J. U.

2013-12-01

The Yucatan 2013 (cruise number 2013/4_ECORD) geophysical and geotechnical hazard site survey took place aboard the R/V Justo Sierra in April 2013. Our study was conducted within the Chicxulub impact crater, encompassing three potential IODP drilling sites. The survey was located ~32 km northwest of Progreso, Mexico; data acquired included ~15.6 km2 of complete multibeam bathymetry coverage, ~435 line km of side scan sonar and CHIRP data, 204 line kilometers of magnetometer data, and 194 line kilometers of surface tow boomer profiles. Based on these data, this portion of the Yucatan Shelf consists of flat-lying, hard limestone rock overlain by isolated ribbons of carbonate sand <1.0 m thick. These ribbons are oriented along NE-SW trends and have smaller scale orthogonal sand-waves (~20-100 m wavelengths and relief of ~0.2-0.6 m) on them. The sand waves are anisotropic with steeper slopes facing the NE. The larger scale morphology can be classified as longitudinal bedforms (ribbons), and the smaller scale transverse bedforms formed in response to a NE-directed flow. This flow direction is inconsistent with the ambient west-directed current conditions, and may therefore be indicative of storm-driven currents. Numerous dissolution pits, ~5-50m in diameter, ~0.2-0.5 m deep with steep (0.1-0.5 gradient) walls, are present in the bare rock regions of most of the study area. These occasionally are floored by rippled, highly reflective (coarse) sediments. We interpret these pits as representing karstic morphology formed during the last sub-aerial exposure of the study area interpreted to have occurred during Holocene times given the present day ~17 m average water depth. A sub-surface reflector imaged on the surface tow boomer data lies 1-3 m below the hard seafloor reflection (sand ribbons are below the vertical resolution of the surface tow boomer), which we interpret as a layer within the limestone bedrock. This reflector is flat-lying and undisturbed throughout the survey area. Therefore, none of these dissolution pits appear to be underlain by a cenote or sink hole. The NW sector of the survey area exhibits a more complex morphology than the alternating ribbon/bare rock morphology elsewhere, including linear scarps (up to ~1 m relief), deeper pitting (up to ~1 m relief), and sinuous, dendritic channeling (up to ~2 m relief). The geologic origin of these features will require further investigation. Sand drifts are present in this region, but are thinner and cover less area. These observations show the dominant modern sediment formation and transport processes on this starved platform are from large storms and hurricanes that place large regions of the platform at wave base. Remaining observed features were generated during times of lower sea level.

Tyrrhena Patera

NASA Image and Video Library

1998-06-08

A color image of the Tyrrhena Patera Region of Mars; north toward top. The scene shows a central circular depression surrounded by circular fractures and highly dissected horizontal sheets. A patera (Latin for shallow dish or saucer) is a volcano of broad areal extent with little vertical relief. This image is a composite of Viking medium-resolution images in black and white and low-resolution images in color. The image extends from latitude 17 degrees S. to 25 degrees S. and from longitude 250 degrees to 260 degrees; Mercator projection. Tyrrhena Patera has a 12-km-diameter caldera at its center surrounded by a 45-km-diameter fracture ring. Around the fracture ring, the terrain is highly eroded forming ragged outward-facing cliffs, as though successive flat-lying layers had been eroded back. Cut into the sequence are several flat-floored channels that extend outward as far as 200 km from the center of the volcano. The structure may be composed of highly erodible ash layers and the channels may be fluvial, with the release of water being triggered by volcanic activity (Carr, 1981, The surface of Mars, Yale Univ. Press, New Haven, 232 p.). http://photojournal.jpl.nasa.gov/catalog/PIA00421

Brownian Dynamics Simulations of Polyelectrolyte Adsorption in Shear Flow

NASA Astrophysics Data System (ADS)

Panwar, Ajay

2005-03-01

The adsorption of polyelectrolytes onto charged surfaces often occurs in microfludic devices and can influence their operation. We employ Brownian dynamics simulations to investigate the effect of a simple shear flow on the adsorption of an isolated polyelectrolyte molecule onto an oppositely charged surface. The polyelectrolyte is modeled as a freely-jointed bead-rod chain where the total charge is distributed uniformly among all the beads, and the beads are allowed to interact with one another and the charged surface through screened Coulombic interactions. The simulations are performed by placing the chain some distance above the surface, and the adsorption behavior is studied as a function of the screening length. Specifically, we look at the components of the radius of gyration, normal and parallel to the adsorbing surface, as functions of the screening length, both in the absence and presence of the flow. We find that in the absence of flow, the chain lies flat and stretched on the adsorbing surface in the limit of weak screening, but attains free solution behavior in the limit of strong screening. In the presence of a shear flow, the chain orientation in the direction of the flow increases with increasing Weissenberg number over the entire range of screening lengths studied. We also find that increasing the strength of the shear flow leads to an increased contact of the chain with the surface compared to the case when no flow is present.

Superconductivity in the two-dimensional Hubbard model

NASA Astrophysics Data System (ADS)

Beenen, J.; Edwards, D. M.

1995-11-01

Quasiparticle bands of the two-dimensional Hubbard model are calculated using the Roth two-pole approximation to the one-particle Green's function. Excellent agreement is obtained with recent Monte Carlo calculations, including an anomalous volume of the Fermi surface near half-filling, which can possibly be explained in terms of a breakdown of Fermi liquid theory. The calculated bands are very flat around the (π,0) points of the Brillouin zone in agreement with photoemission measurements of cuprate superconductors. With doping there is a shift in spectral weight from the upper band to the lower band. The Roth method is extended to deal with superconductivity within a four-pole approximation allowing electron-hole mixing. It is shown that triplet p-wave pairing never occurs. A self-consistent solution with singlet dx2-y2-wave pairing is found and optimal doping occurs when the van Hove singularity, corresponding to the flat band part, lies at the Fermi level. Nearest-neighbor antiferromagnetic correlations play an important role in flattening the bands near the Fermi level and in favoring superconductivity. However, the mechanism for superconductivity is a local one, in contrast to spin-fluctuation exchange models. For reasonable values of the hopping parameter the transition temperature Tc is in the range 10-100 K. The optimum doping δc lies between 0.14 and 0.25, depending on the ratio U/t. The gap equation has a BCS-like form and 2Δmax/kTc~=4.

Geologic evidence for age of deposits at Hueyatlaco archeological site, Vasequillo, Mexico

USGS Publications Warehouse

Steen-McIntyre, V.; Fryxell, R.; Malde, H.E.

1981-01-01

Direct tracing of beds during excavation in May 1973, confirmed that the artifact-bearing layers at Hueyatlaco underlie 10 m of fine-grained, water-laid deposits that constitute part of the wide-spread Valsequillo gravels. Dissection of these deposits by the adjacent Ri??o Atoyac has reached a depth of 50 m. The stratigraphic section at Hueyatlaco includes four distinctive tephra units. The oldest one occupies a small channel in a series of cut-and-fill stream deposits that have yielded bifacial tools. It lies more than a meter above flat-lying, fine-grained beds from which edge-retouched tools have been recovered. The three other tephra units occur higher in the section. Fission-track ages on zircon phenocrysts from two of the younger tephra layers (370,000 ?? 200,000 and 600,000 ?? 340,000 yr, 2??) agree with concordant uranium-series dates for a camel pelvis that was found associated with bifacial tools at Hueyatlaco (245,000 ?? 40,000 yr by 230Th and > 180,000 yr by 231Pa). These dates are compatible with the depth of burial and subsequent dissection of the Hueyatlaco deposits, as well as with the degree of hydration of volcanic glass shards and with the extent of etching of heavy-mineral phenocrysts from within the tephra layers. These findings suggest to us that further search for archaeological remains in deposits as old as those at Hueyatlaco would be warranted. ?? 1981.

Advanced Gas Hydrate Reservoir Modeling Using Rock Physics

DOE Office of Scientific and Technical Information (OSTI.GOV)

McConnell, Daniel

Prospecting for high saturation gas hydrate deposits can be greatly aided with improved approaches to seismic interpretation and especially if sets of seismic attributes can be shown as diagnostic or direct hydrocarbon indicators for high saturation gas hydrates in sands that would be of most interest for gas hydrate production. A large 3D seismic data set in the deep water Eastern Gulf of Mexico was screened for gas hydrates using a set of techniques and seismic signatures that were developed and proven in the Central deepwater Gulf of Mexico in the DOE Gulf of Mexico Joint Industry Project JIP Legmore » II in 2009 and recently confirmed with coring in 2017. A large gas hydrate deposit is interpreted in the data where gas has migrated from one of the few deep seated faults plumbing the Jurassic hydrocarbon source into the gas hydrate stability zone. The gas hydrate deposit lies within a flat-lying within Pliocene Mississippi Fan channel that was deposited outboard in a deep abyssal environment. The uniform architecture of the channel aided the evaluation of a set of seismic attributes that relate to attenuation and thin-bed energy that could be diagnostic of gas hydrates. Frequency attributes derived from spectral decomposition also proved to be direct hydrocarbon indicators by pseudo-thickness that could be only be reconciled by substituting gas hydrate in the pore space. The study emphasizes that gas hydrate exploration and reservoir characterization benefits from a seismic thin bed approach.« less

Global molecular identification from graphs. Neutral and ionized main-group diatomic molecules.

PubMed

James, Bryan; Caviness, Ken; Geach, Jonathan; Walters, Chris; Hefferlin, Ray

2002-01-01

Diophantine equations and inequalities are presented for main-group closed-shell diatomic molecules. Specifying various bond types (covalent, dative, ionic, van der Waals) and multiplicities, it becomes possible to identify all possible molecules. While many of the identified species are probably unstable under normal conditions, they are interesting and present a challenge for computational or experimental analysis. Ionized molecules with net charges of -1, 1, and 2 are also identified. The analysis applies to molecules with atoms from periods 2 and 3 but can be generalized by substituting isovalent atoms. When closed-shell neutral diatomics are positioned in the chemical space (with axes enumerating the numbers of valence electrons of the free atoms), it is seen that they lie on a few parallel isoelectronic series.

Visualization of molecular structures using HoloLens-based augmented reality

PubMed Central

Hoffman, MA; Provance, JB

2017-01-01

Biological molecules and biologically active small molecules are complex three dimensional structures. Current flat screen monitors are limited in their ability to convey the full three dimensional characteristics of these molecules. Augmented reality devices, including the Microsoft HoloLens, offer an immersive platform to change how we interact with molecular visualizations. We describe a process to incorporate the three dimensional structures of small molecules and complex proteins into the Microsoft HoloLens using aspirin and the human leukocyte antigen (HLA) as examples. Small molecular structures can be introduced into the HoloStudio application, which provides native support for rotating, resizing and performing other interactions with these molecules. Larger molecules can be imported through the Unity gaming development platform and then Microsoft Visual Developer. The processes described here can be modified to import a wide variety of molecular structures into augmented reality systems and improve our comprehension of complex structural features. PMID:28815109

Dynamics in higher lying excited states: Valence to Rydberg transitions in the relaxation paths of pyrrole and methylated derivatives

NASA Astrophysics Data System (ADS)

Geng, Ting; Schalk, Oliver; Neville, Simon P.; Hansson, Tony; Thomas, Richard D.

2017-04-01

The involvement of intermediate Rydberg states in the relaxation dynamics of small organic molecules which, after excitation to the valence manifold, also return to the valence manifold is rarely observed. We report here that such a transiently populated Rydberg state may offer the possibility to modify the outcome of a photochemical reaction. In a time resolved photoelectron study on pyrrole and its methylated derivatives, N-methyl pyrrole and 2,5-dimethyl pyrrole, 6.2 eV photons (200 nm) are used to excite these molecules into a bright ππ* state. In each case, a π3p-Rydberg state, either the B1(π3py) or the A2(π3pz) state, is populated within 20-50 fs after excitation. The wavepacket then proceeds to the lower lying A2(πσ*) state within a further 20 fs, at which point two competing reaction channels can be accessed: prompt N-H (N-CH3) bond cleavage or return to the ground state via a conical intersection accessed after ring puckering, the latter of which is predicted to require an additional 100-160 fs depending on the molecule.

Self-assembly of heterogeneous supramolecular structures with uniaxial anisotropy.

PubMed

Ruiz-Osés, M; Gonzalez-Lakunza, N; Silanes, I; Gourdon, A; Arnau, A; Ortega, J E

2006-12-28

Uniaxial anisotropy in two-dimensional self-assembled supramolecular structures is achieved by the coadsorption of two different linear molecules with complementary amine and imide functionalization. The two-dimensional monolayer is defined by a one-dimensional stack of binary chains, which can be forced to line up along steps in vicinal surfaces. The competing driving forces in the self-organization process are discussed in light of the structures observed during single molecule adsorption and coadsorption on flat and vicinal surfaces and the corresponding theoretical calculations.

Fluorescence quenching near small metal nanoparticles.

PubMed

Pustovit, V N; Shahbazyan, T V

2012-05-28

We develop a microscopic model for fluorescence of a molecule (or semiconductor quantum dot) near a small metal nanoparticle. When a molecule is situated close to metal surface, its fluorescence is quenched due to energy transfer to the metal. We perform quantum-mechanical calculations of energy transfer rates for nanometer-sized Au nanoparticles and find that nonlocal and quantum-size effects significantly enhance dissipation in metal as compared to those predicted by semiclassical electromagnetic models. However, the dependence of transfer rates on molecule's distance to metal nanoparticle surface, d, is significantly weaker than the d(-4) behavior for flat metal surface with a sharp boundary predicted by previous calculations within random phase approximation.

Supramolecular engineering through temperature-induced chemical modification of 2H-tetraphenylporphyrin on Ag(111): flat phenyl conformation and possible dehydrogenation reactions.

PubMed

Di Santo, Giovanni; Blankenburg, Stephan; Castellarin-Cudia, Carla; Fanetti, Mattia; Borghetti, Patrizia; Sangaletti, Luigi; Floreano, Luca; Verdini, Alberto; Magnano, Elena; Bondino, Federica; Pignedoli, Carlo A; Nguyen, Manh-Thuong; Gaspari, Roberto; Passerone, Daniele; Goldoni, Andrea

2011-12-16

Scratching the surface: Formation of a monolayer of 2H-tetraphenylporphyrins (2H-TPP) on Ag(111), either by sublimation of a multilayer in the range 525-600 K or by annealing (at the same temperature) a monolayer deposited at room temperature, induces a chemical modification of the molecules. Rotation of the phenyl rings into a flat conformation is observed and tentatively explained, by using DFT calculations, as a peculiar reaction due to molecular dehydrogenation. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The nature of the globular- to fibrous-actin transition.

PubMed

Oda, Toshiro; Iwasa, Mitsusada; Aihara, Tomoki; Maéda, Yuichiro; Narita, Akihiro

2009-01-22

Actin plays crucial parts in cell motility through a dynamic process driven by polymerization and depolymerization, that is, the globular (G) to fibrous (F) actin transition. Although our knowledge about the actin-based cellular functions and the molecules that regulate the G- to F-actin transition is growing, the structural aspects of the transition remain enigmatic. We created a model of F-actin using X-ray fibre diffraction intensities obtained from well oriented sols of rabbit skeletal muscle F-actin to 3.3 A in the radial direction and 5.6 A along the equator. Here we show that the G- to F-actin conformational transition is a simple relative rotation of the two major domains by about 20 degrees. As a result of the domain rotation, the actin molecule in the filament is flat. The flat form is essential for the formation of stable, helical F-actin. Our F-actin structure model provides the basis for understanding actin polymerization as well as its molecular interactions with actin-binding proteins.

A general method for controlling and resolving rotational orientation of molecules in molecule-surface collisions

PubMed Central

Godsi, Oded; Corem, Gefen; Alkoby, Yosef; Cantin, Joshua T.; Krems, Roman V.; Somers, Mark F.; Meyer, Jörg; Kroes, Geert-Jan; Maniv, Tsofar; Alexandrowicz, Gil

2017-01-01

The outcome of molecule–surface collisions can be modified by pre-aligning the molecule; however, experiments accomplishing this are rare because of the difficulty of preparing molecules in aligned quantum states. Here we present a general solution to this problem based on magnetic manipulation of the rotational magnetic moment of the incident molecule. We apply the technique to the scattering of H2 from flat and stepped copper surfaces. We demonstrate control of the molecule's initial quantum state, allowing a direct comparison of differences in the stereodynamic scattering from the two surfaces. Our results show that a stepped surface exhibits a much larger dependence of the corrugation of the interaction on the alignment of the molecule than the low-index surface. We also demonstrate an extension of the technique that transforms the set-up into an interferometer, which is sensitive to molecular quantum states both before and after the scattering event. PMID:28480890

The calculation of force-free fields from discrete flux distributions. [for chromospheric magnetic fields

NASA Technical Reports Server (NTRS)

Sheeley, N. R., Jr.; Harvey, J. W.

1975-01-01

This paper presents particularly simple mathematical formulas for the calculation of force-free fields of constant alpha from the distribution of discrete sources on a flat surface. The advantage of these formulas lies in their physical simplicity and the fact that they can be easily used in practice to calculate the fields. The disadvantage is that they are limited to fields of 'sufficiently small alpha'. These formulas may be useful in the study of chromospheric magnetic fields by the comparison of high-resolution H-alpha photographs and photospheric magnetograms.

Every timelike geodesic in Anti-de Sitter spacetime is a circle of the same radius

NASA Astrophysics Data System (ADS)

Sokołowski, Leszek M.; Golda, Zdzisław A.

2016-10-01

In this paper, we refine and analytically prove an old proposition due to Calabi and Markus on the shape of timelike geodesics of anti-de Sitter space in the ambient flat space. We prove that each timelike geodesic forms in the ambient space a circle of the radius determined by Λ, lying on a Euclidean two-plane. Then, we outline an alternative proof for AdS4. We also make a comment on the shape of timelike geodesics in de Sitter space.

A Literature Review of Archaeological, Historical, and Paleontological Resources of the Sheyenne River Basin in North Dakota

DTIC Science & Technology

1977-01-01

description of the Red River valley area was derived from Shay (1967: 231-237) and Scoby et. al. (1973). The Red River valley per se is flat except where...it is inter- rupted by the Sheyenne delta escarpment and the glacial Lake Agassiz shorelines ( Scoby et. al. 1973: 16). Surface drainage in the area is...very poor with runoff tending to collect in low lying areas ( Scoby et. al. 1973: 23). Prior to inten- sive drainage the area may have possessed many

What Lies Ahead (left-eye)

NASA Technical Reports Server (NTRS)

2004-01-01

This is the left-eye version of the 3-D cylindrical-perspective mosaic showing the view south of the martian crater dubbed 'Bonneville.' The image was taken by the navigation camera on the Mars Exploration Rover Spirit. The rover will travel toward the Columbia Hills, seen here at the upper left. The rock dubbed 'Mazatzal' and the hole the rover drilled in to it can be seen at the lower left. The rover's position is referred to as 'Site 22, Position 32.' This image was geometrically corrected to make the horizon appear flat.

More About Lens Antenna For Mobile/Satellite Communication

NASA Technical Reports Server (NTRS)

Rahmat-Samii, Y.; Bodnar, D. G.; Rainer, B. K.

1990-01-01

Report presents additional details of design of proposed phased-array antenna described in "Lens Antenna for Mobile/Satellite Communication" (NPO-16948). Intended to be compact and to lie flat on top of vehicle on ground. Transmits and receives circularly polarized radiation in frequency ranges of 821 to 825 MHz and 860 to 870 MHz. Transmitting and receiving beams electronically steerable to any of 48 evenly spaced directions to provide complete azimuth coverage, and would be fixed, but wide, in elevation, to provide coverage at elevation angles from 20 degrees to 60 degrees.

Swell-generated Set-up and Infragravity Wave Propagation Over a Fringing Coral Reef: Implications for Wave-driven Inundation of Atoll Islands

NASA Astrophysics Data System (ADS)

Cheriton, O. M.; Storlazzi, C. D.; Rosenberger, K. J.; Quataert, E.; van Dongeren, A.

2014-12-01

The Republic of the Marshall Islands is comprised of 1156 islands on 29 low-lying atolls with a mean elevation of 2 m that are susceptible to sea-level rise and often subjected to overwash during large wave events. A 6-month deployment of wave and tide gauges across two shore-normal sections of north-facing coral reef on the Roi-Namur Island on Kwajalein Atoll was conducted during 2013-2014 to quantify wave dynamics and wave-driven water levels on the fringing coral reef. Wave heights and periods on the reef flat were strongly correlated to the water levels. On the fore reef, the majority of wave energy was concentrated in the incident band (5-25 s); due to breaking at the reef crest, however, the wave energy over the reef flat was dominated by infragravity-band (25-250 s) motions. Two large wave events with heights of 6-8 m at 15 s over the fore reef were observed. During these events, infragravity-band wave heights exceeded the incident band wave heights and approximately 1.0 m of set-up was established over the innermost reef flat. This set-up enabled the propagation of large waves across the reef flat, reaching maximum heights of nearly 2 m on the innermost reef flat adjacent to the toe of the beach. XBEACH models of the instrument transects were able to replicate the incident waves, infragravity waves, and wave-driven set-up across the reef when the hydrodynamic roughness of the reef was correctly parameterized. These events led to more than 3 m of wave-driven run-up and inundation of the island that drove substantial morphological change to the beach face.

Modeling Reef Island Morphodynamics in Profile and Plan View

NASA Astrophysics Data System (ADS)

Ashton, A. D.; Ortiz, A. C.; Lorenzo-Trueba, J.

2016-12-01

Reef islands are carbonate detrital landforms perched atop shallow reef flats of atolls and barrier reef systems. Often comprising the only subaerial, inhabitable land of many island chains and island nations, these low-lying, geomorphically active landforms face considerable hazards from climate change. While there hazards include wave overtopping and groundwater salinization, sea-level rise and wave climate change will affect sediment transport and shoreline dynamics, including the possibility for wholesale reorganization of the islands themselves. Here we present a simplified morphodynamic model that can spatially quantify the potential impacts of climate change on reef islands. Using parameterizations of sediment transport pathways and feedbacks from previously presented XBeach modeling results, we investigate how sea-level rise, change in storminess, and different carbonate production rates can affect the profile evolution of reef islands, including feedbacks with the shallow reef flat that bounds the islands offshore (and lagoonward). Model results demonstrate that during rising sea levels, the reef flat can serve as a sediment trap, starving reef islands of detrital sediment that could otherwise fortify the shore against sea-level-rise-driven erosion. On the other hand, if reef flats are currently shallow (likely due to geologic inheritance or biologic cementation processes) such that sea-level rise does not result in sediment accumulation on the flat, reef island shorelines may be more resilient to rising seas. We extend the model in plan view to examine how long-term (decadal) changes in wave approach direction could affect reef island shoreline orientation. We compare model results to historical and geologic change for different case studies on the Marshall Islands. This simplified modeling approach, focusing on boundary dynamics and mass fluxes, provides a quantitative tool to predict the response of reef island environments to climate change.

Identification and classification of very low frequency waves on a coral reef flat

USGS Publications Warehouse

Gawehn, Matthijs; van Dongeran, Ap; van Rooijen, Arnold; Storlazzi, Curt; Cheriton, Olivia; Reniers, Ad

2016-01-01

Very low frequency (VLF, 0.001–0.005 Hz) waves are important drivers of flooding of low-lying coral reef-islands. In particular, VLF wave resonance is known to drive large wave runup and subsequent overwash. Using a 5 month data set of water levels and waves collected along a cross-reef transect on Roi-Namur Island in the Republic of the Marshall Islands, the observed VLF motions were categorized into four different classes: (1) resonant, (2) (nonresonant) standing, (3) progressive-growing, and (4) progressive-dissipative waves. Each VLF class is set by the reef flat water depth and, in the case of resonance, the incident-band offshore wave period. Using an improved method to identify VLF wave resonance, we find that VLF wave resonance caused prolonged (∼0.5–6.0 h), large-amplitude water surface oscillations at the inner reef flat ranging in wave height from 0.14 to 0.83 m. It was induced by relatively long-period, grouped, incident-band waves, and occurred under both storm and nonstorm conditions. Moreover, observed resonant VLF waves had nonlinear, bore-like wave shapes, which likely have a larger impact on the shoreline than regular, sinusoidal waveforms. As an alternative technique to the commonly used Fast Fourier Transformation, we propose the Hilbert-Huang Transformation that is more computationally expensive but can capture the wave shape more accurately. This research demonstrates that understanding VLF waves on reef flats is important for evaluating coastal flooding hazards.

Identification and classification of very low frequency waves on a coral reef flat

NASA Astrophysics Data System (ADS)

Gawehn, Matthijs; van Dongeren, Ap; van Rooijen, Arnold; Storlazzi, Curt D.; Cheriton, Olivia M.; Reniers, Ad

2016-10-01

Very low frequency (VLF, 0.001-0.005 Hz) waves are important drivers of flooding of low-lying coral reef-islands. In particular, VLF wave resonance is known to drive large wave runup and subsequent overwash. Using a 5 month data set of water levels and waves collected along a cross-reef transect on Roi-Namur Island in the Republic of the Marshall Islands, the observed VLF motions were categorized into four different classes: (1) resonant, (2) (nonresonant) standing, (3) progressive-growing, and (4) progressive-dissipative waves. Each VLF class is set by the reef flat water depth and, in the case of resonance, the incident-band offshore wave period. Using an improved method to identify VLF wave resonance, we find that VLF wave resonance caused prolonged (˜0.5-6.0 h), large-amplitude water surface oscillations at the inner reef flat ranging in wave height from 0.14 to 0.83 m. It was induced by relatively long-period, grouped, incident-band waves, and occurred under both storm and nonstorm conditions. Moreover, observed resonant VLF waves had nonlinear, bore-like wave shapes, which likely have a larger impact on the shoreline than regular, sinusoidal waveforms. As an alternative technique to the commonly used Fast Fourier Transformation, we propose the Hilbert-Huang Transformation that is more computationally expensive but can capture the wave shape more accurately. This research demonstrates that understanding VLF waves on reef flats is important for evaluating coastal flooding hazards.

Nanodiamonds + bacteriochlorin as an infrared photosensitizer for deep-lying tumor diagnostics and therapy

NASA Astrophysics Data System (ADS)

Sharova, A. S.; Maklygina, YU S.; Lisichkin, G. V.; Mingalev, P. G.; Loschenov, V. B.

2016-08-01

The spectroscopic properties of potentially perspective nanostructure: diamond nanoparticles with a surface layer of IR-photosensitizer, bacteriochlorin, were experimentally investigated in this study. Such specific structure of the object encourages enhancement of the drug tropism to the tumor, as well as increasing of photodynamic penetration depth. The size distribution spectra of diamond nanoparticles; diamond nanoparticles, artificially covered with bacteriochlorin molecules layer, in aqueous solution, were obtained during the study. Based on the absorption and fluorescence spectra analysis, the benefits of functional nanostructure as a drug for deep-lying tumor diagnostics and therapy were reviewed.

Energy spectra of vibron and cluster models in molecular and nuclear systems

NASA Astrophysics Data System (ADS)

Jalili Majarshin, A.; Sabri, H.; Jafarizadeh, M. A.

2018-03-01

The relation of the algebraic cluster model, i.e., of the vibron model and its extension, to the collective structure, is discussed. In the first section of the paper, we study the energy spectra of vibron model, for diatomic molecule then we derive the rotation-vibration spectrum of 2α, 3α and 4α configuration in the low-lying spectrum of 8Be, 12C and 16O nuclei. All vibrational and rotational states with ground and excited A, E and F states appear to have been observed, moreover the transitional descriptions of the vibron model and α-cluster model were considered by using an infinite-dimensional algebraic method based on the affine \\widehat{SU(1,1)} Lie algebra. The calculated energy spectra are compared with experimental data. Applications to the rotation-vibration spectrum for the diatomic molecule and many-body nuclear clusters indicate that there are solvable models and they can be approximated very well using the transitional theory.

Quantum computing applied to calculations of molecular energies: CH2 benchmark.

PubMed

Veis, Libor; Pittner, Jiří

2010-11-21

Quantum computers are appealing for their ability to solve some tasks much faster than their classical counterparts. It was shown in [Aspuru-Guzik et al., Science 309, 1704 (2005)] that they, if available, would be able to perform the full configuration interaction (FCI) energy calculations with a polynomial scaling. This is in contrast to conventional computers where FCI scales exponentially. We have developed a code for simulation of quantum computers and implemented our version of the quantum FCI algorithm. We provide a detailed description of this algorithm and the results of the assessment of its performance on the four lowest lying electronic states of CH(2) molecule. This molecule was chosen as a benchmark, since its two lowest lying (1)A(1) states exhibit a multireference character at the equilibrium geometry. It has been shown that with a suitably chosen initial state of the quantum register, one is able to achieve the probability amplification regime of the iterative phase estimation algorithm even in this case.

Surface induced selective deposition of Dysprosium Polyoxometalate on HOPG surface studied by STM and STS

NASA Astrophysics Data System (ADS)

Costa Milan, David; Pinilla Cienfuegos, Elena; Cardona Serra, Salvador; Coronado Miralles, Eugenio; Untiedt Lecuona, Carlos

2013-03-01

Scanning Tunneling Microscope (STM) and scanning Tunnelling spectroscopy (STS) techniques have been used to study the Preyssler type Polyoxometalate K12[DyP5W30O110] molecules deposited on Highly Oriented Pyrolytic Graphite surface (HOPG). Chainlike arrangements of clusters containing two or three molecules, as well as different cluster sizes are observed. As many structural artifacts are present on the graphite surface, like Moiré patterns, that could look like the molecular deposits, we have studied their STS and size to ensure the presence of the POM molecules on the surface. This article shows the possibility of addressing POMs on a flat surface to obtain their electronic properties through STS.

The Flat and Direct Way to R and S Configurations.

ERIC Educational Resources Information Center

Brun, Y.; Leblanc, P.

1983-01-01

Discusses a simple, effective way of teaching S and R configurations for chiral molecules containing asymmetric centers. The method involves converting wedge/spatial representations to Fischer projections and prioritizing groups according to the Cahn-Ingold-Prelog sequence rules. Two examples illustrating the method are included. (JN)

Investigations of structural defects, crystalline perfection, metallic impurity concentration and optical quality of flat-top KDP crystal

NASA Astrophysics Data System (ADS)

Sharma, S. K.; Verma, Sunil; Singh, Yeshpal; Bartwal, K. S.; Tiwari, M. K.; Lodha, G. S.; Bhagavannarayana, G.

2015-08-01

KDP crystal grown using flat-top technique has been characterized using X-ray and optical techniques with the aim of correlating the defects structure and impurity concentration in the crystal with its optical properties. Crystallographic defects were investigated using X-ray topography revealing linear and arc like chains of dislocations and to conclude that defects do not originate from the flat-top part of the crystal. Etching was performed to quantify dislocation defects density. The crystalline perfection of the crystal was found to be high as the FWHM of the rocking curves measured at several locations was consistently low 6-9 arc s. The concentration of Fe metallic impurity quantified using X-ray fluorescence technique was approximately 5 times lower in the flat-top part which falls in pyramidal growth sector as compared to the region near to the seed which lies in prismatic sector. The spectrophotometric characterization for plates cut normal to different crystallographic directions in the flat-top potassium dihydrogen phosphate (FT-KDP) crystal was performed to understand the influence of metallic impurity distribution and growth sectors on the optical transmittance. The transmittance of the FT-KDP crystal at 1064 nm and its higher harmonics (2nd, 3rd, 4th and 5th) was determined from the measured spectra and the lower transmission in the UV region was attributed to increased absorption by Fe metallic impurity at these wavelengths. The results are in agreement with the results obtained using X-ray fluorescence and X-ray topography. Birefringence and Mach-Zehnder interferometry show that except for the region near to the seed crystal the optical homogeneity of the entire crystal was good. The laser-induced damage threshold (LDT) values are in the range 2.4-3.9 GW/cm2. The LDT of the plate taken from the flat-top region is higher than that from the bottom of the crystal, indicating that the flat-top technique has good optical quality and is comparable to those reported using rapid growth technique. The results indicate that the structural defects, crystalline quality and impurity concentration have a correlation with the optical properties of the FT-KDP crystal.

Algebraic Structure of tt * Equations for Calabi-Yau Sigma Models

NASA Astrophysics Data System (ADS)

Alim, Murad

2017-08-01

The tt * equations define a flat connection on the moduli spaces of {2d, \\mathcal{N}=2} quantum field theories. For conformal theories with c = 3 d, which can be realized as nonlinear sigma models into Calabi-Yau d-folds, this flat connection is equivalent to special geometry for threefolds and to its analogs in other dimensions. We show that the non-holomorphic content of the tt * equations, restricted to the conformal directions, in the cases d = 1, 2, 3 is captured in terms of finitely many generators of special functions, which close under derivatives. The generators are understood as coordinates on a larger moduli space. This space parameterizes a freedom in choosing representatives of the chiral ring while preserving a constant topological metric. Geometrically, the freedom corresponds to a choice of forms on the target space respecting the Hodge filtration and having a constant pairing. Linear combinations of vector fields on that space are identified with the generators of a Lie algebra. This Lie algebra replaces the non-holomorphic derivatives of tt * and provides these with a finer and algebraic meaning. For sigma models into lattice polarized K3 manifolds, the differential ring of special functions on the moduli space is constructed, extending known structures for d = 1 and 3. The generators of the differential rings of special functions are given by quasi-modular forms for d = 1 and their generalizations in d = 2, 3. Some explicit examples are worked out including the case of the mirror of the quartic in {\\mathbbm{P}^3}, where due to further algebraic constraints, the differential ring coincides with quasi modular forms.

From belt picking to bin packing

NASA Astrophysics Data System (ADS)

Balslev, Ivar; Eriksen, René D.

2002-10-01

We face the problem of computer-vision aided robot grasping of objects with more or less random positions. This field is of vital importance in the further progress in flexible automation of industrial processes, since conventional methods using fixtures and/or vibration bowls are expensive and inflexible. We study various types of disorder: A) visually isolated objects lying in distinct resting modes on a flat homogenous conveyer belt, B) partially occluded objects lying in distinct resting modes on a flat homogenous conveyer belt, C) visually separated objects, unrestricted object-camera pose, and fully surrounded by background, D) partially occluded objects, unrestricted relative orientation, but with a sizeable fraction of their contour detectable using foreground-background separation, E) partially occluded objects with unrestricted pose and no help from foreground-background separation. The cases A), B), and - to some extend - D) are encountered in belt picking, while case E) is true bin picking. Since physical storage of products and components in industry is based on deep containers with many layers of somewhat disordered objects, the belt-picking concept is only the first step for achieving flexible, unsupervised parts feeding. We have developed and tested a generic, fast, and easily trainable system for the cases A) and B). The system is unique because it handles the perspective effects exactly so there is no restriction concerning object dimensions relative to the distance to the camera. We report on a strategy to be used in treating case C) using the principles developed for the cases A-B). We discuss possible strategies to be employed when going all the way to cases of D) and E).

Testing alternative conceptual models of seawater intrusion in a coastal aquifer using computer simulation, southern California, USA

USGS Publications Warehouse

Nishikawa, Tracy

1997-01-01

Two alternative conceptual models of the physical processes controlling seawater intrusion in a coastal basin in California, USA, were tested to identify a likely principal pathway for seawater intrusion. The conceptual models were tested by using a two-dimensional, finite-element groundwater flow and transport model. This pathway was identified by the conceptual model that best replicated the historical data. The numerical model was applied in cross section to a submarine canyon that is a main avenue for seawater to enter the aquifer system underlying the study area. Both models are characterized by a heterogeneous, layered, water-bearing aquifer. However, the first model is characterized by flat-lying aquifer layers and by a high value of hydraulic conductivity in the basal aquifer layer, which is thought to be a principal conduit for seawater intrusion. The second model is characterized by offshore folding, which was modeled as a very nearshore outcrop, thereby providing a shorter path for seawater to intrude. General conclusions are that: 1) the aquifer system is best modeled as a flat, heterogeneous, layered system; 2) relatively thin basal layers with relatively high values of hydraulic conductivity are the principal pathways for seawater intrusion; and 3) continuous clay layers of low hydraulic conductivity play an important role in controlling the movement of seawater.

Hydrology of the Poverty Bay flats aquifers, New Zealand: recharge mechanisms, evolution of the isotopic composition of dissolved inorganic carbon, and ground-water ages

NASA Astrophysics Data System (ADS)

Taylor, C. B.

1994-06-01

With the exception of water-bearing remnants of earlier fluvial gravels overlying basement, the sediments of the Poverty Bay flats have accumulated during the postglacial period of the past 14 000 years, and have been tilted and deformed by recent tectonism. A sequence of gravel aquifers, separated by poorly permeable silt layers, lies between surface and basement, which is at depths varying between 50 and 200 m. A shallow sand/silt aquifer is situated near the coast. This study applies evidence of chemical and isotopic properties of river and ground water to clarify the recharge mechanisms, chemical evolution and age of the ground water in the aquifers. Particular attention is paid to the evolution of dissolved inorganic carbon content, applying carbon-14 data measured by accelerator mass spectrometry. Most of the ground water is recharged from the Waipaoa River, which flows across the flats and discharges into Poverty Bay. The two deepest aquifers (Matokitoki and Makauri) are both tritium-free; the deeper Matokitoki Gravels yield water of age about 4300 years since recharge (possibly up to 1300 years greater), but the Makauri water is no older than 100-200 years, discharging slowly through overlying aquitards near the limit of closest approach to the present coast.

Synthesis, structure, computational and in-silico anticancer studies of N,N-diethyl-N‧-palmitoylthiourea

NASA Astrophysics Data System (ADS)

Asegbeloyin, Jonnie Niyi; Oyeka, Ebube Evaristus; Okpareke, Obinna; Ibezim, Akachukwu

2018-02-01

A new potential ONS donor ligand N,N-diethyl-N‧-palmitoylthiourea (PACDEA) with the molecular formular C21H42N2OS has been synthesized and characterized by ESI-MS, UV, FTIR 1H and 13C NMR spectroscopy and single X-ray crystallography. The asymmetric molecules crystallized in the centrosymmetric structure of monoclinic crystal system with space group P21/c. In the crystal structure of the compound, molecules are linked in a continuous chain by intermolecular Nsbnd H⋯Odbnd C hydrogen bonds, which stabilized the crystal structure. The palmitoyl moiety and N (2)-ethyl group lie on a plane, while the thiocarbonyl moiety is twisted and lying othorgonal to the plane. Non-covalent interaction (NCI) analysis on the hydrogen bonded solid state structure of the molecule revealed the presence of a significant number of non-covalent interactions including intermolecular hydrogen bonding interactions, Csbnd Hsbnd -lone pair interactions, weak Van der Waals interactions, and steric/ring closure interactions. The NCI analysis also showed the presence of intramolecular stabilizing Csbnd H⋯Odbnd C and Csbnd H⋯Sdbnd C interactions. Docking simulation revealed that the compound interacted favourably with ten selected validated anticancer drug targets, which is an indication that the compound could possess some anticancer properties.

Molecular adsorption at electrolyte/α-Al2O3 interface of aluminum electrolytic capacitor revealed by sum frequency vibrational spectroscopy.

PubMed

Jia, Ming; Hu, Xiaoyu; Liu, Jin; Liu, Yexiang; Ai, Liang

2017-05-21

The operating voltage of an aluminum electrolytic capacitor is determined by the breakdown voltage (U b ) of the Al 2 O 3 anode. U b is related to the molecular adsorption at the Al 2 O 3 /electrolyte interface. Therefore, we have employed sum-frequency vibrational spectroscopy (SFVS) to study the adsorption states of a simple electrolyte, ethylene glycol (EG) solution with ammonium adipate, on an α-Al 2 O 3 surface. In an acidic electrolyte (pH < 6), the Al 2 O 3 surface is positively charged. The observed SFVS spectra show that long chain molecules poly ethylene glycol and ethylene glycol adipate adopt a "lying" orientation at the interface. In an alkaline electrolyte (pH > 8), the Al 2 O 3 surface is negatively charged and the short chain EG molecules adopt a "tilting" orientation. The U b results exhibit a much higher value at pH < 6 compared with that at pH > 8. Since the "lying" long chain molecules cover and protect the Al 2 O 3 surface, U b increases with a decrease of pH. These findings provide new insights to study the breakdown mechanisms and to develop new electrolytes for high operating voltage capacitors.

The Heat of Formation of HNO

NASA Technical Reports Server (NTRS)

Lee, Timothy J.; Dateo, Christopher E.

1995-01-01

The HNO molecule is of interest in both combustion and atmospheric chemistry. For example, Guadagnini et al. have recently presented ab initio potential energy surfaces for the three lowest lying electronic states of HNO and then used these in examining several chemical reactions that take place in the combustion of nitrogen containing fuels and in the oxidation of atmospheric nitrogen. We have previously studied the ground state potential energy surface (i.e., stationary points along the HNO reversible reaction HON path), vibrational spectrum (using an accurate quartic force field), zero-point energy, and bonding of HNO using coupled-cluster ab initio methods. HNO is also very interesting because of the unique nature of its bonding characteristics. That is, the potential energy surface is very flat along the H-N bonding coordinate thereby giving unusual harmonic and fundamental vibrational frequencies, and the H-N bond energy is rather weak in comparison to other H-N bond energies. In fact, using experimental heats of formation for HNO, H, and NO, the H- bond energy is computed to be only 49.9 kcal/ mol (298 K). However, ab initio calculations of isodesmic reaction energies involving HNO, FNO, ClNO, and several other molecules have shown that there is an inconsistency in the experimental heats of formation of the XNO (X double bond H, F, and Cl) species. Hence the motivation for this study was to determine a very accurate (Delta)H(sub f, sup o) value for HNO using state-of-the-art ab initio methods. Based on many recent studies it is evident that the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations, denoted CCSD(T), in conjunction with large one-particle basis sets should be reliable to better than +/- 0.8 kcal/mol for this quantity. The computational methodology is described in the next section followed by our results and discussion. Conclusions are presented in the final section.

The Heat of Formation of HNO

NASA Technical Reports Server (NTRS)

Lee, Timothy J.; Dateo, Christopher E.

1995-01-01

The HNO molecule is of interest in both combustion and atmospheric chemistry. For example, Guadagnini et al. have recently presented ab initio potential energy surfaces for the three lowest lying electronic states of HNO and then used these in examining several chemical reactions that take place in the combustion of nitrogen containing fuels and in the oxidation of atmospheric nitrogen. We have previously studied the ground state potential energy surface (i.e., stationary points along the HNO rev. reaction HON path), vibrational spectrum (using an accurate quartic force field), zero-point energy, and bonding of HNO using coupled-cluster ab initio methods. HNO is also very interesting because of the unique nature of its bonding characteristics. That is, the potential energy surface is very flat along the H-N bonding coordinate thereby giving unusual harmonic and fundamental vibrational frequencies, and the H-N bond energy is rather weak in comparison to other H-N bond energies. In fact, using experimental heats of formation for HO, H, and NO, the H- bond energy is computed to be only 49.9 kcal/ mol (298 K). However, ab initio calculations of isodesmic reaction energies involving HNO, FNO, ClNO, and several other molecules have shown that there is an inconsistency in the experimental heats of formation of the XNO (X=H, F, and Cl) species. Hence the motivation for this study was to determine a very accurate(DELTA)H(sup o)(sub f) value for HNO using state of-the-art ab initio methods. Based on many recent studies it is evident that the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations, denoted CCSD(T), in conjunction with large one-particle basis sets should be reliable to better than +0.8 kcal/mol for this quantity. The computational methodology is described in the next section followed by our results and discussion. Conclusions are presented in the final section.

Communication: Recovering the flat-plane condition in electronic structure theory at semi-local DFT cost

NASA Astrophysics Data System (ADS)

Bajaj, Akash; Janet, Jon Paul; Kulik, Heather J.

2017-11-01

The flat-plane condition is the union of two exact constraints in electronic structure theory: (i) energetic piecewise linearity with fractional electron removal or addition and (ii) invariant energetics with change in electron spin in a half filled orbital. Semi-local density functional theory (DFT) fails to recover the flat plane, exhibiting convex fractional charge errors (FCE) and concave fractional spin errors (FSE) that are related to delocalization and static correlation errors. We previously showed that DFT+U eliminates FCE but now demonstrate that, like other widely employed corrections (i.e., Hartree-Fock exchange), it worsens FSE. To find an alternative strategy, we examine the shape of semi-local DFT deviations from the exact flat plane and we find this shape to be remarkably consistent across ions and molecules. We introduce the judiciously modified DFT (jmDFT) approach, wherein corrections are constructed from few-parameter, low-order functional forms that fit the shape of semi-local DFT errors. We select one such physically intuitive form and incorporate it self-consistently to correct semi-local DFT. We demonstrate on model systems that jmDFT represents the first easy-to-implement, no-overhead approach to recovering the flat plane from semi-local DFT.

Hydraulic fracturing to enhance the remediation of DNAPL in low permeability soils

DOE Office of Scientific and Technical Information (OSTI.GOV)

Murdoch, L.; Slack, B.

1996-08-01

Meager rates of fluid flow are a major obstacle to in situ remediation of low permeability soils. This paper describes methods designed to avoid that obstacle by creating fractures and filling them with sand to increase well discharge and change paths of fluid flow in soil. Gently dipping fractures 10 m in maximum dimension and 1 to 2 cm thick can be created in some contaminated soils at depths of a few in or greater. Hydraulic fractures can also be used to create electrically conductive layers or to deliver granules of chemically or biologically active compounds that will degrade contaminantsmore » in place. Benefits of applying hydraulic fractures to DNAPL recovery include rates of fluid recovery, enhancing upward gradients to improve hydrodynamic stabilization, forming flat-lying reactive curtains to intersect compounds moving downward, or improving the performance of electrokinetics intended to recover compounds dissolved in water. 30 refs., 7 figs., 1 tab.« less

Report of reprocessing of reflection seismic profile X-5 Waste Isolation Pilot Plant site, Eddy County, New Mexico

USGS Publications Warehouse

Miller, John J.

1983-01-01

Seismic reflection profile X-5 exhibits a 7,700 ft long anomalous zone of poor quality to nonexistent reflections between shotpoints 100 and 170, compared to the high-quality, flat-lying, coherent reflections on either side. Results from drill holes in the area suggest 'layer cake' geology with no detectable abnormalities such as faults present. In an attempt to determine whether the anomalous zone of the seismic profile is an artifact or actually indicates a geologic condition, the data were extensively reprocessed using state-of-the-art processing techniques and the following conclusions were made: 1. The field-recorded data in the anomalous zone are of poor quality due to surface conditions and recording parameters used. 2. Reprocessing shows reflectors throughout the anomalous zone at all levels. However, it cannot prove that the reflectors are continuous throughout the anomalous zone. 3. Significant improvement in data quality may be achieved if the line is reshot using carefully determined recording parameters.

Wide-angle flat field telescope

NASA Technical Reports Server (NTRS)

Hallam, K. L.; Howell, B. J.; Wilson, M. E.

1986-01-01

Described is an unobscured three mirror wide angle telescopic imaging system comprised of an input baffle which provides a 20 deg (Y axis) x 30 deg (X axis) field of view, a primary mirror having a convex spherical surface, a secondary mirror having a concave ellipsoidal reflecting surface, a tertiary mirror having a concave spherical reflecting surface. The mirrors comprise mirror elements which are offset segments of parent mirrors whose axes and vertices commonly lie on the system's optical axis. An iris diaphragm forming an aperture stop is located between the secondary and tertiary mirror with its center also being coincident with the optical axis and being further located at the beam waist of input light beams reflected from the primary and secondary mirror surfaces. At the system focus following the tertiary mirror is located a flat detector which may be, for example, a TV imaging tube or a photographic film. When desirable, a spectral transmission filter is placed in front of the detector in close proximity thereto.

Giant-geode endowment of tumuli in the Veia Alta flow, Ametista do Sul

NASA Astrophysics Data System (ADS)

Hartmann, L. A.; Pertille, J.; Duarte, L. C.

2017-08-01

Tumuli are a common feature of pahoehoe basaltic flows, interspersed with pits, and furnished the necessary volume of rock in the Paraná volcanic province for hydrothermal alteration and ballooning to form large cavities (1-2 m common). Filling by amethyst and other minerals resulted in the largest world deposit of geodes, Ametista do Sul. The flat-lying fracture positioned 1 m below the 2-3 m thick geodic level crosses the plateau and is a major guide for exploration and gallery opening. The geodes are limited on the top by the platy joint layer, which is covered by an auto-breccia with undulating lower limit. This wave mimicks and is internal to the structure of tumuli and pits at the surface. This field-oriented survey of galleries selected out of 300 active mines resulted in the description of the internal structure of the remarkable Veia Alta pahoehoe flow, in addition to observations in Uruguay.

Flutter of Hybrid Laminated Flat Panels with Simply Supported Edges in Supersonic Flow

NASA Astrophysics Data System (ADS)

Barai, A.; Durvasula, S.

1994-01-01

Flutter of hybrid laminated flat panels in supersonic flow is studied by using first order shear deformation theory in conjunction with the assumed mode method. Both the quasi-static approximation and piston theory are used for aerodynamic force calculations at supersonic speeds. The flutter stability boundaries are determined by using the frequency coalescence criterion with the quasi-static approximation and Movchan-Krumhaar's criterion with the piston theory aerodynamics. Numerical calculations are presented for hybrid laminates consisting of graphite, Kevlar and glass fibres in an epoxy matrix. The effects of hybridization, shear deformation, ply orientation and aspect ratio are studied. The critical dynamic pressure parameter of a hybrid laminate lies between the values for laminates made with all plies of higher stiffness and with all plies of lower stiffness, respectively. The role of aerodynamic damping is found to be particularly important in determining the aeroelastic stability boundaries of laminated composite panels. Shear flexibility reduces the critical dynamic pressure parameter, but the reduction is insignificant for thin panels.

To Great Depths

NASA Image and Video Library

2017-03-22

Hellas is an ancient impact structure and is the deepest and broadest enclosed basin on Mars. It measures about 2,300 kilometers across and the floor of the basin, Hellas Planitia, contains the lowest elevations on Mars. The Hellas region can often be difficult to view from orbit due to seasonal frost, water-ice clouds and dust storms, yet this region is intriguing because of its diverse, and oftentimes bizarre, landforms. This image from eastern Hellas Planitia shows some of the unusual features on the basin floor. These relatively flat-lying "cells" appear to have concentric layers or bands, similar to a honeycomb. This "honeycomb" terrain exists elsewhere in Hellas, but the geologic process responsible for creating these features remains unresolved. The map is projected here at a scale of 50 centimeters (19.7 inches) per pixel. [The original image scale is 52.2 centimeters (20.6 inches) per pixel (with 2 x 2 binning); objects on the order of 157 centimeters (61.8 inches) across are resolved.] North is up. http://photojournal.jpl.nasa.gov/catalog/PIA21570

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lorenz, J.C.; Branagan, P.; Warpinski, N.R.

A new model suggests that the fracture systems that control permeability in flat-lying fluvial reservoirs are distributed in a continuum of sizes, and occur in subparallel, en echelon patterns. Few high angle ''orthogonal'' fractures exist because this system is created by high pore pressures and relatively low differential horizontal stresses, rather than by structural deformation. Interfracture communication occurs primarily at infrequent, low-angle intersections of fractures. Vertical continuity of such fractures through a reservoir is commonly limited by the numerous lithologic discontinuities inherent in fluvial sandstones. This type of fracture system has been documented in Mesaverde rocks in the Rulison fieldmore » of the Piceance Creek basin, northwestern Colorado, by studies of 4300 ft (1310 m) of core from the US Department of Energy's three Multiwell Experiment wells, and by studies of the excellent nearby outcrops. Well test results and geologic data from core and outcrop support the model. The described natural fracture system has a significant effect on production and stimulation. 16 refs., 15 figs., 1 tab.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lorenz, J.C.; Warpinski, N.R.; Sattler, A.R.

A model is presented that suggests that regional fracture systems commonly control permeability in flat-lying reservoirs. Such fractures are distributed in a continuum of sizes and occur in subparallel, en echelon patterns. Few high-angle, orthogonal fractures exist because this system is created by high pore pressures and relatively low differential horizontal (tectonic) stresses rather than by significant structural deformation. Interfracture communication occurs primarily at infrequent, low-angle intersections of fractures. Vertical continuity of such fractures through a reservoir commonly is limited to the numerous lithologic discontinuities inherent in nonmarine sandstones. This type of fracture system has been documented in Mesaverede rocksmore » in the Rulison field of the Piceance Creek basin, northwestern Colorado, by studies of 4,300 ft (1310 m) of core from the U.S. DOE's three Multiwell Experiment (MWX) wells and by studies of the excellent nearby outcrops. Well test results and geologic data from core and outcrop support the model. The described natural fracture system has a significant effect on production and stimulation.« less

Post-carboniferous tectonics in the Anadarko Basin, Oklahoma: Evidence from side-looking radar imagery

NASA Technical Reports Server (NTRS)

Nielsen, K. C.; Stern, R. J.

1985-01-01

The Anadarko Basin of western Oklahoma is a WNW-ESE elongated trough filled with of Paleozoic sediments. Most models call for tectonic activity to end in Pennsylvanian times. NASA Shuttle Imaging Radar revealed a distinctive and very straight lineament set extending virtually the entire length of the Anadarko Basin. The lineaments cut across the relatively flat-lying Permian units exposed at the surface. The character of these lineaments is seen most obviously as a tonal variation. Major streams, including the Washita and Little Washita rivers, appear to be controlled by the location of the lineaments. Subsurface data indicate the lineaments may be the updip expression of a buried major fault system, the Mountain View fault. Two principal conclusions arise from this analysis: (1) the complex Mountain View Fault system appears to extend southeast to join the Reagan, Sulphur, and/or Mill Creek faults of the Arbuckle Mountains, and (2) this fault system has been reactivated in Permian or younger times.

The Earth is flat when personally significant experiences with the sphericity of the Earth are absent.

PubMed

Carbon, Claus-Christian

2010-07-01

Participants with personal and without personal experiences with the Earth as a sphere estimated large-scale distances between six cities located on different continents. Cognitive distances were submitted to a specific multidimensional scaling algorithm in the 3D Euclidean space with the constraint that all cities had to lie on the same sphere. A simulation was run that calculated respective 3D configurations of the city positions for a wide range of radii of the proposed sphere. People who had personally experienced the Earth as a sphere, at least once in their lifetime, showed a clear optimal solution of the multidimensional scaling (MDS) routine with a mean radius deviating only 8% from the actual radius of the Earth. In contrast, the calculated configurations for people without any personal experience with the Earth as a sphere were compatible with a cognitive concept of a flat Earth. 2010 Elsevier B.V. All rights reserved.

Geologic Map of the Round Spring Quadrangle, Shannon County, Missouri

USGS Publications Warehouse

Orndorff, Randall C.; Weary, David J.

2009-01-01

The Round Spring 7.5-minute quadrangle is located in Shannon County, south-central Missouri on the Salem Plateau of the Ozark Plateaus physiographic province. As much as 1,350 feet (ft) of flat-lying to gently dipping Upper Cambrian and Lower Ordovician rocks, mostly dolomite, overlie Mesoproterozoic volcanic rocks. The bedrock is overlain by unconsolidated residuum, colluvium, terrace deposits, and alluvium. Karst features, such as small sinkholes and caves, have formed in the carbonate rocks, and many streams are spring fed. The topography is a dissected karst plain with elevation ranging from 650 ft along the Current River on the eastern edge of the quadrangle to almost 1,200 ft at various places on the ridge tops. The area is mostly forested but contains some farmlands and includes sections of the Ozark National Scenic Riverways of the National Park Service along the Current River. Geologic mapping for this investigation began in the spring of 2001 and was completed in the spring of 2002.

Two-dimensional character of internal rotation of furfural and other five-member heterocyclic aromatic aldehydes

NASA Astrophysics Data System (ADS)

Bataev, Vadim A.; Pupyshev, Vladimir I.; Godunov, Igor A.

2016-05-01

The features of nuclear motion corresponding to the rotation of the formyl group (CHO) are studied for the molecules of furfural and some other five-member heterocyclic aromatic aldehydes by the use of MP2/6-311G** quantum chemical approximation. It is demonstrated that the traditional one-dimensional models of internal rotation for the molecules studied have only limited applicability. The reason is the strong kinematic interaction of the rotation of the CHO group and out-of-plane CHO deformation that is realized for the molecules under consideration. The computational procedure based on the two-dimensional approximation is considered for low lying vibrational states as more adequate to the problem.

Computational modeling of the effective Young's modulus values of fullerene molecules: a combined molecular dynamics simulation and continuum shell model.

PubMed

Ghavanloo, Esmaeal; Izadi, Razie; Nayebi, Ali

2018-02-28

Estimating the Young's modulus of a structure in the nanometer size range is a difficult task. The reliable determination of this parameter is, however, important in both basic and applied research. In this study, by combining molecular dynamics (MD) simulations and continuum shell theory, we designed a new approach to determining the Young's modulus values of different spherical fullerenes. The results indicate that the Young's modulus values of fullerene molecules decrease nonlinearly with increasing molecule size and understandably tend to the Young's modulus of an ideal flat graphene sheet at large molecular radii. To the best of our knowledge, this is first time that a combined atomistic-continuum method which can predict the Young's modulus values of fullerene molecules with high precision has been reported.

Electronic structure investigation of neutral titanium oxide molecules TixOy

NASA Astrophysics Data System (ADS)

Jeong, K. S.; Chang, Ch; Sedlmayr, E.; Sülzle, D.

2000-09-01

Electronic and structural properties of energetically low-lying isomers of isolated TixOy (x = 1-6, y = 1-12) molecular systems have been investigated by density functional theoretical methods. A variety of stationary points are thoroughly characterized. We report total cluster energies, equilibrium geometries and harmonic vibrational wavenumbers.

Bis(N-ethyl-N-methyl-dithio-carbamato-κS,S')diphenyl-tin(IV).

PubMed

Muthalib, Amirah Faizah; Baba, Ibrahim; Ng, Seik Weng

2010-03-03

The dithio-carbamate anions in the title compound, [Sn(C(6)H(5))(2)(C(4)H(8)NS(2))(2)], chelate to the Sn(IV) atom, which is six-coordinated in a skew-trapezoidal-bipyramidal geometry. The mol-ecule lies across a twofold rotation axis.

Bis(N-isopropyl-N-methyl-dithio-carbamato-κS,S')diphenyl-tin(IV).

PubMed

Muthalib, Amirah Faizah; Baba, Ibrahim; Farina, Yang; Ng, Seik Weng

2010-03-03

The dithio-carbamate anions in the title compound, [Sn(C(6)H(5))(2)(C(5)H(10)NS(2))(2)], chelate to the Sn(IV) atom, which is six-coordinated in a skew-trapezoidal-bipyramidal geometry. The mol-ecule lies across a twofold rotation axis.

AMS fabric and structural record along a strain gradient in an extrusive salt diapir (Kuh-e-Namak, Dashti, Iran)

NASA Astrophysics Data System (ADS)

Zavada, Prokop; Schulmann, Karel; Lexa, Ondrej; Machek, Matej; Roxerova, Zuzana; Kusbach, Vladimir

2016-04-01

The AMS record and the halite fabrics on meso- and micro-scale were studied in detail on a well exposed salt extrusive body in Iran. In the Kuh-e-Namak (Dashti) mountain salt diapir, the deformation structures in colored salt are displayed along longitudinal profiles across the dome and two glaciers that extend from the NE and SW edge of the dome. The profiles from the dome to the frontal parts of the glaciers reveal a continuous strain gradient associated with transposition of the domal salt fabrics by axial fold cleavage development during flow of rock salt over the ridges in the channel. The extruded salt belongs to the Hormuz sequence of Neo-Proterozoic to Early Cambrian age. From central dome towards especially the northern namakier, structural record revealed zonation from; 1) gravitational collapse related recumbent isoclinal folds in the dome, 2) flat normal shears at the edge of the dome, 3) collapsed vertical layering into flat lying transpositional fabric at the toe of the dome, 4) penetrative fold cleavage transposition of earlier fabrics above the topographical ridge in the base of the flow, locally displaying strong transversal constrictional fabrics, 5) banded mylonites with isoclinal rootless folds in subhorizontally banded frontal and marginal domain of the glacier. The AMS fabric in the rock salt is generated primarily by hematite dispersed in the recrystallized halite. The AMS exhibits three main types of fabric symmetry from clustered all directions (K1,K2,K3, orthogonal fabric) to clustered K1 directions with girdle forming K2,K3 axes and clustered K3 directions with girdle of K1 and K2 directions. The AMS fabric clearly reflects the macroscopic fabric transpositions along the entire investigated strain gradient in the rock salt. Magnetic fabrics reveal continuous trends from bimodal to semi-girdle distribution of foliations in folded and cleavage present regions, to magnetic lineation clustering perpendicular to flow in completely refolded domains and to flat lying orthogonal fabric in mylonites at the frontal and marginal edges of the glacier.

Deviation from Normal Boltzmann Distribution of High-lying Energy Levels of Iron Atom Excited by Okamoto-cavity Microwave-induced Plasmas Using Pure Nitrogen and Nitrogen-Oxygen Gases.

PubMed

Wagatsuma, Kazuaki

2015-01-01

This paper describes several interesting excitation phenomena occurring in a microwave-induced plasma (MIP) excited with Okamoto-cavity, especially when a small amount of oxygen was mixed with nitrogen matrix in the composition of the plasma gas. An ion-to-atom ratio of iron, which was estimated from the intensity ratio of ion to atomic lines having almost the same excitation energy, was reduced by adding oxygen gas to the nitrogen MIP, eventually contributing to an enhancement in the emission intensities of the atomic lines. Furthermore, Boltzmann plots for iron atomic lines were observed in a wide range of the excitation energy from 3.4 to 6.9 eV, indicating that plots of the atomic lines having lower excitation energies (3.4 to 4.8 eV) were well fitted on a straight line while those having more than 5.5 eV deviated upwards from the linear relationship. This overpopulation would result from any other excitation process in addition to the thermal excitation that principally determines the Boltzmann distribution. A Penning-type collision with excited species of nitrogen molecules probably explains this additional excitation mechanism, in which the resulting iron ions recombine with captured electrons, followed by cascade de-excitations between closely-spaced excited levels just below the ionization limit. As a result, these high-lying levels might be more populated than the low-lying levels of iron atom. The ionization of iron would be caused less actively in the nitrogen-oxygen plasma than in a pure nitrogen plasma, because excited species of nitrogen molecule, which can provide the ionization energy in a collision with iron atom, are consumed through collisions with oxygen molecules to cause their dissociation. It was also observed that the overpopulation occurred to a lesser extent when oxygen gas was added to the nitrogen plasma. The reason for this was also attributed to decreased number density of the excited nitrogen species due to collisions with oxygen molecule.

Electronic Transitions of Tungsten Monosulfide

NASA Astrophysics Data System (ADS)

Tsang, L. F.; Chan, Man-Chor; Zou, Wenli; Cheung, Allan S. C.

2017-06-01

Electronic transition spectrum of the tungsten monosulfide (WS) molecule in the near infrared region between 725 nm and 885 nm has been recorded using laser ablation/reaction free-jet expansion and laser induced fluorescence spectroscopy. The WS molecule was produced by reacting laser - ablated tungsten atoms with 1% CS_{2} seeded in argon. Fifteen vibrational bands with resolved rotational structure have been recorded and analyzed, which were organized into seven electronic transition systems. The ground state has been identified to be the X^{3}Σ^{-}(0^{+}) state, and the determined vibrational frequency, ΔG_{1/2} and bond length, r_{0}, are respectively 556.7 cm^{-1} and 2.0676 Å. In addition, vibrational bands belong to another transition system involving lower state with Ω = 1 component have also been analyzed. Least-squares fit of the measured line positions yielded molecular constants for the electronic states involved. The low-lying Λ-S states and Ω sub-states of WS have been calculated using state-averaged complete active space self-consistent field (SA-CASSCF) and followed by MRCISD+Q (internally contracted multi-reference configuration interaction with singles and doubles plus Davidson's cluster correction). The active space consists of 10 electrons in 9 orbitals corresponding to the W 5d6s and S 3p shells. The lower molecular orbitals from W 5s5p and S 3s are inactive but are also correlated, and relativistic effective core potential (RECPs) are adopted to replace the core orbitals with 60 (W) and 10 (S) core electrons, respectively. Spin-orbit coupling (SOC) is calculated via the state-interaction (SI) approach with RECP spin-orbit operators using SA-CASSCF wavefunctions, where the diagonal elements in the SOC matrix are replaced by the corresponding MRCISD+Q energies calculated above. Spectroscopic constants and potential energy curves of the ground and many low-lying Λ-S states and Ω sub-states of the WS molecule are obtained. The calculated spectroscopic constants of the ground and low-lying states are generally in good agreement with our experimental determination. This work represents the first experimental investigation of the electronic and molecular structure of the WS molecule.

Stimulated emission by hybrid transitions via a heteronuclear molecule

NASA Astrophysics Data System (ADS)

Dinev, S. G.; Khadzhikhristov, G. B.; Stefanov, I. L.

1990-03-01

An atomic emission, identified as a four-wave parametric emission and stimulated by collision assisted hybrid transition via a heteronuclear molecule, is presented together with a diagram of excitation and emission for the relevant K and NaK energy levels. The cascading emission from the excited 7S or 5D levels to lower-lying atomic states is considered to be insignificant. The dependence of the red signal and the NaK fluorescence on the pump energy is investigated, and the results can be used to indicate the onset of a stimulated process.

Structure-induced switching of interpolymer adhesion at a solid-polymer melt interface.

PubMed

Jiang, Naisheng; Sen, Mani; Zeng, Wenduo; Chen, Zhizhao; Cheung, Justin M; Morimitsu, Yuma; Endoh, Maya K; Koga, Tadanori; Fukuto, Masafumi; Yuan, Guangcui; Satija, Sushil K; Carrillo, Jan-Michael Y; Sumpter, Bobby G

2018-02-14

Here we report a link between the interfacial structure and adhesive property of homopolymer chains physically adsorbed (i.e., via physisorption) onto solids. Polyethylene oxide (PEO) was used as a model and two different chain conformations of the adsorbed polymer were created on silicon substrates via the well-established Guiselin's approach: "flattened chains" which lie flat on the solid and are densely packed, and "loosely adsorbed polymer chains" which form bridges jointing up nearby empty sites on the solid surface and cover the flattened chains. We investigated the adhesion properties of the two different adsorbed chains using a custom-built adhesion testing device. Bilayers of a thick PEO overlayer on top of the flattened chains or loosely adsorbed chains were subjected to the adhesion test. The results revealed that the flattened chains do not show any adhesion even with the chemically identical free polymer on top, while the loosely adsorbed chains exhibit adhesion. Neutron reflectivity experiments corroborated that the difference in the interfacial adhesion is not attributed to the interfacial brodening at the free polymer-adsorbed polymer interface. Instead, coarse-grained molecular dynamics simulation results suggest that the tail parts of the loosely adsorbed chains act as "connector molecules", bridging the free chains and substrate surface and improving the interfacial adhesion. These findings not only shed light on the structure-property relationship at the interface, but also provide a novel approach for developing sticking/anti-sticking technologies through precise control of the interfacial polymer nanostructures.

Design and engineering of organic molecules for customizable Terahertz tags

NASA Astrophysics Data System (ADS)

Ray, Shaumik; Dash, Jyotirmayee; Nallappan, Kathirvel; Kaware, Vaibhav; Basutkar, Nitin; Ambade, Ashootosh; Joshi, Kavita; Pesala, Bala

2014-03-01

Terahertz (THz) frequency band lies between the microwave and infrared region of the electromagnetic spectrum. Molecules having strong resonances in this frequency range are ideal for realizing "Terahertz tags" which can be easily incorporated into various materials. THz spectroscopy of molecules, especially at frequencies below 10 THz, provides valuable information on the low frequency vibrational modes, viz. intermolecular vibrational modes, hydrogen bond stretching, torsional vibrations in several chemical and biological compounds. So far there have been very few attempts to engineer molecules which can demonstrate customizable resonances in the THz frequency region. In this paper, Diamidopyridine (DAP) based molecules are used as a model system to demonstrate engineering of THz resonances (< 10 THz) by fine-tuning the molecular mass and bond strengths. Density Functional Theory (DFT) simulations have been carried out to explain the origin of THz resonances and factors contributing to the shift in resonances due to the addition of various functional groups. The design approach presented here can be easily extended to engineer various organic molecules suitable for THz tags application.

A low-temperature polymorph of m-quinquephenyl.

PubMed

Gomes, Ligia R; Howie, R Alan; Low, John Nicolson; Rodrigues, Ana S M C; Santos, Luís M N B F

2012-12-01

A low-temperature polymorph of 1,1':3',1'':3'',1''':3''',1''''-quinquephenyl (m-quinquephenyl), C(30)H(22), crystallizes in the space group P2(1)/c with two molecules in the asymmetric unit. The crystal is a three-component nonmerohedral twin. A previously reported room-temperature polymorph [Rabideau, Sygula, Dhar & Fronczek (1993). Chem. Commun. pp. 1795-1797] also crystallizes with two molecules in the asymmetric unit in the space group P-1. The unit-cell volume for the low-temperature polymorph is 4120.5 (4) Å(3), almost twice that of the room-temperature polymorph which is 2102.3 (6) Å(3). The molecules in both structures adopt a U-shaped conformation with similar geometric parameters. The structural packing is similar in both compounds, with the molecules lying in layers which stack perpendicular to the longest unit-cell axis. The molecules pack alternately in the layers and in the stacked columns. In both polymorphs, the only interactions between the molecules which can stabilize the packing are very weak C-H...π interactions.

Energy transfer between a nanosystem and its host fluid: A multiscale factorization approach

NASA Astrophysics Data System (ADS)

Sereda, Yuriy V.; Espinosa-Duran, John M.; Ortoleva, Peter J.

2014-02-01

Energy transfer between a macromolecule or supramolecular assembly and a host medium is considered from the perspective of Newton's equations and Lie-Trotter factorization. The development starts by demonstrating that the energy of the molecule evolves slowly relative to the time scale of atomic collisions-vibrations. The energy is envisioned to be a coarse-grained variable that coevolves with the rapidly fluctuating atomistic degrees of freedom. Lie-Trotter factorization is shown to be a natural framework for expressing this coevolution. A mathematical formalism and workflow for efficient multiscale simulation of energy transfer is presented. Lactoferrin and human papilloma virus capsid-like structure are used for validation.

Requirements for the conceptual design of advanced underground coal extraction systems

NASA Technical Reports Server (NTRS)

Gangal, M. D.; Lavin, M. L.

1981-01-01

Conceptual design requirements are presented for underground coal mining systems having substantially improved performance in the areas of production cost and miner safety. Mandatory performance levels are also set for miner health, environmental impact, and coal recovery. In addition to mandatory design goals and constraints, a number of desirable system characteristics are identified which must be assessed in terms of their impact on production cost and their compatibility with other system elements. Although developed for the flat lying, moderately thick seams of Central Appalachia, these requirements are designed to be easily adaptable to other coals.

A high-altitude barium radial injection experiment

NASA Technical Reports Server (NTRS)

Wescott, E. M.; Stenbaek-Nielsen, H. C.; Hallinan, T. J.; Deehr, C. S.; Romick, G. J.; Olson, J. V.; Roederer, J. G.; Sydora, R.

1980-01-01

A rocket launched from Poker Flat, Alaska, carried a new type of high-explosive barium shaped charge to 571 km, where detonation injected a thin disk of barium vapor with high velocity nearly perpendicular to the magnetic field. The TV images of the injection are spectacular, revealing three major regimes of expanding plasma which showed early instabilities in the neutral gas. The most unusual effect of the injection is a peculiar rayed barium-ion structure lying in the injection plane and centered on a 5 km 'black hole' surrounding the injection point. Preliminary electrostatic computer simulations show a similar rayed development.

3. West portal of Tunnel 23, view to north, 135mm ...

Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

3. West portal of Tunnel 23, view to north, 135mm lens. Concrete foundation in right foreground was from 'telltale,' a simple post-and-beam frame that spanned the tracks with lengths of rope suspended from the beam. In the days when brakemen were required to be on, and walk along, the tops of freight cars to set brakes, the 'telltale' ropes would strike the unwary to warn of the tunnel ahead, allowing them to lie flat and avoid being struck by the tunnel portal. - Central Pacific Transcontinental Railroad, Tunnel No. 23, Milepost 132.69, Applegate, Placer County, CA

A piezoelectric bone-conduction bending hearing actuator.

PubMed

Adamson, R B A; Bance, M; Brown, J A

2010-10-01

A prototype of a novel bone-conduction hearing actuator based on a piezoelectric bending actuator is presented. The device lies flat against the skull which would allow it to form the basis of a subcutaneous bone-anchored hearing aid. The actuator excites bending in bone through a local bending moment rather than the application of a point force as with conventional bone-anchored hearing aids. Through measurements of the cochlear velocity created by the actuator in embalmed human heads, the device is shown to exhibit high efficiency, making it a possible alternative to present-day electromagnetic bone-vibration actuators.

Graphene can wreak havoc with cell membranes.

PubMed

Dallavalle, Marco; Calvaresi, Matteo; Bottoni, Andrea; Melle-Franco, Manuel; Zerbetto, Francesco

2015-02-25

Molecular dynamics--coarse grained to the level of hydrophobic and hydrophilic interactions--shows that small hydrophobic graphene sheets pierce through the phospholipid membrane and navigate the double layer, intermediate size sheets pierce the membrane only if a suitable geometric orientation is met, and larger sheets lie mainly flat on the top of the bilayer where they wreak havoc with the membrane and create a patch of upturned phospholipids. The effect arises in order to maximize the interaction between hydrophobic moieties and is quantitatively explained in terms of flip-flops by the analysis of the simulations. Possible severe biological consequences are discussed.

High-temperature stability of the hydrate shell of a Na+ cation in a flat nanopore with hydrophobic walls

NASA Astrophysics Data System (ADS)

Shevkunov, S. V.

2017-11-01

The effect of elevated temperature has on the hydrate shell of a singly charged sodium cation inside a flat nanopore with smooth walls is studied using the Monte Carlo method. The free energy and the entropy of vapor molecule attachment are calculated by means of a bicanonical statistical ensemble using a detailed model of interactions. The nanopore has a stabilizing effect on the hydrate shell with respect to fluctuations and a destabilizing effect with respect to complete evaporation. At the boiling point of water, behavior is observed that is qualitatively similar to behavior at room temperature, but with a substantial shift in the vapor pressure and shell size.

Influence of aliphatic spacer group on adsorption mechanisms of phosphonate derivatives of L-phenylalanine: Surface-enhanced Raman, Raman, and infrared studies

NASA Astrophysics Data System (ADS)

Podstawka, E.; Kudelski, A.; Kafarski, P.; Proniewicz, L. M.

2007-10-01

The nature of phosphonopeptides containing N-terminal L-phenylalanine ( L-Phe), namely L-Phe- DL-NH-CH(CH(CH 3) 2)-PO 3H 2 ( A), L-Phe- L-NH-CH(CH 3)-PO 3H 2 ( B), and L-Phe- DL-NH-CH(CH 2CH 2COOH)-PO 3H 2 ( C) ( Fig. 1 presents molecular structure of these molecules), adsorbed on electrochemically roughened and colloidal silver surfaces has been explored by surface-enhanced Raman spectroscopy (SERS). To reveal adsorption mechanism of these species on the basis of their SERS spectra at first Fourier-transform Raman (FT-RS) and absorption infrared (FT-IR) spectra of non-adsorbed molecules were measured. Examination of enhancement, frequency shifts, and changes in relative intensities of SERS bands due to adsorption and surface roughens variation reveals that the tilted compounds adsorb on the electrochemically roughened silver substrate in similar way, while they behave differently on the colloidal silver surface. A stronger enhancement of in-plane ring vibrations of the L-Phe ring, i.e., ν3 and ν18b (B 2), over these of the A 2 symmetry in all SERS spectra on the electrochemically roughened silver substrate suggests that the ring interacts with this surface adopting slightly deflect orientation from the perpendicular one. Also, enhancement of P dbnd O and -CH 2-/-CH 3 fragments vibrations points out that they are involved in adsorption process on this substrate. This conclusion was drawn on the basis of the enhancement of 1274-1279 and 1138-1152 ( ν(P dbnd O)), 1393-1400 ( δ(CH) + ρb(CNH 2) + ν(C-C dbnd O ) + δ(CH 3)), ˜1455 ( δ(CCH 3/CCH 2) + ρb(CH 3/CH 2), and 1505-1512 cm -1 ( δ(CH 2) + Phe( ν19a)) bands. Although a relative intensity ratio of these bands in the presented SERS spectra is different. On the other hand, on the colloidal silver nanoparticles, the aromatic ring of all molecules is lying flat or takes almost parallel orientation to this surface. Besides, A interacts also via P-terminal group (568, 765, 827, 1040, and 1150 cm -1), whereas B mainly through NH 2-C-(C dbnd O)-CNH-(712 and 1255 cm -1). In the case of C, it adsorbs on the silver colloidal surface mainly through the aromatic ring of L-Phe, while other fragments of the molecule are in close proximity to this surface as comes off the weak enhancement of bands due to the aliphatic vibrations.

Introductory Science Moves beyond "Rocks for Jocks"

ERIC Educational Resources Information Center

Brainard, Jeffrey

2008-01-01

In a survey last year, four-fifths of Americans surveyed could not correctly define "molecule." This is not good news for educators who worry that Americans are ill prepared to compete with other nations and understand political choices involving science. Behind those disturbing numbers lie another, more encouraging, set of poll results intimately…

Solving the Schroedinger Equation of Atoms and Molecules without Analytical Integration Based on the Free Iterative-Complement-Interaction Wave Function

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nakatsuji, H.; Nakashima, H.; Department of Synthetic Chemistry and Biological Chemistry, Graduate School of Engineering, Kyoto University, Nishikyo-ku, Kyoto 615-8510

2007-12-14

A local Schroedinger equation (LSE) method is proposed for solving the Schroedinger equation (SE) of general atoms and molecules without doing analytic integrations over the complement functions of the free ICI (iterative-complement-interaction) wave functions. Since the free ICI wave function is potentially exact, we can assume a flatness of its local energy. The variational principle is not applicable because the analytic integrations over the free ICI complement functions are very difficult for general atoms and molecules. The LSE method is applied to several 2 to 5 electron atoms and molecules, giving an accuracy of 10{sup -5} Hartree in total energy.more » The potential energy curves of H{sub 2} and LiH molecules are calculated precisely with the free ICI LSE method. The results show the high potentiality of the free ICI LSE method for developing accurate predictive quantum chemistry with the solutions of the SE.« less

Two-dimensional character of internal rotation of furfural and other five-member heterocyclic aromatic aldehydes.

PubMed

Bataev, Vadim A; Pupyshev, Vladimir I; Godunov, Igor A

2016-05-15

The features of nuclear motion corresponding to the rotation of the formyl group (CHO) are studied for the molecules of furfural and some other five-member heterocyclic aromatic aldehydes by the use of MP2/6-311G** quantum chemical approximation. It is demonstrated that the traditional one-dimensional models of internal rotation for the molecules studied have only limited applicability. The reason is the strong kinematic interaction of the rotation of the CHO group and out-of-plane CHO deformation that is realized for the molecules under consideration. The computational procedure based on the two-dimensional approximation is considered for low lying vibrational states as more adequate to the problem. Copyright © 2016 Elsevier B.V. All rights reserved.

Excellent Long-Term Stability of Power Conversion Efficiency in Non-Fullerene-Based Polymer Solar Cells Bearing Tricyanovinylene-Functionalized n-Type Small Molecules.

PubMed

Ko, Eun Yi; Park, Gi Eun; Lee, Ji Hyung; Kim, Hyung Jong; Lee, Dae Hee; Ahn, Hyungju; Uddin, Mohammad Afsar; Woo, Han Young; Cho, Min Ju; Choi, Dong Hoon

2017-03-15

New small molecules having modified acceptor strength and π-conjugation length and containing dicyanovinylene (DCV) and tricyanovinylene (TCV) as a strongly electron-accepting unit with indacenodithiophene, IDT(DCV) 2 , IDT(TCV) 2 , and IDTT(TCV) 2 , were synthesized and studied in terms of their applicability to polymer solar cells with PTB7-Th as an electron-donating polymer. Intriguingly, the blended films containing IDT(TCV) 2 and IDTT(TCV) 2 exhibited superior shelf life stabilities of more than 1000 h without any reduction in the initial power conversion efficiency. The low-lying lowest unoccupied molecular orbital energy levels and robust internal morphologies of small TCV-containing molecules could afford excellent shelf life stability.

Statistical analysis plan of the head position in acute ischemic stroke trial pilot (HEADPOST pilot).

PubMed

Olavarría, Verónica V; Arima, Hisatomi; Anderson, Craig S; Brunser, Alejandro; Muñoz-Venturelli, Paula; Billot, Laurent; Lavados, Pablo M

2017-02-01

Background The HEADPOST Pilot is a proof-of-concept, open, prospective, multicenter, international, cluster randomized, phase IIb controlled trial, with masked outcome assessment. The trial will test if lying flat head position initiated in patients within 12 h of onset of acute ischemic stroke involving the anterior circulation increases cerebral blood flow in the middle cerebral arteries, as measured by transcranial Doppler. The study will also assess the safety and feasibility of patients lying flat for ≥24 h. The trial was conducted in centers in three countries, with ability to perform early transcranial Doppler. A feature of this trial was that patients were randomized to a certain position according to the month of admission to hospital. Objective To outline in detail the predetermined statistical analysis plan for HEADPOST Pilot study. Methods All data collected by participating researchers will be reviewed and formally assessed. Information pertaining to the baseline characteristics of patients, their process of care, and the delivery of treatments will be classified, and for each item, appropriate descriptive statistical analyses are planned with comparisons made between randomized groups. For the outcomes, statistical comparisons to be made between groups are planned and described. Results This statistical analysis plan was developed for the analysis of the results of the HEADPOST Pilot study to be transparent, available, verifiable, and predetermined before data lock. Conclusions We have developed a statistical analysis plan for the HEADPOST Pilot study which is to be followed to avoid analysis bias arising from prior knowledge of the study findings. Trial registration The study is registered under HEADPOST-Pilot, ClinicalTrials.gov Identifier NCT01706094.

Novel Na(+) doped Alq3 hybrid materials for organic light-emitting diode (OLED) devices and flat panel displays.

PubMed

Bhagat, S A; Borghate, S V; Kalyani, N Thejo; Dhoble, S J

2015-05-01

Pure and Na(+) -doped Alq3 complexes were synthesized by a simple precipitation method at room temperature, maintaining a stoichiometric ratio. These complexes were characterized by X-ray diffraction, Fourier transform infrared (FTIR), UV/Vis absorption and photoluminescence (PL) spectra. The X-ray diffractogram exhibits well-resolved peaks, revealing the crystalline nature of the synthesized complexes, FTIR confirms the molecular structure and the completion of quinoline ring formation in the metal complex. UV/Vis absorption and PL spectra of sodium-doped Alq3 complexes exhibit high emission intensity in comparison with Alq3 phosphor, proving that when doped in Alq3 , Na(+) enhances PL emission intensity. The excitation spectra of the synthesized complexes lie in the range 242-457 nm when weak shoulders are also considered. Because the sharp excitation peak falls in the blue region of visible radiation, the complexes can be employed for blue chip excitation. The emission wavelength of all the synthesized complexes lies in the bluish green/green region ranging between 485 and 531 nm. The intensity of the emission wavelength was found to be elevated when Na(+) is doped into Alq3 . Because both the excitation and emission wavelengths fall in the visible region of electromagnetic radiation, these phosphors can also be employed to improve the power conversion efficiency of photovoltaic cells by using the solar spectral conversion principle. Thus, the synthesized phosphors can be used as bluish green/green light-emitting phosphors for organic light-emitting diodes, flat panel displays, solid-state lighting technology - a step towards the desire to reduce energy consumption and generate pollution free light. Copyright © 2014 John Wiley & Sons, Ltd.

Subglacial Depositional Processes in the Port Askaig Formation (Neoproterozoic) of Ireland

NASA Astrophysics Data System (ADS)

Knight, J.

2004-12-01

The Port Askaig Formation was deposited during the Vendian glaciation (c. 650 Ma) and is a range of tillites that outcrop discontinuously from Banffshire (Scotland) to Connemara (Ireland). Sedimentary structures commonly observed include dropstones and sediment drapes, interpreted as deposition from a floating glacial ice shelf in a shallow marginal sea. Other structures, such as intersecting clastic dikes, have been interpreted as evidence for subaerial exposure of the tillite surface. Exposures of the Port Askaig Formation were examined at its Irish type area at Kiltyfanned Lough, County Donegal. Here, homogeneous sandy beds with internal planar bedding structures are separated by laminated fine sand beds which have erosional upper surfaces. The laminated beds are clast-free and individual laminae are laterally continuous and undisturbed. Larger clasts lie bed-parallel and are draped by overlying beds. Occasionally drapes are asymmetric with a thickened sediment prow, suggestive of flow direction. The clastic dikes are polygonal in plan view, may be isolated or interconnected, and are often arranged in parallel sheets which pinch out laterally. Internally, the clastic dikes are infilled with coarse sand to gravel. Infills are often aligned parallel to dike margins. The presence of draped and deformed sediments suggest a subglacial environment with free water availability. The flat-lying morphology of clasts also favours a subglacial rather than a full marine environment. The morphology and disposition of clastic dikes is interpreted as due to subglacial hydrofracturing of a till sheet and upward passage of sediment-charged water through the fracture zone, which is known from late Pleistocene and Precambrian tillites elsewhere. Variations in water availability can be reconciled by a sub-ice shelf depositional model with spatial and temporal changes in tidally-induced ice-bed coupling.

Molecular dynamics simulation studies of caffeine aggregation in aqueous solution.

PubMed

Tavagnacco, Letizia; Schnupf, Udo; Mason, Philip E; Saboungi, Marie-Louise; Cesàro, Attilio; Brady, John W

2011-09-22

Molecular dynamics simulations were carried out on a system of eight independent caffeine molecules in a periodic box of water at 300 K, representing a solution near the solubility limit for caffeine at room temperature, using a newly developed CHARMM-type force field for caffeine in water. Simulations were also conducted for single caffeine molecules in water using two different water models (TIP3P and TIP4P). Water was found to structure in a complex fashion around the planar caffeine molecules, which was not sensitive to the water model used. As expected, extensive aggregation of the caffeine molecules was observed, with the molecules stacking their flat faces against one another like coins, with their methylene groups staggered to avoid steric clashes. A dynamic equilibrum was observed between large n-mers, including stacks with all eight solute molecules, and smaller clusters, with the calculated osmotic coefficient being in acceptable agreement with the experimental value. The insensitivity of the results to water model and the congruence with experimental thermodynamic data suggest that the observed stacking interactions are a realistic representation of the actual association mechanism in aqueous caffeine solutions.

Extending airborne electromagnetic surveys for regional active layer and permafrost mapping with remote sensing and ancillary data, Yukon Flats ecoregion, central Alaska

USGS Publications Warehouse

Pastick, Neal J.; Jorgenson, M. Torre; Wylie, Bruce K.; Minsley, Burke J.; Ji, Lei; Walvoord, Michelle Ann; Smith, Bruce D.; Abraham, Jared D.; Rose, Joshua R.

2013-01-01

Machine-learning regression tree models were used to extrapolate airborne electromagnetic resistivity data collected along flight lines in the Yukon Flats Ecoregion, central Alaska, for regional mapping of permafrost. This method of extrapolation (r = 0.86) used subsurface resistivity, Landsat Thematic Mapper (TM) at-sensor reflectance, thermal, TM-derived spectral indices, digital elevation models and other relevant spatial data to estimate near-surface (0–2.6-m depth) resistivity at 30-m resolution. A piecewise regression model (r = 0.82) and a presence/absence decision tree classification (accuracy of 87%) were used to estimate active-layer thickness (ALT) (< 101 cm) and the probability of near-surface (up to 123-cm depth) permafrost occurrence from field data, modelled near-surface (0–2.6 m) resistivity, and other relevant remote sensing and map data. At site scale, the predicted ALTs were similar to those previously observed for different vegetation types. At the landscape scale, the predicted ALTs tended to be thinner on higher-elevation loess deposits than on low-lying alluvial and sand sheet deposits of the Yukon Flats. The ALT and permafrost maps provide a baseline for future permafrost monitoring, serve as inputs for modelling hydrological and carbon cycles at local to regional scales, and offer insight into the ALT response to fire and thaw processes.

A seismic study of Yucca Mountain and vicinity, southern Nevada; data report and preliminary results

USGS Publications Warehouse

Hoffman, L.R.; Mooney, W.D.

1983-01-01

From 1980 to 1982, the U.S. Geological Survey conducted seismic refraction studies at the Nevada Test Site to aid in an investigation of the regional crustal structure at a possible nuclear waste repository site near Yucca Mountain. Two regionally distributed deployments and one north-south deployment recorded nuclear events. First arrival times from these deployments were plotted on a location map and contoured to determine traveltime delays. The results indicate delays as large as 0.5 s in the Yucca Mountain and Crater Flat areas relative to the Jackass Flats area. A fourth east-west deployment recorded a chemical explosion and was interpreted using a two-dimensional computer raytracing technique. Delays as high as 0.7 s were observed over Crater Flat and Yucca Mountain. The crustal model derived from this profile indicates that Paleozoic rocks, which outcrop to the east at Skull Mountain and the Calico Hills, and to the west at Bare Mountain, lie at a minimum depth of 3 km beneath part of Yucca Mountain. These results confirm earlier estimates based on the modeling of detailed gravity data. A mid-crustal boundary at 15 ? 2 km beneath Yucca Mountain is evidenced by a prominent reflection recorded beyond 43 km range at 1.5 s reduced time. Other mid-crustal boundaries have been identified at 24 and 30 km and the total crustal thickness is 35 km.

Flat bases of invariant polynomials and P-matrices of E{sub 7} and E{sub 8}

DOE Office of Scientific and Technical Information (OSTI.GOV)

Talamini, Vittorino

2010-02-15

Let G be a compact group of linear transformations of a Euclidean space V. The G-invariant C{sup {infinity}} functions can be expressed as C{sup {infinity}} functions of a finite basic set of G-invariant homogeneous polynomials, sometimes called an integrity basis. The mathematical description of the orbit space V/G depends on the integrity basis too: it is realized through polynomial equations and inequalities expressing rank and positive semidefiniteness conditions of the P-matrix, a real symmetric matrix determined by the integrity basis. The choice of the basic set of G-invariant homogeneous polynomials forming an integrity basis is not unique, so it ismore » not unique the mathematical description of the orbit space too. If G is an irreducible finite reflection group, Saito et al. [Commun. Algebra 8, 373 (1980)] characterized some special basic sets of G-invariant homogeneous polynomials that they called flat. They also found explicitly the flat basic sets of invariant homogeneous polynomials of all the irreducible finite reflection groups except of the two largest groups E{sub 7} and E{sub 8}. In this paper the flat basic sets of invariant homogeneous polynomials of E{sub 7} and E{sub 8} and the corresponding P-matrices are determined explicitly. Using the results here reported one is able to determine easily the P-matrices corresponding to any other integrity basis of E{sub 7} or E{sub 8}. From the P-matrices one may then write down the equations and inequalities defining the orbit spaces of E{sub 7} and E{sub 8} relatively to a flat basis or to any other integrity basis. The results here obtained may be employed concretely to study analytically the symmetry breaking in all theories where the symmetry group is one of the finite reflection groups E{sub 7} and E{sub 8} or one of the Lie groups E{sub 7} and E{sub 8} in their adjoint representations.« less

Self-dual monopoles and toda molecules

NASA Astrophysics Data System (ADS)

Ganoulis, N.; Goddard, P.; Olive, D.

1982-07-01

Stable static solutions to a gauge field theory with a Higgs field in the adjoint representation and with vanishing self-coupling are self-dual in the sense of Bogomolny. Leznov and Saveliev showed that a specific form of spherical symmetry reduces these equations to a modified form of the Toda molecule equations associated with the overall gauge symmetry G. Values of the constants of integration are found in terms of the distant Higgs field, guaranteeing regularity of the solution at the origin. The expressions hold for any simple Lie group G, depending on G via its root system.

2-tert-Butylamino-4-chloro-6-ethylamino-1,3,5-triazine: a structure with Z' = 4 containing two different molecular conformations and two independent chains of hydrogen-bonded R(2)2(8) rings.

PubMed

Quesada, Antonio; Fontecha, Maria A; López, Maria V; Low, John N; Glidewell, Christopher

2008-08-01

The title compound (trivial name terbutylazine), C(9)H(16)ClN(5), (I), crystallizes with Z' = 4 in the space group Pca2(1), and equal numbers of molecules adopt two different conformations for the ethylamine groups. The four independent molecules form two approximately enantiomorphic pairs. Eight independent N-H...N hydrogen bonds link the molecules into two independent chains of R(2)(2)(8) rings, in which the arrangement of the alkylamine substituents in the independent molecules precludes any further crystallographic symmetry. The significance of this study lies in its finding of two distinct molecular conformations within the structure and two distinct ways in which the molecules are organized into hydrogen-bonded chains, and in its comparison of the hydrogen-bonded structure of (I) with those of analogous 1,3,5-triazines and pyrimidines.

Binding configurations and intramolecular strain in single-molecule devices.

PubMed

Rascón-Ramos, Habid; Artés, Juan Manuel; Li, Yuanhui; Hihath, Joshua

2015-05-01

The development of molecular-scale electronic devices has made considerable progress over the past decade, and single-molecule transistors, diodes and wires have all been demonstrated. Despite this remarkable progress, the agreement between theoretically predicted conductance values and those measured experimentally remains limited. One of the primary reasons for these discrepancies lies in the difficulty to experimentally determine the contact geometry and binding configuration of a single-molecule junction. In this Article, we apply a small-amplitude, high-frequency, sinusoidal mechanical signal to a series of single-molecule devices during junction formation and breakdown. By measuring the current response at this frequency, it is possible to determine the most probable binding and contact configurations for the molecular junction at room temperature in solution, and to obtain information about how an applied strain is distributed within the molecular junction. These results provide insight into the complex configuration of single-molecule devices, and are in excellent agreement with previous predictions from theoretical models.

Geology and coal resources of the Hanging Woman Creek Study Area, Big Horn and Powder River Counties, Montana

USGS Publications Warehouse

Culbertson, William Craven; Hatch, Joseph R.; Affolter, Ronald H.

1978-01-01

In an area of 7,200 acres (29 sq km) In the Hanging Woman Creek study area, the Anderson coal bed contains potentially surface minable resources of 378 million short tons (343 million metric tons) of subbituminous C coal that ranges in thickness from 26 to 33 feet (7.9-10.1 m) at depths of less than 200 feet (60 m). Additional potentially surface minable resources of 55 million short tons (50 million metric tons) are contained in the 9-12 foot (2.7-3.7 m) thick Dietz coal bed which lies 50-100 feet (15-30 m) below the Anderson. Analyses of coal from 5 core holes indicates that the Anderson bed contains 0.4 percent sulfur, 5 percent ash, and has a heating value of 8,540 Btu/lb (4,750 Kcal/kg). The trace element content of the coal is generally similar to other coals in the Powder River Basin. The two coal beds are in the Fort Union Formation of Paleocene age which consists of sandstone, siltstone, shale, coal beds, and locally impure limestone. A northeast-trending normal fault through the middle of the area, downthrown on the southeast side, has displaced the generally flat lying strata as much as 300 feet (91 m). Most of the minable coal lies northwest of this fault.

Wave Transformation over a Fringing Coral Reef and the Importance of Low-Frequency Waves and Offshore Water Levels to Runup and Island Overtopping

NASA Astrophysics Data System (ADS)

Cheriton, O. M.; Storlazzi, C. D.; Rosenberger, K. J.

2016-02-01

Low-lying, reef-fringed islands are susceptible to sea-level rise and often subjected to overwash and flooding during large wave events. To quantify wave dynamics and wave-driven water levels on fringing coral reefs, wave gauges and a current meter were deployed for 5 months across two shore-normal transects on Roi-Namur, an atoll island in the Republic of the Marshall Islands. These observations captured two large wave events that had maximum wave heights greater than 6 m and peak periods of 16 s over the fore reef. The larger event coincided with a peak spring tide, leading to energetic, highly-skewed infragravity (0.04-0.004 Hz) and very low frequency (0.004-0.001 Hz) waves at the shoreline, which reached heights of 1.0 and 0.7 m, respectively. Water surface elevations, combined with wave runup, exceeded 3.7 m at the innermost reef flat adjacent to the toe of the beach, resulting in flooding of inland areas. This overwash occurred during a 3-hr time window that coincided with high tide and maximum low-frequency reef flat wave heights. The relatively low-relief characteristics of this narrow reef flat may further drive shoreline amplification of low-frequency waves due to resonance modes. These results demonstrate how the coupling of high offshore water levels with low-frequency reef flat wave energetics can lead to large impacts along atoll and fringing reef-lined shorelines, such as island overwash. These observations lend support to the hypothesis that predicted higher sea levels will lead to more frequent occurrences of both extreme shoreline runup and island overwash, threatening the sustainability of these islands.

Observations of wave transformation over a fringing coral reef and the importance of low-frequency waves and offshore water levels to runup, overwash, and coastal flooding

NASA Astrophysics Data System (ADS)

Cheriton, Olivia M.; Storlazzi, Curt D.; Rosenberger, Kurt J.

2016-05-01

Many low-lying tropical islands are susceptible to sea level rise and often subjected to overwash and flooding during large wave events. To quantify wave dynamics and wave-driven water levels on fringing coral reefs, a 5 month deployment of wave gauges and a current meter was conducted across two shore-normal transects on Roi-Namur Island in the Republic of the Marshall Islands. These observations captured two large wave events that had waves with maximum heights greater than 6 m with peak periods of 16 s over the fore reef. The larger event coincided with a peak spring tide, leading to energetic, highly skewed infragravity (0.04-0.004 Hz) and very low frequency (0.004-0.001 Hz) waves at the shoreline, which reached heights of 1.0 and 0.7 m, respectively. Water surface elevations, combined with wave runup, reached 3.7 m above the reef bed at the innermost reef flat adjacent to the toe of the beach, resulting in flooding of inland areas. This overwash occurred during a 3 h time window that coincided with high tide and maximum low-frequency reef flat wave heights. The relatively low-relief characteristics of this narrow reef flat may further drive shoreline amplification of low-frequency waves due to resonance modes. These results (1) demonstrate how the coupling of high offshore water levels with low-frequency reef flat wave energetics can lead to large impacts along fringing reef-lined shorelines, such as island overwash, and (2) lend support to the hypothesis that predicted higher sea levels will lead to more frequent occurrences of these extreme events, negatively impacting coastal resources and infrastructure.

Observations of wave transformation over a fringing coral reef and the importance of low-frequency waves and offshore water levels to runup, overwash, and coastal flooding

USGS Publications Warehouse

Cheriton, Olivia; Storlazzi, Curt; Rosenberger, Kurt

2016-01-01

Many low-lying tropical islands are susceptible to sea level rise and often subjected to overwash and flooding during large wave events. To quantify wave dynamics and wave-driven water levels on fringing coral reefs, a 5 month deployment of wave gauges and a current meter was conducted across two shore-normal transects on Roi-Namur Island in the Republic of the Marshall Islands. These observations captured two large wave events that had waves with maximum heights greater than 6 m with peak periods of 16 s over the fore reef. The larger event coincided with a peak spring tide, leading to energetic, highly skewed infragravity (0.04–0.004 Hz) and very low frequency (0.004–0.001 Hz) waves at the shoreline, which reached heights of 1.0 and 0.7 m, respectively. Water surface elevations, combined with wave runup, reached 3.7 m above the reef bed at the innermost reef flat adjacent to the toe of the beach, resulting in flooding of inland areas. This overwash occurred during a 3 h time window that coincided with high tide and maximum low-frequency reef flat wave heights. The relatively low-relief characteristics of this narrow reef flat may further drive shoreline amplification of low-frequency waves due to resonance modes. These results (1) demonstrate how the coupling of high offshore water levels with low-frequency reef flat wave energetics can lead to large impacts along fringing reef-lined shorelines, such as island overwash, and (2) lend support to the hypothesis that predicted higher sea levels will lead to more frequent occurrences of these extreme events, negatively impacting coastal resources and infrastructure.

Crossed Molecular Beam Studies and Dynamics of Decomposition of Chemically Activated Radicals

DOE R&D Accomplishments Database

Lee, Y. T.

1973-09-01

The power of the crossed molecular beams method in the investigation of the dynamics of chemical reactions lies mainly in the direct observation of the consequences of single collisions of well controlled reactant molecules. The primary experimental observations which provide information on reaction dynamics are the measurements of angular and velocity distributions of reaction products.

High-performance noncontact thermal diode via asymmetric nanostructures

NASA Astrophysics Data System (ADS)

Shen, Jiadong; Liu, Xianglei; He, Huan; Wu, Weitao; Liu, Baoan

2018-05-01

Electric diodes, though laying the foundation of modern electronics and information processing industries, suffer from ineffectiveness and even failure at high temperatures. Thermal diodes are promising alternatives to relieve above limitations, but usually possess low rectification ratios, and how to obtain a high-performance thermal rectification effect is still an open question. This paper proposes an efficient contactless thermal diode based on the near-field thermal radiation of asymmetric doped silicon nanostructures. The rectification ratio computed via exact scattering theories is demonstrated to be as high as 10 at a nanoscale gap distance and period, outperforming the counterpart flat-plate diode by more than one order of magnitude. This extraordinary performance mainly lies in the higher forward and lower reverse radiative heat flux within the low frequency band compared with the counterpart flat-plate diode, which is caused by a lower loss and smaller cut-off wavevector of nanostructures for the forward and reversed scheme, respectively. This work opens new routes to realize high performance thermal diodes, and may have wide applications in efficient thermal computing, thermal information processing, and thermal management.

Metal dependent motif transition in a self-assembled monolayer of bipyridine derivatives via coordination: An STM study.

PubMed

Wang, Yi; Yuan, Qunhui; Xu, Hongbo; Zhu, Xuefeng; Gan, Wei

2016-07-21

Low-dimensional molecular motifs with diversity developed via the on-surface chemistry are attracting growing interest for their potential in advanced nanofabrication. In this work, scanning tunneling microscopy was employed to investigate the in situ and ex situ metal coordinations between 4,4'-ditetradecyl-2,2'-bipyridine (bpy) and Zn(ii) or Cu(ii) ions at a highly oriented pyrolytic graphite (HOPG)/1-phenyloctane interface under ambient conditions. The results demonstrate that the bpy adopts a flat-lying orientation with its substituted alkyl chains in a tail-to-tail arrangement in a bpy monolayer. For the in situ coordination, the bpy/Zn(ii) and bpy/Cu(ii) complexes are aligned in edge-on fashions, wherein the bpy stands vertically on the HOPG surface and interdigitates at the alkyl chains. In the two-dimensional arrays of ex situ coordinated complexes, metal dependent motifs have been observed with Zn(ii) and Cu(ii), wherein the bipyridine moieties are parallel to the graphite surface. These results suggest that the desired on-surface coordination architectures may be achieved by the intentional selection of the metal centers.

Disparate Tectonic Settings of Devastating Earthquakes in Mexico, September 2017

NASA Astrophysics Data System (ADS)

Li, J.; Chen, W. P.; Ning, J.

2017-12-01

Large earthquakes associated with thrust faulting along the plate interface typically pose the highest seismic risk along subduction zones. However, both damaging earthquakes in Mexico of September 2017 are notable exceptions. The Tehuantepec event on the 8th (Mw 8.1) occurred just landward of the trench but is associated with normal faulting, akin to the large (Ms 8) historical event of 1931 that occurred about 200 km to the northwest along this subduction zone. The Puebla earthquake (on the 19th, Mw 7.1) occurred almost 300 km away from the trench where seismic imaging had indicated that the flat-lying slab steepens abruptly and plunges aseismically into the deep mantle. Here we show that both types of tectonic settings are in fact common along a large portion of the Mexican subduction zone, thus identifying source zones of potentially damaging earthquakes away from the plate interface. Additionally, modeling of broadband waveforms made clear that another significant event (Mw 6.1) on the 23rd, is associated with shallow normal faulting in the upper crust, not directly related to the two damaging earthquakes.

Fine-tuning with brane-localized flux in 6D supergravity

NASA Astrophysics Data System (ADS)

Niedermann, Florian; Schneider, Robert

2016-02-01

There are claims in the literature that the cosmological constant problem could be solved in a braneworld model with two large (micron-sized) supersymmetric extra dimensions. The mechanism relies on two basic ingredients: first, the cosmological constant only curves the compact bulk geometry into a rugby shape while the 4D curvature stays flat. Second, a brane-localized flux term is introduced in order to circumvent Weinberg's fine-tuning argument, which otherwise enters here through a backdoor via the flux quantization condition. In this paper, we show that the latter mechanism does not work in the way it was designed: the only localized flux coupling that guarantees a flat on-brane geometry is one which preserves the scale invariance of the bulk theory. Consequently, Weinberg's argument applies, making a fine-tuning necessary again. The only remaining window of opportunity lies within scale invariance breaking brane couplings, for which the tuning could be avoided. Whether the corresponding 4D curvature could be kept under control and in agreement with the observed value will be answered in our companion paper [1].

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sasakura, Naoki

The tensor model is discussed as theory of dynamical fuzzy spaces in order to formulate gravity on fuzzy spaces. The numerical analyses of the tensor models possessing Gaussian background solutions have shown that the low-lying long-wavelength fluctuations around the backgrounds are in remarkable agreement with the geometric fluctuations on flat spaces in the general relativity. It has also been shown that part of the orthogonal symmetry of the tensor model spontaneously broken by the backgrounds agrees with the local translation symmetry of the general relativity. Thus the tensor model provides an interesting model of simultaneous emergence of space, the generalmore » relativity, and its local translation symmetry.« less

Municipal waste processing apparatus

DOEpatents

Mayberry, John L.

1988-01-01

Municipal waste materials are processed by crushing the materials so that pieces of noncombustible material are smaller than a selected size and pieces of combustible material are larger than the selected size. The crushed materials are placed on a vibrating mesh screen conveyor belt having openings which pass the smaller, noncombustible pieces of material, but do not pass the larger, combustible pieces of material. Pieces of material which become lodged in the openings of the conveyor belt may be removed by cylindrical deraggers or pressurized air. The crushed materials may be fed onto the conveyor belt by a vibrating feed plate which shakes the materials so that they tend to lie flat.

Effect of gamma-ray irradiation on the surface states of MOS tunnel junctions

NASA Technical Reports Server (NTRS)

Ma, T. P.; Barker, R. C.

1974-01-01

Gamma-ray irradiation with doses up to 8 megarad produces no significant change on either the C(V) or the G(V) characteristics of MOS tunnel junctions with intermediate oxide thicknesses (40-60 A), whereas the expected flat-band shift toward negative electrode voltages occurs in control thick oxide capacitors. A simple tunneling model would explain the results if the radiation-generated hole traps are assumed to lie below the valence band of the silicon. The experiments also suggest that the observed radiation-generated interface states in conventional MOS devices are not due to the radiation damage of the silicon surface.

Rarefied flow past a flat plate at incidence

NASA Technical Reports Server (NTRS)

Dogra, Virendra K.; Moss, James N.; Price, Joseph M.

1988-01-01

Results of a numerical study using the direct simulation Monte Carlo (DSMC) method are presented for the transitional flow about a flat plate at 40 deg incidence. The plate has zero thickness and a length of 1.0 m. The flow conditions simulated are those experienced by the Shuttle Orbiter during reentry at 7.5 km/s. The range of freestream conditions are such that the freestream Knudsen number values are between 0.02 and 8.4, i.e., conditions that encompass most of the transitional flow regime. The DSMC simulations show that transitional effects are evident when compared with free molecule results for all cases considered. The calculated results demonstrate clearly the necessity of having a means of identifying the effects of transitional flow when making aerodynamic flight measurements as are currently being made with the Space Shuttle Orbiter vehicles. Previous flight data analyses have relied exclusively on adjustments in the gas-surface interaction models without accounting for the transitional effect which can be comparable in magnitude. The present calculations show that the transitional effect at 175 km would increase the Space Shuttle Orbiter lift-drag ratio by 90 percent over the free molecule value.

Quantifying wall turbulence via a symmetry approach: A Lie group theory

NASA Astrophysics Data System (ADS)

She, Zhen-Su; Chen, Xi; Hussain, Fazle

2017-11-01

We present a symmetry-based approach which yields analytic expressions for the mean velocity and kinetic energy profiles from a Lie-group analysis. After verifying the dilation-group invariance of the Reynolds averaged Navier-Stokes equation in the presence of a wall, we select a stress and energy length function as similarity variables which are assumed to have a simple dilation-invariant form. Three kinds of (local) invariant forms of the length functions are postulated, a combination of which yields a multi-layer formula giving its distribution in the entire flow region normal to the wall. The mean velocity profile is then predicted using the mean momentum equation, which yields, in particular, analytic expressions for the (universal) wall function and separate wake functions for pipe and channel - which are validated by data from direct numerical simulations (DNS). Future applications to a variety of wall flows such as flows around flat plate or airfoil, in a Rayleigh-Benard cell or Taylor-Couette system, etc., are discussed, for which the dilation group invariance is valid in the wall-normal direction.

Precise, Self-Limited Epitaxy of Ultrathin Organic Semiconductors and Heterojunctions Tailored by van der Waals Interactions.

PubMed

Wu, Bing; Zhao, Yinghe; Nan, Haiyan; Yang, Ziyi; Zhang, Yuhan; Zhao, Huijuan; He, Daowei; Jiang, Zonglin; Liu, Xiaolong; Li, Yun; Shi, Yi; Ni, Zhenhua; Wang, Jinlan; Xu, Jian-Bin; Wang, Xinran

2016-06-08

Precise assembly of semiconductor heterojunctions is the key to realize many optoelectronic devices. By exploiting the strong and tunable van der Waals (vdW) forces between graphene and organic small molecules, we demonstrate layer-by-layer epitaxy of ultrathin organic semiconductors and heterostructures with unprecedented precision with well-defined number of layers and self-limited characteristics. We further demonstrate organic p-n heterojunctions with molecularly flat interface, which exhibit excellent rectifying behavior and photovoltaic responses. The self-limited organic molecular beam epitaxy (SLOMBE) is generically applicable for many layered small-molecule semiconductors and may lead to advanced organic optoelectronic devices beyond bulk heterojunctions.

State-selective optimization of local excited electronic states in extended systems

NASA Astrophysics Data System (ADS)

Kovyrshin, Arseny; Neugebauer, Johannes

2010-11-01

Standard implementations of time-dependent density-functional theory (TDDFT) for the calculation of excitation energies give access to a number of the lowest-lying electronic excitations of a molecule under study. For extended systems, this can become cumbersome if a particular excited state is sought-after because many electronic transitions may be present. This often means that even for systems of moderate size, a multitude of excited states needs to be calculated to cover a certain energy range. Here, we present an algorithm for the selective determination of predefined excited electronic states in an extended system. A guess transition density in terms of orbital transitions has to be provided for the excitation that shall be optimized. The approach employs root-homing techniques together with iterative subspace diagonalization methods to optimize the electronic transition. We illustrate the advantages of this method for solvated molecules, core-excitations of metal complexes, and adsorbates at cluster surfaces. In particular, we study the local π →π∗ excitation of a pyridine molecule adsorbed at a silver cluster. It is shown that the method works very efficiently even for high-lying excited states. We demonstrate that the assumption of a single, well-defined local excitation is, in general, not justified for extended systems, which can lead to root-switching during optimization. In those cases, the method can give important information about the spectral distribution of the orbital transition employed as a guess.

The low-lying quartet electronic states of group 14 diatomic borides XB (X = C, Si, Ge, Sn, Pb)

NASA Astrophysics Data System (ADS)

Pontes, Marcelo A. P.; de Oliveira, Marcos H.; Fernandes, Gabriel F. S.; Da Motta Neto, Joaquim D.; Ferrão, Luiz F. A.; Machado, Francisco B. C.

2018-04-01

The present work focuses in the characterization of the low-lying quartet electronic and spin-orbit states of diatomic borides XB, in which X is an element of group 14 (C, Si, Ge, Sn, PB). The wavefunction was obtained at the CASSCF/MRCI level with a quintuple-ζ quality basis set. Scalar relativistic effects were also taken into account. A systematic and comparative analysis of the spectroscopic properties for the title molecular series was carried out, showing that the (1)4Π→X4Σ- transition band is expected to be measurable by emission spectroscopy to the GeB, SnB and PbB molecules, as already observed for the lighter CB and SiB species.

Asymmetric Grenada Basin and its Relation with Aves Ridge and Lesser Antilles Arc : Preliminary Results from Cruise GARANTI

NASA Astrophysics Data System (ADS)

Lallemand, S.; Lebrun, J. F.

2017-12-01

The Grenada Basin is a crescent-shape basin in a back-arc position relative to the Lesser Antilles arc. About 140 km wide, 3000 m deep and with a flat topography in its southern part, the basin shallows, narrows and becomes rougher northward. Its structural and genetic relations with the N-S-trending, ca.1000 m deep, Aves Ridge to the west, previously interpreted as the ante-Eocene remnant arc and the Lesser Antilles modern volcanic arc are debated. The GARANTI deep-seismic survey across the Grenada Basin (May-June 2017 French R/V L'Atalante), acquired two transverse (E-W) and one longitudinal (N-S), ca. 300 km long, wide-angle seismic lines shot using a 6473 in3 seismic source array, and recorded by 40 ocean bottom seismometers together with ca. 3500 km of 720-traces seismic reflection lines. This data set revealed a clear asymmetry along both N-S and E-W directions. To the North and to the West, the crust beneath the basin is rather thick and non-oceanic, whereas it is probably oceanic to the southeast. We pay special attention to structural relations between the basin itself and the Aves Ridge in one hand and the Antilles Arc in the other hand. The basin is filled by up to 7km of flat-lying sediments, thickening eastward and showing no apparent deformation. The Lesser Antilles arc margin is abrupt and does not appear to be the conjugate of the Aves Ridge margin. Fourteen dredges were collected, half of them were taken along the east flank of the Aves Ridge facing the deep Grenada basin. Evidences of past Cenozoic emersion of the Aves Ridge were found from drowned reef seamounts lying down to 1100 m bsl. Further analyses should better portrait the tectonic evolution of the Lesser Antilles back-arc area. GARANTI Scientific Team : A. Agranier, D. Arcay, F. Audemard, M.-A. Bassetti, M.-O. Beslier, M. Boucard, J.-J. Cornée, M. Fabre, A. Gay, D. Graindorge, A. Heuret, F. Klingelhoefer, M. Laigle, J.-L. Léticée, D. Malengros, B. Marcaillou, B. Mercier de Lépinay, P. Moréna, P. Münch, E. Oliot, D. Oregioni, C. Padron, M. Philippon, F. Quillévéré, G. Ratzov, L. Schenini, B. Yates, F. Zami

Crystal structure of bis-(N-methyl-N-phenyl-amino)-tris-ulfane.

PubMed

Barany, George; Henley, Matthew J; Polski, Lauren A; Schroll, Alayne L; Young, Victor G

2015-07-01

The title compound, C14H16N2S3, crystallized with two independent mol-ecules [(1 a ) and (1 b )] in the asymmetric unit. Both mol-ecules display a pseudo-trans conformation. The two consecutive S-S bond lengths of the tris-ulfane unit of mol-ecule (1 a ) are 2.06 (3) and 2.08 (3) Å, and 2.08 (3) and 2.07 (2) Å for mol-ecule (1 b ). Torsion angles about each of the two S-S bonds are 86.6 (2) and 87.0 (2)° for (1 a ), and -84.6 (2) and -85.9 (2)° for (1 b ). The core atoms, viz. the N-S-S-S-N moiety, of the two mol-ecules superimpose well if one is inverted on the other, but the phenyl groups do not. Thus, the two units are essentially conformational enanti-omers. In mol-ecule (1 a ), the two phenyl rings are inclined to one another by 86.7 (3)°, and in mol-ecule (1 b ), by 81.1 (3)°. In the crystal, mol-ecules are linked via C-H⋯π inter-actions, forming sheets lying parallel to (010).

Electron-impact excitation of gas-phase uracil

NASA Astrophysics Data System (ADS)

Chernyshova, I. V.; Kontros, J. E.; Markush, P. P.; Borovik, A. A.; Shpenik, O. B.

2012-11-01

The low lying excited states of uracil have been studied using electron energy-loss spectroscopy. In addition to the dipole allowed transitions to the singlet states, the two lowest triplet states are also observed. In the uracil molecule, the singlet electronic states have been found, being blue-shifted by about 0.5 eV as compared to the UV-absorption results.

New insights into the electrochemical desorption of alkanethiol SAMs on gold

PubMed Central

Pensa, Evangelina; Vericat, Carolina; Grumelli, Doris; Salvarezza, Roberto C.; Park, Sung Hyun; Longo, Gabriel S.; Szleifer, Igal

2012-01-01

A combination of Polarization Modulation Infrared Reflection Absorption Spectroscopy (PMIRRAS) under electrochemical control, Electrochemical Scanning Tunneling Microscopy (ECSTM) and Molecular Dynamics (MD) simulations has been used to shed light on the reductive desorption process of dodecanethiol (C12) and octadecanethiol (C18) SAMs on gold in aqueous electrolytes. Experimental PMIRRAS, ECSTM and MD simulations data for C12 desorption are consistent with formation of randomly distributed micellar aggregates stabilized by Na+ ions, coexisting with a lying-down phase of molecules. The analysis of pit and Au island coverage before and after desorption is consistent with the thiolate-Au adatoms models. On the other hand, PMIRRAS and MD data for C18 indicate that the desorbed alkanethiolates adopt a Na+ ion-stabilized bilayer of interdigitated alkanethiolates, with no evidence of lying down molecules. MD simulations also show that both the degree of order and tilt angle of the desorbed alkanethiolates change with the surface charge on the metal, going from bilayers to micelles. These results demonstrate the complexity of the alkanethiol desorption in the presence of water and the fact that chain length and counterions play a key role in a complex structure. PMID:22870508

1-(2,4-Di-nitro-phen-yl)-2-[(E)-(3,4,5-tri-meth-oxy-benzyl-idene)]hydrazine.

PubMed

Chantrapromma, Suchada; Ruanwas, Pumsak; Boonnak, Nawong; Chidan Kumar, C S; Fun, Hoong-Kun

2014-02-01

Mol-ecules of the title compound, C16H16N4O7, are not planar with a dihedral angle of 5.50 (11)° between the substituted benzene rings. The two meta-meth-oxy groups of the 3,4,5-tri-meth-oxy-benzene moiety lie in the plane of the attached ring [Cmeth-yl-O-C-C torsion angles -0.1 (4)° and -3.7 (3)°] while the para-meth-oxy substituent lies out of the plane [Cmeth-yl-O-C-C, -86.0 (3)°]. An intra-molecular N-H⋯O hydrogen bond involving the 2-nitro substituent generates an S(6) ring motif. In the crystal structure, mol-ecules are linked by weak C-H⋯O inter-actions into screw chains, that are arranged into a sheet parallel to the bc plane. These sheets are connected by π-π stacking inter-actions between the nitro and meth-oxy substituted aromatic rings with a centroid-centroid separation of 3.9420 (13) Å. C-H⋯π contacts further stabilize the two-dimensional network.

Ab initio calculations of the electronic structure of the low-lying states for the ultracold LiYb molecule

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tohme, Samir N.; Korek, Mahmoud, E-mail: mahmoud.korek@bau.edu.lb, E-mail: fkorek@yahoo.com; Awad, Ramadan

Ab initio techniques have been applied to investigate the electronic structure of the LiYb molecule. The potential energy curves have been computed in the Born–Oppenheimer approximation for the ground and 29 low-lying doublet and quartet excited electronic states. Complete active space self-consistent field, multi-reference configuration interaction, and Rayleigh Schrödinger perturbation theory to second order calculations have been utilized to investigate these states. The spectroscopic constants, ω{sub e}, R{sub e}, B{sub e}, …, and the static dipole moment, μ, have been investigated by using the two different techniques of calculation with five different types of basis. The eigenvalues, E{sub v}, themore » rotational constant, B{sub v}, the centrifugal distortion constant, D{sub v}, and the abscissas of the turning points, R{sub min} and R{sub max}, have been calculated by using the canonical functions approach. The comparison between the values of the present work, calculated by different techniques, and those available in the literature for several electronic states shows a very good agreement. Twenty-one new electronic states have been studied here for the first time.« less

Gas-phase lifetimes of nucleobase analogues by picosecond pumpionization and streak techniques.

PubMed

Blaser, Susan; Frey, Hans-Martin; Heid, Cornelia G; Leutwyler, Samuel

2014-01-01

The picosecond (ps) timescale is relevant for the investigation of many molecular dynamical processes such as fluorescence, nonradiative relaxation, intramolecular vibrational relaxation, molecular rotation and intermolecular energy transfer, to name a few. While investigations of ultrafast (femtosecond) processes of biological molecules, e.g. nucleobases and their analogues in the gas phase are available, there are few investigations on the ps time scale. We have constructed a ps pump-ionization setup and a ps streak camera fluorescence apparatus for the determination of lifetimes of supersonic jet-cooled and isolated molecules and clusters. The ps pump-ionization setup was used to determine the lifetimes of the nucleobase analogue 2-aminopurine (2AP) and of two 2AP˙(H2O)n water cluster isomers with n=1 and 2. Their lifetimes lie between 150 ps and 3 ns and are strongly cluster-size dependent. The ps streak camera setup was used to determine accurate fluorescence lifetimes of the uracil analogue 2-pyridone (2PY), its self-dimer (2PY)2, two isomers of its trimer (2PY)3 and its tetramer (2PY)4, which lie in the 7-12 ns range.

Understanding the electronic structure of CdSe quantum dot-fullerene (C{sub 60}) hybrid nanostructure for photovoltaic applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sarkar, Sunandan; Rajbanshi, Biplab; Sarkar, Pranab, E-mail: pranab.sarkar@visva-bharati.ac.in

2014-09-21

By using the density-functional tight binding method, we studied the electronic structure of CdSe quantum dot(QD)-buckminsterfullerene (C{sub 60}) hybrid systems as a function of both the size of the QD and concentration of the fullerene molecule. Our calculation reveals that the lowest unoccupied molecular orbital energy level of the hybrid CdSeQD-C{sub 60} systems lies on the fullerene moiety, whereas the highest occupied molecular orbital (HOMO) energy level lies either on the QD or the fullerene depending on size of the CdSe QD. We explored the possibility of engineering the energy level alignment by varying the size of the CdSe QD.more » With increase in size of the QD, the HOMO level is shifted upward and crosses the HOMO level of the C{sub 60}-thiol molecule resulting transition from the type-I to type-II band energy alignment. The density of states and charge density plot support these types of band gap engineering of the CdSe-C{sub 60} hybrid systems. This type II band alignment indicates the possibility of application of this nanohybrid for photovoltaic purpose.« less

Single-order laser high harmonics in XUV for ultrafast photoelectron spectroscopy of molecular wavepacket dynamics.

PubMed

Fushitani, Mizuho; Hishikawa, Akiyoshi

2016-11-01

We present applications of extreme ultraviolet (XUV) single-order laser harmonics to gas-phase ultrafast photoelectron spectroscopy. Ultrashort XUV pulses at 80 nm are obtained as the 5th order harmonics of the fundamental laser at 400 nm by using Xe or Kr as the nonlinear medium and separated from other harmonic orders by using an indium foil. The single-order laser harmonics is applied for real-time probing of vibrational wavepacket dynamics of I 2 molecules in the bound and dissociating low-lying electronic states and electronic-vibrational wavepacket dynamics of highly excited Rydberg N 2 molecules.

Potential energy surfaces of the low-lying electronic states of the Li + LiCs system

NASA Astrophysics Data System (ADS)

Jasik, P.; Kilich, T.; Kozicki, J.; Sienkiewicz, J. E.

2018-03-01

Ab initio quantum chemistry calculations are performed for the mixed alkali triatomic system. Global minima of the ground and first excited doublet states of the trimer are found and Born-Oppenheimer potential energy surfaces of the Li atom interacting with the LiCs molecule were calculated for these states. The lithium atom is placed at various distances and bond angles from the lithium-caesium dimer. Three-body nonadditive forces of the Li2Cs molecule in the global minimum are investigated. Dimer-atom interactions are found to be strongly attractive and may be important in the experiments, particularly involving cold alkali polar dimers.

Selectivity of Glycine for Facets on Gold Nanoparticles.

PubMed

Shao, Qing; Hall, Carol K

2018-04-05

The performance of nanoparticles in medical applications depends on their interactions with various molecules. Despite extensive research on this subject, it remains unclear where on an inhomogeneous nanoparticle molecules prefer to adsorb. Here we investigate the selectivity of glycine molecules for facets on five bare gold nanoparticles with diameters from 1.0 to 5.0 nm. Well-tempered metadynamics simulations are conducted to calculate the adsorption free-energy landscapes of a glycine molecule on various locations for the five gold nanoparticles in explicit water. We also calculate the glycine molecule's adsorption free energies on the five gold nanoparticles in vacuum and on three flat gold surfaces as a reference. The simulation results show that glycine molecules prefer to adsorb on the (110) facet for the 1.0 and 2.0 nm nanoparticles, the edges for the 3.0 nm nanoparticle, and the (111) facet for the 4.0 and 5.0 nm nanoparticles in water. The effect of water solvent on the selectivity is investigated through comparing the adsorption free-energy landscapes for glycine molecules on the nanoparticles in water and in vacuum. The area of the facet plays a key role in determining the selectivity of glycine molecules for the different facets, especially the shift of the selectivity as the nanoparticle diameter changes. Our simulations suggest that nanoparticle size and shape can be engineered to control the preferred adsorption location of molecules.

Challenge of urban sewage disposal in a karst region: Mérida, Yucátan, Mexico

NASA Astrophysics Data System (ADS)

Perry, E. C.; Villasuso, M.

2013-05-01

Four hydrogeologic factors influence urban sewage management on the northern Yucátan (Mexico) Peninsula: 1) lack of rivers capable of transporting and/or oxidizing sewage, 2) near-surface flat-lying, porous, permeable limestone and dolomite with shallow layers of variable permeability but without major subsurface aquitards, 3) rapid groundwater transmission, penetration of seawater inland beneath a fresh water lens, and a flat water table only a few meters below land surface and controlled by sea level, 4) near absence of soil cover. Mérida, Yucátan (population approaching one million, approximately the world's 450th most populous city) has no central sewage system. The water table beneath the city is consistently only 7-9 m below land surface, and the 40 m-thick fresh water lens, which is the sole source of municipal, industrial, and agricultural water, directly overlies a marine intrusion of modified seawater composition. The old city has an estimated 130,000 drains feeding untreated household waste directly into the permeable karst aquifer. Numerous storm drains send street runoff directly to the aquifer. In addition, industries, hotels, and some subdivisions have unmonitored injection wells that pump untreated wastewater into the underlying saline intrusion. Some injection wells have flow problems possibly because of low aquifer permeability within the saline intrusion. Deep injection is also problematic because density contrast with saline intrusion water can produce a gravity imbalance, and high sulfate water can react with organic waste to produce H2S. Some city water supply wells are reportedly affected by inflation of the water table beneath the city, by local upconing of saline water, and by nitrate contamination. Paradoxically, Mérida with an abundant, easily contaminated source of fresh water, lacks streams to transport sewage off-site, and thus shares some water supply/sewage treatment problems with cities in arid regions. Recently, compact, efficient systems that provide almost tertiary-level sewage treatment have been developed and installed in various localities worldwide. Fitting the old parts of Mérida with several such systems would be less disruptive than blasting a monolithic sewer network through the city's rocky base, and it would minimize the problem of pumping sewage in an almost completely flat-lying area. Appropriate reuse of water from such local treatment facilities would be more flexible than from a single central system. Furthermore, injecting water into the aquifer after secondary or tertiary treatment would be a huge improvement over pumping of untreated "aguas negras" into the saline intrusion. Finally, there is a renaissance of sorts in sewage treatment technology, and it would be much easier to upgrade a number of individual systems as they became obsolete than to replace a monolithic central system. Safe, effective operation and monitoring of the suggested of sewage system would be challenging. Yet, as more cities join those 500 world-wide that now have populations approaching or exceeding one million, use of streams to export pollution may become infeasible. Perhaps Mérida can become a model to demonstrate that people can safely process and reuse their own wastewater.

Molecular Dynamics Simulation Studies of Caffeine Aggregation in Aqueous Solution

PubMed Central

Tavagnacco, Letizia; Schnupf, Udo; Mason, Philip E.; Saboungi, Marie-Louise; Cesàro, Attilio; Brady, John W.

2011-01-01

Molecular dynamics simulations were carried out on a system of eight independent caffeine molecules in a periodic box of water at 300 K, representing a solution near the solubility limit for caffeine at room temperature, using a newly-developed CHARMM-type force field for caffeine in water. Simulations were also conducted for single caffeine molecules in water using two different water models (TIP3P and TIP4P). Water was found to structure in a complex fashion around the planar caffeine molecules, which was not sensitive to the water model used. As expected, extensive aggregation of the caffeine molecules was observed, with the molecules stacking their flat faces against one another like coins, with their methylene groups staggered to avoid steric clashes. A dynamic equilibrum was observed between large n-mers, including stacks with all eight solute molecules, and smaller clusters, with the calculated osmotic coefficient being in acceptable agreement with the experimental value. The insensitivity of the results to water model and the congruence with experimental thermodynamic data suggest that the observed stacking interactions are a realistic representation of the actual association mechanism in aqueous caffeine solutions. PMID:21812485

Effects of nanorod structure and conformation of fatty acid self-assembled layers on superhydrophobicity of zinc oxide surface.

PubMed

Badre, Chantal; Dubot, P; Lincot, Daniel; Pauporte, Thierry; Turmine, Mireille

2007-12-15

Superhydrophobic surfaces have been prepared from nanostructured zinc oxide layers by a treatment with fatty acid molecules. The layers are electrochemically deposited from an oxygenated aqueous zinc chloride solution. The effects of the layer's structure, from a dense film to that of a nanorod array, as well as that of the properties of the fatty acid molecules based on C18 chains are described. A contact angle (CA) as high as 167 degrees is obtained with the nanorod structure and the linear saturated molecule (stearic acid). Lower values are found with molecules having an unsaturated bond on C9, in particular with a cis conformation (140 degrees ). These results, supplemented by infrared spectroscopy, indicate an enhancement of the sensitivity to the properties of the fatty acid molecules (conformation, flexibility, saturated or not) when moving from the flat surface to the nanostructured surface. This is attributed to a specific influence of the structure of the tops of the rods and lateral wall properties on the adsorption and organization of the molecules. CA measurements show a very good stability of the surface in time if stored in an environment protected from UV radiations.

Magnetic field dependent electronic transport of Mn4 single-molecule magnet.

NASA Astrophysics Data System (ADS)

Haque, F.; Langhirt, M.; Henderson, J. J.; Del Barco, E.; Taguchi, T.; Christou, G.

2010-03-01

We have performed single-electron transport measurements on a Mn4 single-molecule magnet (SMM) in where amino groups were added to electrically protect the magnetic core and to increase the stability of the molecule when deposited on the single-electron transistor (SET) chip. A three-terminal SET with nano-gap electro-migrated gold electrodes and a naturally oxidized Aluminum back gate. Experiments were conducted at temperatures down to 230mK in the presence of high magnetic fields generated by a superconducting vector magnet. Mn4 molecules were deposited from solution to form a mono-layer. The optimum deposition time was determined by AFM analysis on atomically flat gold surfaces. We have observed Coulomb blockade an electronic excitations that curve with the magnetic field and present zero-field splitting, which represents evidence of magnetic anisotropy. Level anticrossings and large excitations slopes are associated with the behavior of molecular states with high spin values (S ˜ 9), as expected from Mn4.

SPM for functional identification of individual biomolecules

NASA Astrophysics Data System (ADS)

Ros, Robert; Schwesinger, Falk; Padeste, Celestino; Plueckthun, Andreas; Anselmetti, Dario; Guentherodt, Hans-Joachim; Tiefenauer, Louis

1999-06-01

The identification of specific binding molecules is of increasing interest in the context of drug development based on combinatorial libraries. Scanning Probe Microscopy (SPM) is the method of choice to image and probe individual biomolecules on a surface. Functional identification of biomolecules is a first step towards screening on a single molecule level. As a model system we use recombinant single- chain Fv fragment (scFv) antibody molecules directed against the antigen fluorescein. The scFv's are covalently immobilized on a flat gold surface via the C-terminal cysteine, resulting in a high accessibility of the binding site. The antigen is immobilized covalently via a long hydrophilic spacer to the silicon nitride SPM-tip. This arrangement allows a direct measurement of binding forces. Thus, closely related antibody molecules differing in only one amino acid at their binding site could be distinguished. A novel SPM-software has been developed which combines imaging, force spectroscopic modes, and online analysis. This is a major prerequisite for future screening methods.

High-Performance Simulations of the Diffusion Characteristics of a Pentacene Derivative on Gold Surfaces

NASA Astrophysics Data System (ADS)

Miller, Ryan; Larson, Amanda; Pohl, Karsten

Pentacene serves as a backbone for several molecules that provide attractive qualities for organic photovoltaic devices. One of these pentacene derivatives is 5 6,7-trithiapentacene-13-one (TTPO), which is unique in that it achieves its lowest energy configuration on Au(1 1 1) surfaces with the thiol group angled down towards the surface, allowing many molecules to pack closely together and form molecular nanowires. However, TTPO diffuses on flat surfaces, making it difficult for the self-assembly process to be initiated. With the help of the low-energy sites in surface defects and Au(7 8 8) step edges, TTPO molecules can be anchored in place on surfaces, allowing for chain formation to begin. By using high-performance Density Functional Theory based molecular dynamics calculations, the molecules can be shown to stay localized to these bonding sites and serve as a basis for chain formation. In addition, by simulating various temperatures with a Nose-Hoover thermostat, we can analyze how temperature affects anchoring ability and diffusion properties.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Igor V. Litvinyuk, and Itzik Ben-Itzhak

Our principal goal was the experimental demonstration of Laser-Induced Electron Diffraction (LIED). Key steps along the development of this experimental technique have been accomplished and reported in the publications listed in this brief report. We started with measuring 3D electron momenta spectra in aligned nitrogen and oxygen molecules. Chakra Maharjan (Ph.D. student of Lew Cocke) was a lead researcher on this project. Although Chakra succeeded in obtaining those spectra, we were scooped by the publication of identical results in Science by the NRC Ottawa group. Our results were never published as a refereed article, but became a part of Chakra'smore » Ph.D. dissertation. That Science paper was the first experimental demonstration of Laser-Induced Electron Diffraction (LIED). Chakra also worked on wavelength dependence of 3D ATI spectra of atoms and molecules using tunable OPA pulses. Another Ph.D. student, Maia Magrakvelidze (her GRA was funded by the grant), started working on COLTRIMS experiments using OPA pulses (1800 nm wavelength). After some initial experiments it became apparent that COLTRIMS did not yield sufficient count rates of electrons in the high-energy part of the spectrum to see diffraction signatures with acceptable statistics (unfavorable scaling of the electron yield with laser wavelength was partly to blame). Nevertheless, Maia managed to use COLTRIMS and OPA to measure the angular dependence of the tunneling ionization rate in D{sub 2} molecules. Following the initial trial experiments, the decision was made to switch from COLTRIMS to VMI in order to increase the count rates by a factor of {approx}100, which may have given us a chance to see LIED. Research Associate Dr. Sankar De (his salary was funded by the grant), in collaboration with Matthias Kling's group (then at MPQ Garching), proceeded to design a special multi-electrode VMI spectrometer for capturing high-energy ATI electrons and to install it in place of COLTRIMS inside our experimental chamber. That apparatus was later used for the first demonstration of field-free orientation in CO using two-color laser pulses as well as for a series of other experiments, such as pump-probe studies of molecular dynamics with few-cycle laser pulses, control of electron localization in dissociating hydrogen molecules using two-color laser pulses, and ATI spectra of Xe ionized by two-color laser pulses. In parallel, Dipanwita Ray (Ph.D. student of Lew Cocke) worked on measuring angle-resolved ATI spectra of noble gases using a stereo-ATI phasemeter as a TOF electron spectrometer. She observed the angular diffraction structures in 3D ATI spectra of Ar, Kr and Xe, which were interpreted in terms of the Quantitative Rescattering theory newly developed by C.D. Lin. We also attempted to use a much more powerful OPA (five times more energy per pulse than the one we had at JRML) available at the Advanced Laser Light Source (ALLS) in Montreal to observe LIED. Two visits to ALLS by the PI, Igor Litvinyuk, and one visit by the PI's Ph.D. student (Irina Bocharova) were funded by the grant. Though we failed to observe LIED (the repetition rate of the ALLS OPA was too low at only 100 Hz), this international collaboration resulted in several publications on other related subjects, such as the wavelength dependence of laser Coulomb explosion of hydrogen, the wavelength dependence of non-sequential double ionization of neon and argon, the demonstration of charge-resonance enhanced ionization in CO{sub 2}, and the study of non-elastic scattering processes in H{sub 2}. Theoretical efforts to account for the hydrogen Coulomb explosion experiment resulted in another paper by Maia Magrakvelidze as lead author. Although for various reasons we failed to achieve our main goal of observing LIED, we salute the recent success in this endeavor by Lou DiMauro's group (with theoretical support from our KSU colleague C.D. Lin) published in Nature, which validates our approach.« less

Optical Spectroscopy of Nano Materials and Structures

NASA Astrophysics Data System (ADS)

Guo, Wenhao

In this thesis, nanostructures and nanomaterials ranging from 3D to OD will be studied compresively, by using optical methods. Firstly, for 3D and 2D nanomaterials, nanoporous zeolite crystals, such as AFI and AEL are introduced as host materials to accommodate diatomic iodine molecules. Polarized Raman spectroscopy is utilized to identify the two configurations of iodine molecules to stay in the channels of AEL: the lying mode (the bond of the two atoms is parallel to the direction of the channels) and the standing mode (the bond is perpendicular to the direction of the channels). The lying mode and standing mode are switchable and can be well controlled by the amount of water molecules inside the crystal, revealed by both molecule dynamics simulation and experiment observation. With more water molecules inside, iodine molecules choose to stay in the standing mode, while with less water molecules, iodine molecules prefer to lie along the channel. Therefore, the configurations of molecules could be precisely controlled, globally by the surrounding pressure and temperature, and locally by the laser light. Ii is believed that this easy and reversible control of single molecule will be valuable in nanostructured devices, such as molecular sieving or molecular detection. Secondly, for 1D case, the PL spectrum of ZnO nanowire under uniaxial strain is studied. When a ZnO nanowire is bent, besides the lattice constant induced bandgap change on the tensile and compressive sides, there is a piezoelectric field generated along the cross section. This piezoelectric potential, together with the bandgap changes induced by the deformation, will redistribute the electrons excited by incident photons from valence band to conduction band. As a result, the electrons occupying the states at the tensile side will largely outnumbered the ones at the compressive side. Therefore, the PL spectrum we collected at the whole cross section will manifest a redshift, other than the peak broadening which is caused by the bandgap change. The experimental results confirm our speculation. When we make the nanowire straight again, the redshift disappears. It is believed that this piezoelectric effect is very important to the application of nanowires, and it would benefit the actual design and fabrication for the electronic devices for the next generation. Lastly, as for the OD case, the charge transfer mechanism occurring at the interface between graphene and ZnO QDs is investigated. We fabricate a hybrid structure by placing ZnO QDs on top of graphene. With UV light illumination on this device, it will generate electron-hole pairs inside QDs. Before they recombine, the holes will be separated and trapped into the surface states, and discharge the oxygen ions adsorbed on the surface of QDs. The unpaired electrons are then transferred to the graphene layer with a relative long lifetime. After the UV light is switched off, the oxygen molecules will re-adsorb to the QDs surface, capture electrons and recover the graphene's transport properties. Therefore, this hybrid device shows an ultrasensitive response to on-off of the UV laser, with a photoconductive gain as high as 10 7, which can be utilized for practical graphene-based UV sensors and detectors with very high responsivity. This gain can be further enhanced by another 2-3 orders by increasing source-drain voltage, shortening the sample's length, etc. It is believed that optical spectroscopy provides a convenient, efficient and useful method to study the nanomaterials and nanostructures. It is easy to set up, has no harm or degradation to the sample, and could go beyond the diffraction limit. With appropriate design and creative ideas, optical spectroscopy can be further explored, and will boost the development of nanoscience and technology. (Abstract shortened by UMI.).

Electrostatic Repulsion-Induced Desorption of Dendritic Viologen-Arranged Molecules Anchored on a Gold Surface through a Gold-Thiolate Bond Leading to a Tunable Molecular Template.

PubMed

Kawauchi, Takehiro; Kojima, Takahiro; Sakaguchi, Hiroshi; Iyoda, Tomokazu

2018-06-05

We investigated the adsorption and desorption behavior of self-assembled monolayers (SAMs) on gold derived from dendritic viologen-arranged molecules with an ω-mercaptodecyl group (A n, n (dendritic generation) = 0-3) at the apex of the dendritic structure in polar solvents. The adsorption of the dendritic molecules occurred quickly and saturated within a few minutes in an acetonitrile/ethanol (1/1, v/v) mixture at a concentration of 2 mM. Atomic force microscopy images of the SAMs showed flat surfaces regardless of the dendritic generation because the peripheral viologen units were closely packed at the surface of the molecular layer. Individual A3 molecules immobilized on the substrate were observed by scanning tunneling microscopy measurements of a mixed SAM with decanethiol. The desorption behaviors of dendritic molecules from the A n-SAMs in several solvents such as water were also investigated. The spontaneous desorption of the A n-SAM occurred more rapidly than that of a conventional n-alkanethiol SAM. However, the desorption was inhibited by adding electrolytes such as NaNO 3 due to the shielding effect on the electrostatic repulsion between the dendritic molecules. These results indicate that the surface density of the dendritic molecules can be controlled through the desorption.

Benzamide-picric acid (1/1).

PubMed

Sivaramkumar, M S; Velmurugan, R; Sekar, M; Ramesh, P; Ponnuswamy, M N

2010-06-26

In the title compound, C(7)H(7)NO·C(6)H(3)N(3)O(7), one of the nitro groups of the picric acid mol-ecule lies in the plane of the attached benzene ring [dihedral angle = 1.4 (1)°] while the other two are twisted away by 9.9 (1) and 30.3 (1)°. In the benzamide mol-ecule, the amide group is almost coplanar with the benzene ring [dihedral angle = 4.4 (1)°]. An intra-molecular O-H⋯O hydrogen bond generates an S6 ring motif. In the crystal, mol-ecules are linked into a ribbon-like structure along the b axis by O-H⋯O and N-H⋯O inter-molecular hydrogen bonds. In addition, C-H⋯O hydrogen bonds and short O⋯O contacts [2.828 (2) Å] are observed.

Selectivity in the inelastic rotational scattering of D2 and HD molecules from graphite: Similarities and differences respect to the H2 case

NASA Astrophysics Data System (ADS)

Rutigliano, Maria; Pirani, Fernando

2018-03-01

The inelastic scattering of D2 and HD molecules impinging on a graphite surface in well-defined initial roto-vibrational states has been studied by using the computational setup recently developed to characterize important selectivities in the molecular dynamics occurring at the gas-surface interface. In order to make an immediate comparison of determined elastic and inelastic scattering probabilities, we considered for D2 and HD molecules the same initial states, as well as the same collision energy range, previously selected for the investigation of H2 behaviour. The analysis of the back-scattered molecules shows that, while low-lying initial vibrational states are preserved, the medium-high initial ones give rise to final states covering the complete ladder of vibrational levels, although with different probability for the various cases investigated. Moreover, propensities in the formation of the final rotational states are found to depend strongly on the initial ones, on the collision energy, and on the isotopologue species.

Water supply for the Nuclear Rocket Development Station at the U.S. Atomic Energy Commission's Nevada Test Site

USGS Publications Warehouse

Young, Richard Arden

1972-01-01

The Nuclear Rocket Development Station, in Jackass Flats, occupies about 123 square miles in the southwestern part of the U.S. Atomic Energy Commission's Nevada Test Site. Jackass Flats, an intermontane valley bordered by highlands on all sides except for a drainage outlet in the southwestern corner, has an average annual rainfall of 4 inches. Jackass Flats is underlain by alluvium, colluvium, and volcanic rocks of Cenozoic age and, at greater depth, by sedimentary rocks of Paleozoic age. The alluvium and the colluvium lie above the saturated zone throughout nearly all of Jackass Flats. The Paleozoic sedimentary rocks contain limestone and dolomite units that are excellent water producers elsewhere ; however, these units are too deep in Jackass Flats to be economic sources of water. The only important water-producing unit known in the vicinity of the Nuclear Rocket Development Station is a welded-tuff aquifer, the Topopah Spring Member of the Paintbrush Tuff, which receives no significant recharge. This member contains about 500 feet of highly fractured rock underlying an area 11 miles long and 3 miles wide in western Jackass Flats. Permeability of the aquifer is derived mostly from joints and fractures; however, some permeability may be derived from gas bubbles in the upper part of the unit. Transmissivity, obtained from pumping tests, ranges from 68,000 to 488,000 gallons per day per foot. Volume of the saturated part of the aquifer is about 3.5 cubic miles, and the average specific yield probably ranges from 1 to 5 percent. The volume of ground water in storage is probably within the range of 37-187 billion gallons. This large amount of water should be sufficient to supply the needs of the Nuclear Rocket Development Station for many years. Water at the Nuclear Rocket Development Station is used for public supply, construction, test-cell coolant, exhaust cooling, and thermal shielding during nuclear reactor and engine testing, and washdown. Present (1967) average consumption of water is 520,000 gallons per day--all supplied by one well. This supply well and a standby well have a production capability of 1.6 million gallons per day--adequate for present needs. Water in the welded-tuff aquifer is of the sodium bicarbonate type. Dissolved-solids content of the water in Jackass Flats is in the general range 230 milligrams per liter in the western part to 890 milligrams per liter in the eastern part.

KSC-00dig065

NASA Image and Video Library

2000-10-31

The cracked cleat on the crawler-transporter track that stalled the rollout of Space Shuttle Endeavour lies on the ground near Launch Pad 39B. The cracked cleat forced the reverse of the rollout back outside the pad gate so the cleat could be repaired on flat ground before moving up the incline to the top of the pad. Endeavour is scheduled to be launched Nov. 30 at 10:01 p.m. EST on mission STS-97, the sixth construction flight to the International Space Station. Its payload includes the P6 Integrated Truss Structure and a photovoltaic (PV) module, with giant solar arrays that will provide power to the Station. The mission includes two spacewalks to complete the solar array connections

On new scaling group of transformation for Prandtl-Eyring fluid model with both heat and mass transfer

NASA Astrophysics Data System (ADS)

Rehman, Khalil Ur; Malik, Aneeqa Ashfaq; Malik, M. Y.; Tahir, M.; Zehra, Iffat

2018-03-01

A short communication is structured to offer a set of scaling group of transformation for Prandtl-Eyring fluid flow yields by stretching flat porous surface. The fluid flow regime is carried with both heat and mass transfer characteristics. To seek solution of flow problem a set of scaling group of transformation is proposed by adopting Lie approach. These transformations are used to step down the partial differential equations into ordinary differential equations. The reduced system is solved by numerical method termed as shooting method. A self-coded algorithm is executed in this regard. The obtain results are elaborated by means of figures and tables.

Localization in abelian Chern-Simons theory

NASA Astrophysics Data System (ADS)

McLellan, B. D. K.

2013-02-01

Chern-Simons theory on a closed contact three-manifold is studied when the Lie group for gauge transformations is compact, connected, and abelian. The abelian Chern-Simons partition function is derived using the Faddeev-Popov gauge fixing method. The partition function is then formally computed using the technique of non-abelian localization. This study leads to a natural identification of the abelian Reidemeister-Ray-Singer torsion as a specific multiple of the natural unit symplectic volume form on the moduli space of flat abelian connections for the class of Sasakian three-manifolds. The torsion part of the abelian Chern-Simons partition function is computed explicitly in terms of Seifert data for a given Sasakian three-manifold.

Recrystallization of tubules from natural lotus (Nelumbo nucifera) wax on a Au(111) surface

PubMed Central

Wandelt, Klaus

2011-01-01

Summary We present here the first results on the self-assembly of tubules of natural wax from lotus leaves on a single crystal Au(111) surface. A comparison of the tubule growth on Au(111) to that on HOPG is discussed. Although the tubule formation on both Au(111) and HOPG takes place on an intermediate wax film which should mask the substrate properties, the tubule orientations differ. In contrast to a vertical tubule orientation on HOPG, the tubules lie flat on Au(111). Taking into account the physical properties of HOPG and Au(111), we put forward a hypothesis which can explain the different tubule orientations on both substrates. PMID:21977438

Topography of the northern hemisphere of Mars from the Mars Orbiter Laser Altimeter

NASA Technical Reports Server (NTRS)

Smith, D. E.; Zuber, M. T.; Frey, H. V.; Garvin, J. B.; Head, J. W.; Muhleman, D. O.; Pettengill, G. H.; Phillips, R. J.; Solomon, S. C.; Zwally, H. J.;

Municipal waste processing apparatus

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mayberry, J L

1987-01-15

Municipal waste materials are processed by crushing the materials so that pieces of noncombustible material are smaller than a selected size and pieces of combustible material are larger than the selected size. The crushed materials are placed on a vibrating mesh screen conveyor belt having openings which pass the smaller, noncombustible pieces of material, but do not pass the larger, combustible pieces of material. Pieces of material which become lodged in the openings of the conveyor belt may be removed by cylindrical deraggers or pressurized air. The crushed materials may be fed onto the conveyor belt by a vibrating feedmore » plate which shakes the materials so that they tend to lie flat.« less

The Spectrum of VY Canis Majoris in 2000 February

NASA Astrophysics Data System (ADS)

Wallerstein, George; Gonzalez, Guillermo

2001-08-01

We present the current (2000 February) status of the optical spectrum of the irregularly variable M supergiant VY CMa, based on high-resolution CCD spectra. The emission spectrum is largely unchanged over the past 43 yr, with low-lying atomic lines as well as the molecules TiO and ScO in emission. Tables of observed wavelengths for both identified and unidentified lines are presented.

A modified dynamical model of drying process of polymer blend solution coated on a flat substrate

NASA Astrophysics Data System (ADS)

Kagami, Hiroyuki

2008-05-01

We have proposed and modified a model of drying process of polymer solution coated on a flat substrate for flat polymer film fabrication. And for example numerical simulation of the model reproduces a typical thickness profile of the polymer film formed after drying. Then we have clarified dependence of distribution of polymer molecules on a flat substrate on a various parameters based on analysis of numerical simulations. Then we drove nonlinear equations of drying process from the dynamical model and the fruits were reported. The subject of above studies was limited to solution having one kind of solute though the model could essentially deal with solution having some kinds of solutes. But nowadays discussion of drying process of a solution having some kinds of solutes is needed because drying process of solution having some kinds of solutes appears in many industrial scenes. Polymer blend solution is one instance. And typical resist consists of a few kinds of polymers. Then we introduced a dynamical model of drying process of polymer blend solution coated on a flat substrate and results of numerical simulations of the dynamical model. But above model was the simplest one. In this study, we modify above dynamical model of drying process of polymer blend solution adding effects that some parameters change with time as functions of some variables to it. Then we consider essence of drying process of polymer blend solution through comparison between results of numerical simulations of the modified model and those of the former model.

Observing Organic Molecules in Interstellar Gases: Non Equilibrium Excitation.

NASA Astrophysics Data System (ADS)

Wiesenfeld, Laurent; Faure, Alexandre; Remijan, Anthony; Szalewicz, Krzysztof

2014-06-01

In order to observe quantitatively organic molecules in interstellar gas, it is necessary to understand the relative importance of photonic and collisional excitations. In order to do so, collisional excitation transfer rates have to be computed. We undertook several such studies, in particular for H_2CO and HCOOCH_3. Both species are observed in many astrochemical environments, including star-forming regions. We found that those two molecules behave in their low-lying rotational levels in an opposite way. For cis methyl-formate, a non-equilibrium radiative transfer treatment of rotational lines is performed, using a new set of theoretical collisional rate coefficients. These coefficients have been computed in the temperature range 5 to 30 K by combining coupled-channel scattering calculations with a high accuracy potential energy surface for HCOOCH_3 -- He. The results are compared to observations toward the Sagittarius B2(N) molecular cloud. A total of 2080 low-lying transitions of methyl formate, with upper levels below 25 K, were treated. These lines are found to probe a cold (30 K), moderately dense (n ˜ 104 cm-3) interstellar gas. In addition, our calculations indicate that all detected emission lines with a frequency below 30 GHz are collisionally pumped weak masers amplifying the background of Sgr B2(N). This result demonstrates the generality of the inversion mechanism for the low-lying transitions of methyl formate. For formaldehyde, we performed a similar non-equilibrium treatment, with H_2 as the collisional partner, thanks to the accurate H_2CO - H_2 potential energy surface . We found very different energy transfer rates for collisions with para-H_2 (J=0) and ortho-H_2 (J=1). The well-known absorption against the cosmological background of the 111→ 101 line is shown to depend critically on the difference of behaviour between para and ortho-H_2, for a wide range of H_2 density. We thank the CNRS-PCMI French national program for continuous support and the CHESS Herschel KP program for travel supports. Discussions with C. Ceccarelli, P. Hily-Blant and S. Maret are acknowledged.

XenoSite server: a web-available site of metabolism prediction tool.

PubMed

Matlock, Matthew K; Hughes, Tyler B; Swamidass, S Joshua

2015-04-01

Cytochrome P450 enzymes (P450s) are metabolic enzymes that process the majority of FDA-approved, small-molecule drugs. Understanding how these enzymes modify molecule structure is key to the development of safe, effective drugs. XenoSite server is an online implementation of the XenoSite, a recently published computational model for P450 metabolism. XenoSite predicts which atomic sites of a molecule--sites of metabolism (SOMs)--are modified by P450s. XenoSite server accepts input in common chemical file formats including SDF and SMILES and provides tools for visualizing the likelihood that each atomic site is a site of metabolism for a variety of important P450s, as well as a flat file download of SOM predictions. XenoSite server is available at http://swami.wustl.edu/xenosite. © The Author 2014. Published by Oxford University Press. All rights reserved. For Permissions, please email: journals.permissions@oup.com.

Chiral Asymmetric Structures in Aspartic Acid and Valine Crystals Assessed by Atomic Force Microscopy.

PubMed

Teschke, Omar; Soares, David Mendez

2016-03-29

Structures of crystallized deposits formed by the molecular self-assembly of aspartic acid and valine on silicon substrates were imaged by atomic force microscopy. Images of d- and l-aspartic acid crystal surfaces showing extended molecularly flat sheets or regions separated by single molecule thick steps are presented. Distinct orientation surfaces were imaged, which, combined with the single molecule step size, defines the geometry of the crystal. However, single molecule step growth also reveals the crystal chirality, i.e., growth orientations. The imaged ordered lattice of aspartic acid (asp) and valine (val) mostly revealed periodicities corresponding to bulk terminations, but a previously unreported molecular hexagonal lattice configuration was observed for both l-asp and l-val but not for d-asp or d-val. Atomic force microscopy can then be used to identify the different chiral forms of aspartic acid and valine crystals.

Evolution of the long-wavelength, subduction-driven topography of South America since 150 Ma

NASA Astrophysics Data System (ADS)

Flament, N. E.; Gurnis, M.; Williams, S.; Bower, D. J.; Seton, M.; Müller, D.

2014-12-01

Subduction to the west of South America spans 6000 km along strike and has been active for over 250 Myr. The influence of the history of subduction on the geodynamics of South America has been profound, driving mountain building and arc volcanism in the Andean Cordillera. Here, we investigate the long-wavelength changes in the topography of South America associated with subduction and plate motion and their interplay with the lithospheric deformation associated with the opening of the South Atlantic. We pay particular attention to the topographic expression of flat-lying subduction zones. We develop time-dependent geodynamic models of mantle flow and lithosphere deformation to investigate the evolution of South American dynamic and total topography since the late Jurassic (150 Ma). Our models are semi-empirical because the computational cost of fully dynamic, evolutionary models is still prohibitive. We impose the kinematics of global plate reconstructions with deforming continents in forward global mantle convection models with compositionally distinct crust and continental lithosphere embedded within the thermal lithosphere. The shallow thermal structure of subducting slabs is imposed, allowing us to investigate the evolution of dynamic topography around flat slab segments in time-dependent models. Multiple cases are used to investigate how the evolution of South American dynamic topography is influenced by mantle viscosity, the kinematics of the opening of the South Atlantic and alternative scenarios for recent and past flat-slab subduction. We predict that the migration of South America over sinking oceanic lithosphere resulted in continental tilt to the west until ~ 45 Ma, inverting to an eastward tilt thereafter. This first-order result is consistent with the reversal of the drainage of the Amazon River system. We investigate which scenarios of flat-slab subduction since the Eocene are compatible with geological constraints on the evolution of the Solimoes Basin, the Chaco Basin, the Sierras Pampeanas and the Central Patagonian Basin. To broadly constrain mantle viscosity, we compare models to the total subsidence inferred from well data offshore Argentina and Brazil, and to mantle tomography, since the initial and boundary conditions are based on independent plate reconstructions.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Kozlov, I K

In this paper we study topological properties of an integrable case for Euler's equations on the Lie algebra so(4), which can be regarded as an analogue of the classical Kovalevskaya case in rigid body dynamics. In particular, for all values of the parameters of the system under consideration, the bifurcation diagrams of the momentum mapping are constructed, the types of critical points of rank 0 are determined, the bifurcations of Liouville tori are described, and the loop molecules are computed for all singular points of the bifurcation diagrams. It follows from the obtained results that some topological properties of the classicalmore » Kovalevskaya case can be obtained from the corresponding properties of the considered integrable case on the Lie algebra so(4) by taking a natural limit. Bibliography: 21 titles.« less

Isomerization of one molecule observed through tip enhanced Raman spectroscopy

NASA Astrophysics Data System (ADS)

Zhang, Yanxing; Lee, Joonhee; Apkarian, Vartkess A.; Wu, Ruqian; Ruqian Wu, Yanxing Zhang Team; Joonhee Lee, Vartkess A. Apkarian Team

While exploring photoisomerization of azobenzyl thiols (ABT) adsorbed on Au(111), through joint scanning tunneling microscopy (STM) and tip-enhanced Raman scattering (TERS) studies, the reversible photoisomerization of one molecule is captured in TERS trajectories. The apparently heterogeneously photo-catalyzed reaction is assigned to cis-trans isomerization of an outlier, which is chemisorbed on the silver tip of the STM. In order to clarify the role of the silver tip of the STM, we perform systematic density functional theory (DFT) calculations. The results show that compared with the case on the flat Ag(111) surface, the energy difference between trans and cis states of ABT decrease as we add one silver atom or a tetrahedron silver cluster on Ag(111) surface which mimic the geometry of a silver tip. In particular, the trans stretches away from the surface on the tetrahedral silver cluster, and the energy difference between trans and cis decreases to 0.27 eV, from ~1 eV for ABT on the flat Ag(111) surface. This significantly increases the possibility of cis-trans isomerization, as observed in our experiments. Work was supported by the National Science Foundation Center for Chemical Innovation on Chemistry at the Space-Time Limit (CaSTL) under Grant No. CHE-1414466.

Concept of a selective tumour therapy and its evaluation by near-infrared fluorescence imaging and flat-panel volume computed tomography in mice.

PubMed

Alves, Frauke; Dullin, Christian; Napp, Joanna; Missbach-Guentner, Jeannine; Jannasch, Katharina; Mathejczyk, Julia; Pardo, Luis A; Stühmer, Walter; Tietze, Lutz-F

2009-05-01

Conventional chemotherapy of cancer has its limitations, especially in advanced and disseminated disease and suffers from lack of specificity. This results in a poor therapeutic index and considerable toxicity to normal organs. Therefore, many efforts are made to develop novel therapeutic tools against cancer with the aim of selectively targeting the drug to the tumour site. Drug delivery strategies fundamentally rely on the identification of good-quality biomarkers, allowing unequivocal discrimination between cancer and healthy tissue. At present, antibodies or antibody fragments have clearly proven their value as carrier molecules specific for a tumour-associated molecular marker. This present review draws attention to the use of near-infrared fluorescence (NIRF) imaging to investigate binding specificity and kinetics of carrier molecules such as monoclonal antibodies. In addition, flat-panel volume computed tomography (fpVCT) will be presented to monitor anatomical structures in tumour mouse models over time in a non-invasive manner. Each imaging device sheds light on a different aspect; functional imaging is applied to optimise the dose schedule and the concept of selective tumour therapies, whereas anatomical imaging assesses preclinically the efficacy of novel tumour therapies. Both imaging techniques in combination allow the visualisation of functional information obtained by NIRF imaging within an adequate anatomic framework.

Ultrafast Spectroscopic Studies of Two-Photon States in Third Order Optical Processes of Dye Chromophores.

NASA Astrophysics Data System (ADS)

Yu, Yi-Zhong

1995-01-01

Conjugated organic and polymeric materials usually have large, nonresonant third order optical nonlinearity due to correlations of their delocalized pi -electrons. Most materials studied so far show positive values of third order nonlinear susceptibility when all frequencies that generate the third order effect are below any optical transition. A new class of organic molecules, namely indole squarylium (ISQ) and anilinium squarylium (BSQ), exhibit negative < gamma(-omega_4;omega_1, omega_2,omega_3)> when all three frequencies, omega_1, omega_2 and omega_3, lie below the first electronic transition. Although quantum many-electron calculations based on multiple-excitation configuration interaction have shown that the negative third order coefficient is essentially due to the contribution from high-lying two-photon states, the field of experimental studies exploring the microscopic origins of the negative squaraines remains uncultivated. The work presented in this thesis involves extensive experimental investigation of squaraines using techniques such as time-resolved transit absorption spectroscopy and saturable absorption. Theoretical simulations studying nonlinear absorption behavior of a simplified two-level system with ultrashort pulses are also presented. Part of the thesis is dedicated to the development, fabrication and characterization of our ultrafast laser system which offers tunable femtosecond pulses at wavelengths from UV to IR and served as a major tool in the experimental measurements. The dynamics of the population inversion between the ground state and the first excited state was also investigated through time-resolved experiments. The experiment results agree well with the theoretical predictions. Strong couplings between the gateway state and high-lying two-photon states were observed in BSQ squarylium molecules, which suggested a complete quantum calculation with multiple energy levels is required to correctly describe the negative third order effect.

Mobility and persistence of methane in groundwater in a controlled-release field experiment

NASA Astrophysics Data System (ADS)

Cahill, Aaron G.; Steelman, Colby M.; Forde, Olenka; Kuloyo, Olukayode; Emil Ruff, S.; Mayer, Bernhard; Ulrich Mayer, K.; Strous, Marc; Cathryn Ryan, M.; Cherry, John A.; Parker, Beth L.

2017-03-01

Expansion of shale gas extraction has fuelled global concern about the potential impact of fugitive methane on groundwater and climate. Although methane leakage from wells is well documented, the consequences on groundwater remain sparsely studied and are thought by some to be minor. Here we present the results of a 72-day methane gas injection experiment into a shallow, flat-lying sand aquifer. In our experiment, although a significant fraction of methane vented to the atmosphere, an equal portion remained in the groundwater. We find that methane migration in the aquifer was governed by subtle grain-scale bedding that impeded buoyant free-phase gas flow and led to episodic releases of free-phase gas. The result was lateral migration of gas beyond that expected by groundwater advection alone. Methane persisted in the groundwater zone despite active growth of methanotrophic bacteria, although much of the methane that vented into the vadose zone was oxidized. Our findings demonstrate that even small-volume releases of methane gas can cause extensive and persistent free phase and solute plumes emanating from leaks that are detectable only by contaminant hydrogeology monitoring at high resolution.

Characterization of the seismically imaged Tuscarora fold system and implications for layer parallel shortening in the Pennsylvania salient

NASA Astrophysics Data System (ADS)

Mount, Van S.; Wilkins, Scott; Comiskey, Cody S.

2017-12-01

The Tuscarora fold system (TFS) is located in the Pennsylvania salient in the foreland of the Valley and Ridge province. The TFS is imaged in high quality 3D seismic data and comprises a system of small-scale folds within relatively flat-lying Lower Silurian Tuscarora Formation strata. We characterize the TFS structures and infer layer parallel shortening (LPS) directions and magnitudes associated with deformation during the Alleghany Orogeny. Previously reported LPS data in our study area are from shallow Devonian and Carboniferous strata (based on outcrop and core analyses) above the shallowest of three major detachments recognized in the region. Seismic data allows us to characterize LPS at depth in strata beneath the shallow detachment. Our LPS data (orientations and inferred magnitudes) are consistent with the shallow data leading us to surmise that LPS during Alleghanian deformation fanned around the salient and was distributed throughout the stratigraphic section - and not isolated to strata above the shallow detachment. We propose that a NW-SE oriented Alleghanian maximum principal stress was perturbed by deep structure associated with the non-linear margin of Laurentia resulting in fanning of shortening directions within the salient.

Morphology of Florida Escarpment chemosynthetic brine seep community sites

DOE Office of Scientific and Technical Information (OSTI.GOV)

Paull, C.K.; Spiess, F.N.; Curray, J.R.

1988-01-01

The Florida Escarpment near 26/sup 0/N was surveyed with Deep-Two, Seabeam, and GLORIA in the area where chemosynthetic communities were discovered via ALVIN in the abyssal Gulf of Mexico. Seabeam bathymetry and GLORIA images indicate that the escarpment is a generally straight cliff with average slopes of about 45/sup 0/ from 2,200 to more than 3,250 m. The escarpment's face is cut by 2-km wide box canyons whose head walls are as steep as the intervening escarpment's face. The shapes of these canyons are difficult to explain with the traditional models of canyon formation. Sidescan sonar images and bottom photographsmore » reveal that the escarpment's face is composed of a series of long, straight bedding-plane terraces which are truncated along nearly vertical orthogonal joints. Exposure of these truncated strata indicate the face of the escarpment is eroded. The contact between the basal escarpment and the flat-lying abyssal hemipelagic sediments is abrupt. Apparently, chemosynthetic communities line extensive sections of the escarpment base where reduced brines seep out into the sea floor. The morphology suggests joints and deep seeps are controlling factors in scarp retreat.« less

Automatic identification of watercourses in flat and engineered landscapes by computing the skeleton of a LiDAR point cloud

NASA Astrophysics Data System (ADS)

Broersen, Tom; Peters, Ravi; Ledoux, Hugo

2017-09-01

Drainage networks play a crucial role in protecting land against floods. It is therefore important to have an accurate map of the watercourses that form the drainage network. Previous work on the automatic identification of watercourses was typically based on grids, focused on natural landscapes, and used mostly the slope and curvature of the terrain. We focus in this paper on areas that are characterised by low-lying, flat, and engineered landscapes; these are characteristic to the Netherlands for instance. We propose a new methodology to identify watercourses automatically from elevation data, it uses solely a raw classified LiDAR point cloud as input. We show that by computing twice a skeleton of the point cloud-once in 2D and once in 3D-and that by using the properties of the skeletons we can identify most of the watercourses. We have implemented our methodology and tested it for three different soil types around Utrecht, the Netherlands. We were able to detect 98% of the watercourses for one soil type, and around 75% for the worst case, when we compared to a reference dataset that was obtained semi-automatically.

Deccan volcanism and K-T boundary signatures

NASA Technical Reports Server (NTRS)

Murali, A. V.; Schuraytz, B. C.; Parekh, P. P.

1988-01-01

The Deccan Traps in the Indian subcontinent represent one of the most extensive flood basalt provinces in the world. These basalts occur mainly as flat-lying, subaerially erupted tholeiitic lava flows, some of which are traceable for distances of more than 100 km. Offshore drilling and geophysical surveys indicate that a part of the Deccan subsided or was downfaulted to the west beneath the Arabian Sea. The presence of 1 to 5 m thick intertrappean sediments deposited by lakes and rivers indicates periods of quiescence between eruptions. The occurrence of numerous red bole beds among the flows suggests intense weathering of flow tops between eruptive intervals. Although the causative relationship of the Cretaceous-Tertiary (K-T) biotic extinctions to Deccan volcanism is debatable, the fact that the main Deccan eruptions straddle the K-T event appears beyond doubt from the recent Ar-40/Ar-39 ages of various Deccan flows. This temporal relationship of the K-T event with Deccan volcanism makes the petrochemical signatures of the entire Deccan sequence (basalt flows, intercalated intertrappean sediments, infratrappean Lameta beds (with dinosaur fossils), and the bole beds) pertinent to studies of the K-T event. The results of ongoing study is presented.

Prograding coastal facies associations in the Vryheid formation (Permian) at Effingham quarries near Durban, South Africa

NASA Astrophysics Data System (ADS)

Tavener-Smith, R.

1982-05-01

This paper describes and interprets a flat-lying, sandstone—siltstone sequence 70 m thick in three disused quarries. The beds comprise the lowest part of the Vryheid Formation (middle Ecca) in the Durban vicinity. The sequence is conveniently divisible into two parts: the Lower Division constitutes a prograding beach barrier association, while the upper one represents a back barrier lagoonal complex. Fourteen sedimentary facies are described and interpreted to represent a range of depositional environments including open water shelf silts, sandy shoreface and littoral deposits, organic-rich muds and peats of lagoonal origin, a tidal inlet, washover fans and a fluvial channel sand. Among the conclusions reached are that the local middle Ecca coastline extended in a northwest to southeast direction and that progradation was towards the southwest; that the coastline was microtidal and that stormy conditions were common with prevalent palaeowinds from the northwest. The absence of invertebrate body fossils in these strata is attributed to penecontemporaneous solution of shelly remains. This is the first time that a coastal sequence has been identified on the southeast margin of the Main Karoo Basin of South Africa

Geologic Map of the Wilderness and Handy Quadrangles, Oregon, Carter, and Ripley Counties, Missouri

USGS Publications Warehouse

Harrison, Richard W.; McDowell, Robert C.

2003-01-01

The bedrock exposed in the Wilderness and Handy Quadrangles, Missouri, comprises Early Ordovician aged dolomite, sandstone, and chert. The sedimentary rocks are nearly flat-lying except where they are adjacent to faults. The carbonate rocks are karstified and the area contains numerous sinkholes, springs, caves, and losing-streams. This map is one of several being produced under the U.S. Geological Survey National Cooperative Geologic Mapping Program to provide geologic data applicable to land-use problems in the Ozarks of south-central Missouri. Ongoing and potential industrial and agricultural development in the Ozarks region has presented issues of ground-water quality in karst areas. These quadrangles contain significant areas of the Mark Twain National Forest, including part of the Eleven Point National Scenic Riverway and the Irish Wilderness Roadless Area. A National Park in this region (Ozark National Scenic Riverways, Missouri ) is concerned about the effects of activities in areas outside of their stewardship on the water resources that define the heart of this Park. This task applies geologic mapping and karst investigations to address issues surrounding competing land use in south-central Missouri. For more information see: http://geology.er.usgs.gov/eespteam/Karst/index.html

Geologic map of the Fremont quadrangle, Shannon, Carter, and Oregon Counties, Missouri

USGS Publications Warehouse

Orndorff, Randall C.

2003-01-01

The bedrock exposed in the Fremont Quadrangle, Missouri, comprises Early Ordovician aged dolomite, sandstone, and chert. The sedimentary rocks are nearly flat-lying except where they are adjacent to faults. The carbonate rocks are karstified and the area contains numerous sinkholes, springs, caves, and losing-streams. This map is one of several being produced under the U.S. Geological Survey National Cooperative Geologic Mapping Program to provide geologic data applicable to land-use problems in the Ozarks of south-central Missouri. Ongoing and potential industrial and agricultural development in the Ozarks region has presented issues of ground-water quality in karst areas. National Park in this region (Ozark National Scenic Riverways, Missouri) is concerned about the effects of activities in areas outside of their stewardship on the water resources that define the heart of this Park. This task applies geologic mapping and karst investigations to address issues surrounding competing land use in south-central Missouri. This task keeps geologists from the USGS associated with the park and allows the Parks to utilize USGS expertise and aid the NPS on how to effectively use geologic maps for Park management. For more information see: http://geology.er.usgs.gov/eespteam/Karst/index.html

Molecular traffic jams on DNA.

PubMed

Finkelstein, Ilya J; Greene, Eric C

2013-01-01

All aspects of DNA metabolism-including transcription, replication, and repair-involve motor enzymes that move along genomic DNA. These processes must all take place on chromosomes that are occupied by a large number of other proteins. However, very little is known regarding how nucleic acid motor proteins move along the crowded DNA substrates that are likely to exist in physiological settings. This review summarizes recent progress in understanding how DNA-binding motor proteins respond to the presence of other proteins that lie in their paths. We highlight recent single-molecule biophysical experiments aimed at addressing this question, with an emphasis placed on analyzing the single-molecule, ensemble biochemical, and in vivo data from a mechanistic perspective.

(S)-N-[1-(5-Benzyl-sulfan-yl-1,3,4-oxa-diazol-2-yl)-2-phenyl-eth-yl]-4-methyl-benzene-sulfonamide.

PubMed

Syed, Tayyaba; Hameed, Shahid; Jones, Peter G

2011-11-01

The title compound, C(24)H(23)N(3)O(3)S(2), crystallizes with two independent mol-ecules in the asymmetric unit. They differ essentially in the orientation of the tolyl rings, between which there is π-π stacking (centroid-centroid distance = 3.01 Å). The absolute configuration was confirmed by the determination of the Flack parameter [x = 0.008 (9)]. In the crystal, mol-ecules are connected by two classical N-H⋯N hydrogen bonds and two weak but very short C-H⋯O(sulfon-yl) inter-actions, forming layers lying parallel to the bc plane.

A 2:1 co-crystal of 2-methyl-benzoic acid and N,N'-bis-(pyridin-4-ylmeth-yl)ethanedi-amide: crystal structure and Hirshfeld surface analysis.

PubMed

Syed, Sabrina; Jotani, Mukesh M; Halim, Siti Nadiah Abdul; Tiekink, Edward R T

2016-03-01

The asymmetric unit of the title 2:1 co-crystal, 2C8H8O2·C14H14N4O2, comprises an acid mol-ecule in a general position and half a di-amide mol-ecule, the latter being located about a centre of inversion. In the acid, the carb-oxy-lic acid group is twisted out of the plane of the benzene ring to which it is attached [dihedral angle = 28.51 (8)°] and the carbonyl O atom and methyl group lie approximately to the same side of the mol-ecule [hy-droxy-O-C-C-C(H) torsion angle = -27.92 (17)°]. In the di-amide, the central C4N2O2 core is almost planar (r.m.s. deviation = 0.031 Å), and the pyridyl rings are perpendicular, lying to either side of the central plane [central residue/pyridyl dihedral angle = 88.60 (5)°]. In the mol-ecular packing, three-mol-ecule aggregates are formed via hy-droxy-O-H⋯N(pyrid-yl) hydrogen bonds. These are connected into a supra-molecular layer parallel to (12[Formula: see text]) via amide-N-H⋯O(carbon-yl) hydrogen bonds, as well as methyl-ene-C-H⋯O(amide) inter-actions. Significant π-π inter-actions occur between benzene/benzene, pyrid-yl/benzene and pyrid-yl/pyridyl rings within and between layers to consolidate the three-dimensional packing.

The G value in plasma and radiation chemistry

NASA Technical Reports Server (NTRS)

Baird, James K.; Miller, George P.; Li, Ning

1990-01-01

The application of the G-value concept to plasma chemistry is considered. A general formula which expresses the G value for a general reaction in terms of experimentally controllable parameters is derived by applying simple gas-dynamic theory to a plasma reactor with straight walls. The formula expresses the G value as a function of the electrical power absorbed, the fraction of molecules transformed, and the flow rate of the gas entering the reactor. The formula was applied to the ammonia plasma radio-frequency discharge data of d'Agostino et al. (1981); the results showed that the G(-NH3) value lies in the range of 6.0-20 molecules/100 eV, depending on the conditions. This similarity of the G(-NH3) value with Peterson's (1974) range 2.7-10 found for the gas-phase radiolysis of ammonia, suggests that there might be a common reaction mechanism initiated by inelastic electron-molecule collisions.

2,3-Diamino-pyridinium sorbate-sorbic acid (1/1).

PubMed

Hemamalini, Madhukar; Goh, Jia Hao; Fun, Hoong-Kun

2012-01-01

In the title mol-ecular salt-adduct, C(5)H(8)N(3) (+)·C(6)H(7)O(2) (-)·C(6)H(8)O(2), the 2,3-diamino-pyridinium cation is essentially planar, with a maximum deviation of 0.013 (2) Å, and is protanated at its pyridine N atom. The sorbate anion and sorbic acid mol-ecules exist in extended conformations. In the crystal, the protonated N atom and one of the two amino-group H atoms are hydrogen bonded to the sorbate anion through a pair of N-H⋯O hydrogen bonds, forming an R(1) (2)(6) ring motif. The carboxyl groups of the sorbic acid mol-ecules and the carboxyl-ate groups of the sorbate anions are connected via O-H⋯O hydrogen bonds. Furthermore, the ion pairs and neutral mol-ecules are connected via inter-molecular N-H⋯O hydrogen bonds, forming sheets lying parallel to (100).

Theoretical investigation of the molecular structure of the isoquercitrin molecule

NASA Astrophysics Data System (ADS)

Cornard, J. P.; Boudet, A. C.; Merlin, J. C.

1999-09-01

Isoquercitrin is a glycosilated flavonoid that has received a great deal of attention because of its numerous biological effects. We present a theoretical study on isoquercitrin using both empirical (Molecular Mechanics (MM), with MMX force field) and quantum chemical (AM1 semiempirical method) techniques. The most stable structures of the molecule obtained by MM calculations have been used as input data for the semiempirical treatment. The position and orientation of the glucose moiety with regard to the remainder of the molecule have been investigated. The flexibility of isoquercitrin principally lies in rotations around the inter-ring bond and the sugar link. In order to know the structural modifications generated by the substitution by a sugar, geometrical parameters of quercetin (aglycon) and isoquercitrin have been compared. The good accordance between theoretical and experimental electronic spectra permits to confirm the reliability of the structural model.

Formation mechanism and mechanics of dip-pen nanolithography using molecular dynamics.

PubMed

Wu, Cheng-Da; Fang, Te-Hua; Lin, Jen-Fin

2010-03-02

Molecular dynamics simulations are used to investigate the mechanisms of molecular transference, pattern formation, and mechanical behavior in the dip-pen nanolithography (DPN) process. The effects of deposition temperature were studied using molecular trajectories, the meniscus characteristic, surface absorbed energy, and pattern formation analysis. At the first transferred stage (at the initial indentation depth), the conformation of SAM molecules lies almost on the substrate surface. The molecules start to stand on the substrate due to the pull and drag forces at the second transferred stage (after the tip is pulled up). According to the absorbed energy behavior, the second transferred stage has larger transferred amounts and the transfer rate is strongly related to temperature. When molecules were deposited at low temperature (e.g., room temperature), the pattern shape was more highly concentrated. The pattern shape at high temperatures expanded and the area increased because of good molecular diffusion.

Origin of an extensive network of non-tectonic synclines in Eocene limestones of the Western Desert, Egypt

NASA Astrophysics Data System (ADS)

Tewksbury, Barbara J.; Tarabees, Elhamy A.; Mehrtens, Charlotte J.

2017-12-01

Satellite images of the Western Desert of Egypt display conspicuous sinuous color patterning that previous workers have interpreted as erosional flutes formed by catastrophic flooding. Our work with high resolution satellite imagery shows that the patterning is not erosional but, rather, the result of a network of thousands of narrow synclines in the Eocene bedrock capping the Limestone Plateau. Synclines form as isolated, 200-400 meter-wide downwarps in otherwise flat-lying strata. Limb dips are shallow, and doubly plunging hinges form multiple basin closures along syncline lengths. Anticlines form ;accidentally; in inter-syncline areas where two adjacent synclines lie close together. Synclines have two dominant orientations, WNW-ESE and NNW-SSE, parallel to two prominent joint and fault sets, and synclines branch, merge, and change orientation along their lengths. Synclines are all at the same scale with neither larger structures nor parasitic structures and are best described as non-tectonic sag synclines. An Egypt-wide inventory reveals that these synclines are both confined to Eocene limestones and developed, albeit it sporadically, over nearly 100,000 km2. The syncline network predates plateau gravels of the Katkut Formation, which have been interpreted as Oligocene or early Miocene in age, and the network is cut by faults related to Western Desert extension associated with Red Sea rifting. The mechanism that caused sag of overlying layers is not clear. Modern karst collapse, subsurface dissolution of evaporites, and collapse of paleokarst are all unlikely mechanisms given the timing of formation and the underlying stratigraphy. Silica diagenesis and downslope mobilization of underlying shales are possibilities, although uncertainty about the origin of silica in the limestones, plus the consistency of syncline orientations over large areas, make these models problematic. Hypogene karst, perhaps related to aggressive fluids associated with basaltic intrusions, may be the model most consistent with the admittedly limited data we currently have for the network.

Renormalization group flows and continual Lie algebras

NASA Astrophysics Data System (ADS)

Bakas, Ioannis

2003-08-01

We study the renormalization group flows of two-dimensional metrics in sigma models using the one-loop beta functions, and demonstrate that they provide a continual analogue of the Toda field equations in conformally flat coordinates. In this algebraic setting, the logarithm of the world-sheet length scale, t, is interpreted as Dynkin parameter on the root system of a novel continual Lie algebra, denoted by Script G(d/dt;1), with anti-symmetric Cartan kernel K(t,t') = delta'(t-t'); as such, it coincides with the Cartan matrix of the superalgebra sl(N|N+1) in the large-N limit. The resulting Toda field equation is a non-linear generalization of the heat equation, which is integrable in target space and shares the same dissipative properties in time, t. We provide the general solution of the renormalization group flows in terms of free fields, via Bäcklund transformations, and present some simple examples that illustrate the validity of their formal power series expansion in terms of algebraic data. We study in detail the sausage model that arises as geometric deformation of the O(3) sigma model, and give a new interpretation to its ultra-violet limit by gluing together two copies of Witten's two-dimensional black hole in the asymptotic region. We also provide some new solutions that describe the renormalization group flow of negatively curved spaces in different patches, which look like a cane in the infra-red region. Finally, we revisit the transition of a flat cone C/Zn to the plane, as another special solution, and note that tachyon condensation in closed string theory exhibits a hidden relation to the infinite dimensional algebra Script G(d/dt;1) in the regime of gravity. Its exponential growth holds the key for the construction of conserved currents and their systematic interpretation in string theory, but they still remain unknown.

Geologic map of the Chisos Mountains, Big Bend National Park, Texas

USGS Publications Warehouse

Bohannon, Robert G.

2011-01-01

The Chisos Mountains form some of the highest ground in Texas, second only to Guadalupe Peak near the New Mexico border. The northern half of the range is mostly above 5,500 feet with Emory Peak the high point at 7,825 feet. The mountains are centrally located in Big Bend National Park between Panther Junction and Punta de la Sierra. Big Bend National Park lies near the diffuse border between the Great Plains Province to the northeast and the Sonoran section of the Basin-and-Range structural province to the west and southwest. These geologically unique regions are distinguished from one another by large differences in their landscape and by the amount and style of internal structural deformation. The Great Plains Province is characterized by flat-lying or gently dipping sedimentary strata, low topographic relief, shallow stream valleys, and by a general lack of faulting. Very little active deposition is occurring on the plains, except in the bottoms of active stream valleys. In southwestern Texas the plains stand at average elevations of 2,000 to 3,300 feet and slope gently east toward the Mississippi River and the Gulf of Mexico. The Great Plains have remained relatively unchanged for the last 65 million years, except that they have been uplifted to their present height from lower elevations probably in the last 5 million years. The Basin-and-Range province is characterized by linear parallel mountain ranges, deep sediment-filled valleys, and high structural and topographic relief. The eastern part of the province is at a slightly higher average elevation than the plains. The province is known for its complex patterns of Cenozoic faulting. Today it bears little resemblance to the way it was during the Paleocene when the entire Trans-Pecos region was a simple lowland that was near or slightly below sea level.

Volcanic Evolution in the Galapagos: The Geochemistry and Petrology of Espanola Island

NASA Astrophysics Data System (ADS)

McGuire, M.; Varga, K. C.; Harpp, K. S.; Geist, D.; Hall, M. L.

2015-12-01

The Galapagos Archipelago consists of a series of volcanic islands located ~1,000 km west of South America that are thought to be the result of a mantle plume. The southeasternmost island, Espanola, is one of the smallest of the major islands, measuring only 7 by 14 km and reaching an elevation of 200 m. Espanola is also the oldest island in the chain, with K-Ar dates from 3.01 ± 0.11 to 3.31 ± 0.36 million years (Hall et al. 1983; White et al., 1993). The southern coast is defined by cliffs that exceed 100 m in height, made up of nearly flat-lying lavas that are each several meters thick. The northern coastline consists of lavas that dip gently toward the ocean from the highlands, as well as remnants of eroded cinder cones. Paleomagnetic measurements made in the field indicate that the western half of the island is reversely polarized, whereas most lavas measured across the eastern half are normally polarized. Major element analyses of samples from across the island indicate that fractional crystallization is the dominant process controlling chemical variations in Espanola lavas, suggesting a relatively long-lived magmatic plumbing system. Stratigraphically constrained chemical variations suggest the magma chamber may have experienced periodic replenishment by compositionally homogeneous primitive melts. Variable fluid-mobile trace element concentrations provide some evidence for contributions from ancient, recycled oceanic crust to the parental melts. Espanola lavas have more depleted Sr and Pb radiogenic isotope ratios than either Floreana or Fernandina, and lie on a mixing curve between the composition of the plume and that of the depleted upper mantle. Between ~3 and 8 Ma, the Galapagos Spreading Center was closer to the Galapagos plume than it is today. Given that Espanola was constructed during the same period, the depleted isotopic signatures suggest that plume-ridge interaction may have been a strong influence on the island's geochemical composition.

Adsorption-induced symmetry reduction of metal-phthalocyanines studied by vibrational spectroscopy

NASA Astrophysics Data System (ADS)

Sforzini, J.; Bocquet, F. C.; Tautz, F. S.

2017-10-01

We investigate the vibrational properties of Pt- and Pd-phthalocyanine (PtPc and PdPc) molecules on Ag(111) with high-resolution electron energy loss spectroscopy (HREELS). In the monolayer regime, both molecules exhibit long-range order. The vibrational spectra prove a flat adsorption geometry. The redshift of specific vibrational modes suggests a moderate interaction of the molecules with the substrate. The presence of asymmetric vibrational peaks indicates an interfacial dynamical charge transfer (IDCT). The molecular orbital that is involved in IDCT is the former Eg lowest unoccupied molecular orbital (LUMO) of the molecules that becomes partially occupied upon adsorption. A group-theoretical analysis of the IDCT modes, based on calculated vibrational frequencies and line shape fits, provides proof for the reduction of the symmetry of the molecule-substrate complex from fourfold D4 h to C2 v(σv) , Cs(σv) , or C2 and the ensuing lifting of the degeneracy of the former LUMO of the molecule. The vibration-based analysis of orbital degeneracies, as carried out here for PtPc/Ag(111) and PdPc/Ag(111), is particularly useful whenever the presence of multiple molecular in-plane orientations at the interface makes the analysis of orbital degeneracies with angle-resolved photoemission spectroscopy difficult.

Bay-annulated indigo (BAI) as an excellent electron accepting building block for high performance organic semiconductors

DOEpatents

Liu, Yi; He, Bo; Pun, Andrew

2015-11-24

A novel electron acceptor based on bay-annulated indigo (BAI) was synthesized and used for the preparation of a series of high performance donor-acceptor small molecules and polymers. The resulting materials possess low-lying LUMO energy level and small HOMO-LUMO gaps, while their films exhibited high crystallinity upon thermal treatment, commensurate with high field effect mobilities and ambipolar transfer characteristics.

Bay-annulated indigo (BAI) as an excellent electron accepting building block for high performance organic semiconductors

DOEpatents

Liu, Yi; He, Bo; Pun, Andrew

2016-04-19

A novel electron acceptor based on bay-annulated indigo (BAI) was synthesized and used for the preparation of a series of high performance donor-acceptor small molecules and polymers. The resulting materials possess low-lying LUMO energy level and small HOMO-LUMO gaps, while their films exhibited high crystallinity upon thermal treatment, commensurate with high field effect mobilities and ambipolar transfer characteristics.

Titan's Ammonia Feature

NASA Technical Reports Server (NTRS)

Smythe, W.; Nelson, R.; Boryta, M.; Choukroun, M.

2011-01-01

NH3 has long been considered an important component in the formation and evolution of the outer planet satellites. NH3 is particularly important for Titan, since it may serve as the reservoir for atmospheric nitrogen. A brightening seen on Titan starting in 2004 may arise from a transient low-lying fog or surface coating of ammonia. The spectral shape suggests the ammonia is anhydrous, a molecule that hydrates quickly in the presence of water.

Study of clusters using negative ion photodetachment spectroscopy

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhao, Yuexing

1995-12-01

The weak van der Waals interaction between an open-shell halogen atom and a closed-shell atom or molecule has been investigated using zero electron kinetic energy (ZEKE) spectroscopy. This technique is also applied to study the low-lying electronic states in GaAs and GaAs -. In addition, the spectroscopy and electron detachment dynamics of several small carbon cluster anions are studied using resonant multiphoton detachment spectroscopy.

Low-lying excited states by constrained DFT

NASA Astrophysics Data System (ADS)

Ramos, Pablo; Pavanello, Michele

2018-04-01

Exploiting the machinery of Constrained Density Functional Theory (CDFT), we propose a variational method for calculating low-lying excited states of molecular systems. We dub this method eXcited CDFT (XCDFT). Excited states are obtained by self-consistently constraining a user-defined population of electrons, Nc, in the virtual space of a reference set of occupied orbitals. By imposing this population to be Nc = 1.0, we computed the first excited state of 15 molecules from a test set. Our results show that XCDFT achieves an accuracy in the predicted excitation energy only slightly worse than linear-response time-dependent DFT (TDDFT), but without incurring into problems of variational collapse typical of the more commonly adopted ΔSCF method. In addition, we selected a few challenging processes to test the limits of applicability of XCDFT. We find that in contrast to TDDFT, XCDFT is capable of reproducing energy surfaces featuring conical intersections (azobenzene and H3) with correct topology and correct overall energetics also away from the intersection. Venturing to condensed-phase systems, XCDFT reproduces the TDDFT solvatochromic shift of benzaldehyde when it is embedded by a cluster of water molecules. Thus, we find XCDFT to be a competitive method among single-reference methods for computations of excited states in terms of time to solution, rate of convergence, and accuracy of the result.

Comparison of Oxygen Gauche Effects in Poly(Oxyethylene) and Poly(ethylene terephtylene) Based on Quantum Chemistry Calculations

NASA Technical Reports Server (NTRS)

Jaffe, Richard; Han, Jie; Yoon, Do; Langhoff, Stephen R. (Technical Monitor)

1997-01-01

The so-called oxygen gauche effect in poly(oxyethylene) (POE) and its model molecules such as 1,2-dimethoxyethane (DME) and diglyme (CH3OC2H4OC2H4OCH3) is manifested in the preference for gauche C-C bond conformations over trans. This has also been observed for poly(ethylene terephthalate) (PET). Our previous quantum chemistry calculations demonstrated that the large C-C gauche population in DME is due, in part, to a low-lying tg +/- g+ conformer that exhibits a substantial 1,5 CH ... O attraction. New calculations will be described that demonstrate the accuracy of the original quantum chemistry calculations. In addition, an extension of this work to model molecules for PET will be presented. It is seen that the C-C gauche preference is much stronger in 1,2 diacetoxyethane than in DME. In addition, there exist low-lying tg +/- g+/- and g+/-g+/-g+/- conformers that exhibit 1,5 CH ... O attractions involving the carbonyl oxygens. It is expected that the -O-C-C-O- torsional properties will be quite different in these two polymers. The quantum chemistry results are used to parameterize rotational isomeric states models (RIS) and force fields for molecular dynamics simulations of these polymers.

Crystal structure of bis-[(phenyl-methanamine-κN)(phthalocyaninato-κ(4) N)zinc] phenyl-methan-amine tris-olvate.

PubMed

Shamsudin, Norzianah; Tan, Ai Ling; Wimmer, Franz L; Young, David J; Tiekink, Edward R T

2015-09-01

The asymmetric unit of the title compound, 2[Zn(C32H16N8)(C7H9N)]·3C7H9N, comprises two independent complex mol-ecules and three benzyl-amine solvent mol-ecules. Each complex mol-ecule features a penta-coordinated Zn(2+) ion within a square-pyramidal geometry, whereby the N5 donor set is defined by four atoms of the phthalocyaninate dianion (PC) and an N-bound benzyl-amine mol-ecule; it is the relative orientations of the latter that differentiate between the independent complex mol-ecules. The uncoordinated benzyl-amine mol-ecules display different conformations in the structure, with syn-Car-Car-Cm-N (ar = aromatic, m = methyl-ene) torsion angles spanning the range -28.7 (10) to 35.1 (14)°. In the crystal, N-H⋯N and N-H⋯π inter-actions lead to supra-molecular layers in the ab plane. The layers have a zigzag topology, have the coordinating and non-coordinating benzyl-amine mol-ecules directed to the inside, and present the essentially flat PC resides to the outside. This arrangement enables adjacent layers to associate via π-π inter-actions [inter-centroid distance between pyrrolyl and fused-benzene rings = 3.593 (2) Å] so that a three-dimensional architecture is formed.

Hydrothermal uranium deposits containing molybdenum and fluorite in the Marysvale volcanic field, west-central Utah

USGS Publications Warehouse

Cunningham, C.G.; Rasmussen, J.D.; Steven, T.A.; Rye, R.O.; Rowley, P.D.; Romberger, S.B.; Selverstone, J.

1998-01-01

Uranium deposits containing molybdenum and fluorite occur in the Central Mining Area, near Marysvale, Utah, and formed in an epithermal vein system that is part of a volcanic/hypabyssal complex. They represent a known, but uncommon, type of deposit; relative to other commonly described volcanic-related uranium deposits, they are young, well-exposed and well-documented. Hydrothermal uranium-bearing quartz and fluorite veins are exposed over a 300 m vertical range in the mines. Molybdenum, as jordisite (amorphous MoS2, together with fluorite and pyrite, increase with depth, and uranium decreases with depth. The veins cut 23-Ma quartz monzonite, 20-Ma granite, and 19-Ma rhyolite ash-flow tuff. The veins formed at 19-18 Ma in a 1 km2 area, above a cupola of a composite, recurrent, magma chamber at least 24 ?? 5 km across that fed a sequence of 21- to 14-Ma hypabyssal granitic stocks, rhyolite lava flows, ash-flow tuffs, and volcanic domes. Formation of the Central Mining Area began when the intrusion of a rhyolite stock, and related molybdenite-bearing, uranium-rich, glassy rhyolite dikes, lifted the fractured roof above the stock. A breccia pipe formed and relieved magmatic pressures, and as blocks of the fractured roof began to settle back in place, flat-lying, concave-downward, 'pull-apart' fractures were formed. Uranium-bearing, quartz and fluorite veins were deposited by a shallow hydrothermal system in the disarticulated carapace. The veins, which filled open spaces along the high-angle fault zones and flat-lying fractures, were deposited within 115 m of the ground surface above the concealed rhyolite stock. Hydrothermal fluids with temperatures near 200??C, ??18OH2O ~ -1.5, ?? -1.5, ??DH2O ~ -130, log fO2 about -47 to -50, and pH about 6 to 7, permeated the fractured rocks; these fluids were rich in fluorine, molybdenum, potassium, and hydrogen sulfide, and contained uranium as fluoride complexes. The hydrothermal fluids reacted with the wallrock resulting in precipitation of uranium minerals. At the deepest exposed levels, wall-rocks were altered to sericite; and uraninite, coffinite, jordisite, fluorite, molybdenite, quartz, and pyrite were deposited in the veins. The fluids were progressively oxidized and cooled at higher levels in the system by boiling and degassing; iron-bearing minerals in wall rocks were oxidized to hematite, and quartz, fluorite, minor siderite, and uraninite were deposited in the veins. Near the ground surface, the fluids were acidified by condensation of volatiles and oxidation of hydrogen sulfide in near-surface, steam-heated, ground waters; wall rocks were altered to kaolinite, and quartz fluorite, and uraninite were deposited in veins. Secondary uranium minerals, hematite, and gypsum formed during supergene alteration later in the Cenozoic when the upper part of the mineralized system was exposed by erosion.

Csub60/Collapsed Carbon Nanotube Hybrids: A Variant of Peapods (Open Access)

DTIC Science & Technology

2015-01-02

fullerenes , collapsed carbon nanotubes, silocrystals Hybrid nanostructures are of great interest due to thepotential for engineering new materials with...tunable physical and chemical properties. An example is the so-called nanotube “peapod” first described by Smith et al.,1 where fullerene C60 molecules...an interesting derivative of CNTs. It has been theoretically shown that CNTs are prone to collapse into a nearly flat, ribbon- like configuration if

Electron tomographic analysis of cytokinesis in the brown alga Silvetia babingtonii (Fucales, Phaeophyceae).

PubMed

Nagasato, Chikako; Kajimura, Naoko; Terauchi, Makoto; Mineyuki, Yoshinobu; Motomura, Taizo

2014-11-01

In brown algae, membrane resources for the new cell partition during cytokinesis are mainly flat cisternae (FCs) and Golgi-derived vesicles. We used electron tomography coupled with rapid freezing/freeze substitution of zygotes to clarify the structure of transient membrane compartments during cytokinesis in Silvetia zygotes. After mitosis, an amorphous membranous structure, considered to be an FC intermediate was observed near endoplasmic reticulum clusters, lying between two daughter nuclei. FCs were arrayed at the cytokinetic plane, and a tubular membranous network was formed around them. This network might be formed by the consecutive fusion of spherical vesicles that are linked to the edges of FCs to form a membranous network (MN). At the initial stage of the formation of a membranous sac (MS) from the MN, the MS had flat and swollen parts, with the latter showing membranous tunnels. Coated pits were detected with high frequency at the swollen parts of the MS. This observation indicated that membranous tunnels disappeared by recycling of excess membrane via endocytosis, and the swollen part became flat. The MN appeared at the edges of the growing MS. MN and the MN-MS complex were observed along the cytokinetic plane in several spaces. The MS expanded by the incorporation of MN or other MS in its neighborhood. With the maturation of the new cell partition membrane, the thickness of the MS became constant and the membrane cavity disappeared. The changes in the surface area and volume of the transient membrane compartment during cytokinesis were analyzed from the tomographic data.

Theory of attosecond delays in molecular photoionization.

PubMed

Baykusheva, Denitsa; Wörner, Hans Jakob

2017-03-28

We present a theoretical formalism for the calculation of attosecond delays in molecular photoionization. It is shown how delays relevant to one-photon-ionization, also known as Eisenbud-Wigner-Smith delays, can be obtained from the complex dipole matrix elements provided by molecular quantum scattering theory. These results are used to derive formulae for the delays measured by two-photon attosecond interferometry based on an attosecond pulse train and a dressing femtosecond infrared pulse. These effective delays are first expressed in the molecular frame where maximal information about the molecular photoionization dynamics is available. The effects of averaging over the emission direction of the electron and the molecular orientation are introduced analytically. We illustrate this general formalism for the case of two polyatomic molecules. N 2 O serves as an example of a polar linear molecule characterized by complex photoionization dynamics resulting from the presence of molecular shape resonances. H 2 O illustrates the case of a non-linear molecule with comparably simple photoionization dynamics resulting from a flat continuum. Our theory establishes the foundation for interpreting measurements of the photoionization dynamics of all molecules by attosecond metrology.

Molecular layers of ZnPc and FePc on Au(111) surface: Charge transfer and chemical interaction

NASA Astrophysics Data System (ADS)

Ahmadi, Sareh; Shariati, M. Nina; Yu, Shun; Göthelid, Mats

2012-08-01

We have studied zinc phthalocyanine (ZnPc) and iron phthalocyanine (FePc) thick films and monolayers on Au(111) using photoelectron spectroscopy and x-ray absorption spectroscopy. Both molecules are adsorbed flat on the surface at monolayer. ZnPc keeps this orientation in all investigated coverages, whereas FePc molecules stand up in the thick film. The stronger inter-molecular interaction of FePc molecules leads to change of orientation, as well as higher conductivity in FePc layer in comparison with ZnPc, which is reflected in thickness-dependent differences in core-level shifts. Work function changes indicate that both molecules donate charge to Au; through the π-system. However, the Fe3d derived lowest unoccupied molecular orbital receives charge from the substrate when forming an interface state at the Fermi level. Thus, the central atom plays an important role in mediating the charge, but the charge transfer as a whole is a balance between the two different charge transfer channels; π-system and the central atom.

Effect of lattice-gas atoms on the adsorption behaviour of thioether molecules.

PubMed

Pan, Yi; Yang, Bing; Hulot, Catherine; Blechert, Siegfried; Nilius, Niklas; Freund, Hans-Joachim

2012-08-21

Using STM topographic imaging and spectroscopy, we have investigated the adsorption of two thioether molecules, 1,2-bis(phenylthio)benzene and (bis(3-phenylthio)-phenyl)sulfane, on noble and transition metal surfaces. The two substrates show nearly antipodal behaviour. Whereas complexes with one or two protruding centres are observed on Au(111), only flat and uniform ad-structures are found on NiAl(110). The difference is ascribed to the possibility of the thioethers to form metal-organic complexes by coordinating lattice-gas atoms on the Au(111), while only the pristine molecules adsorb on the alloy surface. The metal coordination in the first case is driven by the formation of strong Au-S bonds and enables the formation of characteristic monomer, dimer and chain-like structures of the thioethers, using the Au atoms as linkers. A similar mechanism is not available on the NiAl, because no lattice gas develops at this surface at room temperature. Our work demonstrates how surface properties, i.e. the availability of mobile ad-species, determine the interaction of organic molecules with metallic substrates.

Amphiphile-Induced Reorganization of Nematic Liquid Crystals at Aqueous Interfaces

NASA Astrophysics Data System (ADS)

Rahimi, Amin; Ramezani-Dakhel, Hadi; Pendery, Joel; Abbott, Nicholas; de Pablo, Juan; Juan de Pablo Team, Prof; Nicholas Abbott Collaboration, Prof

Recent studies have shown that ordering transitions in 4-cyano-4'-pentylbiphenyl (5CB) molecules can be triggered by the self-assembly of specific amphiphiles near a flat aqueous-LC interface. In the absence of adsorbed amphiphiles, LC molecules adopt a parallel orientation at the aqueous interface. Self-assembly of amphiphile molecules at the LC-aqueous interface triggers a spontaneous reorientation of the LC at the aqueous interface. A number of observations indicate that the hydrophilic headgroup of the surfactant has marginal effect on the orientation of 5CB whereas the aliphatic tail structure, length, and conformation greatly affect the ordering of the LC. The structural reorganization of liquid crystals at aqueous interfaces has been primarily ascribed to a weakening of the surface anchoring strength induced by amphiphile molecules. Such explanations, however, have only been supported by a posteriorimicroscopic observations. The underlying mechanism of such an ordering transition and the effect of amphiphile structure remain poorly understood. Here, we study the nature of molecular interactions between amphiphiles, 5CB, and water to understand the mechanism of ordering transitions using atomistic molecular dynamics simulations.

A structural analysis of the Minas da Panasqueira vein network and related fracture generations

NASA Astrophysics Data System (ADS)

Jacques, Dominique; Vieira, Romeu; Muchez, Philippe; Sintubin, Manuel

2014-05-01

The Minas da Panasqueira is a world-class W-Cu-Sn vein-type deposit, situated within the Central Iberian Zone of the Palaeozoic Iberian Massif (Portugal). The deposit consists of a network of subhorizontal, sill-like massive quartz veins situated above the southwestern extremity of a greisen cupola, within regionally metamorphosed, isoclinally folded, lower-greenschist slates and greywackes. The greisen cupola is part of a larger intrusive complex, emplaced during the late- to post-tectonic stage of the Variscan orogeny. The late-Variscan granitoid(s) underlying the Panasqueira deposit is considered to have served as a major metal source. The structure of the network of subhorizontal extension veins, consists of numerous planar vein lobes that are separated by host-rock bridges and merge at branch-points. A structural analysis demonstrates that not only within the Panasqueira mine, but also on a more regional scale, one or more generations of flat-lying fractures are present. The veins clearly exploited these pre-existing discontinuities, as confirmed by (1) the vein geometry being directly influenced by variations in the orientation of the initial fracture sets and (2) the geometry of the rock bridges and overlapping vein morphologies, consistently showing straight-line propagating crack tips. If veining is governed by a preferential, strongly developed anisotropy in the host rock, the hypothesis of vein lobes and rock bridges forming during propagation of the parent crack by tip-line bifurcation and confinement processes (Foxford et al., 2000) does not seem plausible. Instead, we propose that the rock bridges formed from several, initially separate and small veinlets that eventually overlapped in an en echelon arrangement during progressive propagation and inflation. Bending of the rock bridges and incipient vein rotation indicate that veining occurred near the brittle-ductile transition. Using a quantitative analysis of bridge orientations, vein aspect ratios and tip lines, we try to sort out if a dominant σ2 propagation direction, typical for hydrofractures, exists within the vein network. By doing so, we can evaluate whether the subhorizontal vein network formed under a compressive stress regime, or was mainly dictated by the strength anisotropy of the rocks under near-isotropic stress conditions of σhmax ≡ σhmin. The regional dominance of subhorizontal aplites, pegmatites and hydrothermal veins, exploiting subhorizontal fracture networks, occurs over a wide area of more than 100 km2 along the Serra de Estrela granitic massif (Derré et al., 1986). This orientation contrasts with the more common vertical attitude of granite-related hydrothermal veins, observed throughout the Iberian massif. A detailed orientation analysis of the fracture sets should allow to explore the possible causes of this particular late orogenic, flat-lying fracture network related to the granitic intrusion. References Derré, C., Lecolle, M., Roger, G., Tavares de Freitas Carvalho, J., 1986. Tectonics, magmatism, hydrothermalism and sets of flat joints locally filled by Sn-W, aplite-pegmatite and quartz veins, southeastern border of the Serra de Estrela granitic massif (Beira Baixa, Portugal). Ore Geology Reviews 1, 43-56. Foxford, K. A., Nicholson, R., Polya, D. A., and Hebblethwaite, R. P. B., 2000. Extensional failure and hydraulic valving at Minas da Panasqueira, Portugal; evidence from vein spatial distributions, displacements and geometries. Journal of Structural Geology 22, 1065-1086.

The interplay between pH sensitivity and label-free protein detection in immunologically modified nano-scaled field-effect transistor.

PubMed

Shalev, Gil; Rosenwaks, Yossi; Levy, Ilan

2012-01-15

We present experimental results in order to establish a correlation between pH sensitivity of immunologically modified nano-scaled field-effect transistor (NS-ImmunoFET) with their sensing capacity for label-free detection. The NS-ImmunoFETs are fabricated from silicon-on-insulator (SOI) wafers and are fully-depleted with thickness of ~20 nm. The data shows that higher sensitivity to pH entails enhanced sensitivity to analyte detection. This suggests that the mechanism of analyte detection as pure electrostatic perturbation induced by antibody-analyte interaction is over simplified. The fundamental assumption, in existing models for field-effect sensing mechanism assumes that the analyte molecules do not directly interact with the surface but rather stand 'deep' in the solution and away from the dielectric surface. Recent studies clearly provide contradicting evidence demonstrating that antibodies lie down flat on the surface. These observations led us to propose that the proteins that cover the gate area intimately interact with active sites on the surface thus forming a network of interacting sites. Since sensitivity to pH is directly correlated with the amount of amphoteric sites, we witness a direct correlation between sensitivity to pH and analyte detection. The highest and lowest threshold voltage shift for a label-free and specific detection of 6.5 nM IgG were 40 mV and 2.3 mV for NS-ImmunoFETs with pH sensitivity of 35 mV/decade and 15 mV/decade, respectively. Finally, physical modeling of the NS-ImmunoFET is presented and charge of a single IgG protein at pH 6 is calculated. The obtained value is consistent with charge of IgG protein cited in literature. Copyright © 2011 Elsevier B.V. All rights reserved.

Organization of lipids in avian stratum corneum: Changes with temperature and hydration.

PubMed

Champagne, Alex M; Allen, Heather C; Bautista-Jimenez, Robin C; Williams, Joseph B

2016-02-01

In response to increases in ambient temperature (Ta), many animals increase total evaporative water loss (TEWL) through their skin and respiratory passages to maintain a constant body temperature, a response that compromises water balance. In birds, cutaneous water loss (CWL) accounts for approximately 65% of TEWL at thermoneutral temperatures. Although the proportion of TEWL accounted for by CWL decreases to only 25% at high Ta, the magnitude of CWL still increases, suggesting changes in the barrier function of the skin. The stratum corneum (SC) is composed of flat, dead cells called corneocytes embedded in a matrix of lipids, many of which arrange in layers called lamellae. The classes of lipids that comprise these lamellae, and their attendant physical properties, determine the rate of CWL. We measured CWL at 25, 30, 35, and 40 °C in House Sparrows (Passer domesticus) caught in the winter and summer, and in sparrows acclimated to warm and cold lab environments. We then used Fourier transform infrared spectroscopy to measure lipid-lipid and lipid-water interactions in the SC under different conditions of temperature and hydration, and correlated these results with lipid classes in the SC. As CWL increased at higher temperatures, the amount of gauche defects in lipid alkyl chains increased, indicating that lipid disorder is partially responsible for higher CWL at high temperatures. However, variation in CWL between groups could not be explained by the amount of gauche defects, and this remaining variation may be attributed to greater amounts of cerebrosides in birds with low CWL, as the sugar moieties of cerebrosides lie outside lipid lamellae and form strong hydrogen bonds with water molecules. Copyright © 2015 Elsevier Ireland Ltd. All rights reserved.

Scanning force microscopy and fluorescence microscopy of microcontact printed antibodies and antibody fragments.

PubMed

LaGraff, John R; Chu-LaGraff, Quynh

2006-05-09

Unlabeled primary immunoglobulin G (IgG) antibodies and its F(ab')2 and Fc fragments were attached to oxygen-plasma-cleaned glass substrates using either microcontact printing (MCP) or physical adsorption during bath application from dilute solutions. Fluorescently labeled secondary IgGs were then bound to surface-immobilized IgG, and the relative surface coverage was determined by measuring the fluorescence intensity. Results indicated that the surface coverage of IgG increased with increasing protein solution concentration for both MCP and bath-applied IgG and that a greater concentration of IgG was transferred to a glass substrate using MCP than during physisorption during bath applications. Scanning force microscopy (SFM) showed that patterned MCP IgG monolayers were 5 nm in height, indicating that IgG molecules lie flat on the substrate. After incubation with a secondary IgG, the overall line thickness increased to around 15 nm, indicating that the secondary IgG was in a more vertical orientation with respect to the substrate. The surface roughness of these MCP patterned IgG bilayers as measured by SFM was observed to increase with increasing surface coverage. Physisorption of IgG to both unmodified patterned polydimethylsiloxane (PDMS) stamps and plasma-cleaned glass substrates was modeled by Langmuir adsorption kinetics yielding IgG binding constants of K(MCP) = 1.7(2) x 10(7) M(-1) and K(bath) = 7.8(7) x 10(5) M(-1), respectively. MCP experiments involving primary F(ab')2 and Fc fragments incubated in fluorescently labeled fragment-specific secondary IgGs were carried out to test for the function and orientation of IgG. Finally, possible origins of MCP stamping defects such as pits, pull outs, droplets, and reverse protein transfer are discussed.

Photoswitching in azobenzene self-assembled monolayers capped on zinc oxide: nanodots vs nanorods.

PubMed

Shah, Syed Mujtaba; Martini, Cyril; Ackermann, Jörg; Fages, Frédéric

2012-02-01

We report the synthesis and spectroscopic characterization of nanohybrid structures consisting of an azobenzene compound grafted on the surface of zinc oxide nanoparticles. Characteristic bathochromic shifts indicate that the azobenzene photochromic molecules self-assemble onto the surface of the nanocrystals. The extent of packing is dependent on the shape of the nanoparticle. ZnO nanorods, with flat facets, enable a tighter organization of the molecules in the self-assembled monolayer than in the case of nanodots that display a more curvated shape. Consistently, the efficiency of photochromic switching of the self-assembled monolayer on ZnO nanoparticles is also shown to be strongly affected by nanoparticle shape. Copyright © 2011 Elsevier Inc. All rights reserved.

Novel surface diffusion characteristics for a robust pentacene derivative on Au(1 1 1) surfaces

NASA Astrophysics Data System (ADS)

Miller, Ryan A.; Larson, Amanda; Pohl, Karsten

2017-06-01

Molecular dynamics simulations have been performed in both the ab initio and classical mechanics frameworks of 5,6,7-trithiapentacene-13-one (TTPO) molecules on flat Au(1 1 1) surfaces. Results show new surface diffusion characteristics including a strong preference for the molecule to align its long axis parallel to the sixfold Au(1 1 1) symmetry directions and subsequently diffuse along these close-packed directions, and a calculated activation energy for diffusion of 0.142 eV, about four times larger than that for pure pentacene on Au. The temperature-dependent diffusion coefficients were calculated to help quantify the molecular mobility during the experimentally observed process of forming self-assembled monolayers on gold electrodes.

Explaining rISC and 100% efficient TADF (Conference Presentation)

NASA Astrophysics Data System (ADS)

Monkman, Andrew P.; Etherington, Marc; Graves, David; Data, Przemyslaw; Dos Santos, Paloma Lays; Nobuyasu, Roberto; Baiao Dias, Fernando M.

2016-09-01

Detailed photophysical measurements of intramolecular charge transfer (ICT) states have been made both in solution and solid state. Temperature dependent time resolved emission, delayed emission and photoinduced absorption are used to map the energy levels involved in molecule decay, and through detailed kinetic modelling of the thermally activated processes observed, true electron exchange energies and other energy barriers of the systems determined with the real states involved in the reversed intersystem crossing mechanism elucidated. For specific donor acceptor molecules, the CT singlet and local triplet states (of donor or acceptor) are found to be the lowest lying excited states of the molecule with very small energy barrier between them ? kT. In these cases the decay kinetics of the molecules become significantly different to normal molecules, and the effect of rapid recycling between CT singlet and local triplet states is observed which gives rise to the true triplet harvesting mechanism in TADF. Using a series of different TADF emitters we will show how the energy level ordering effects or does not effect TADF and how ultimate OLED performance is dictated by energy level ordering, from 5% to 22% external quantum efficiency. From this understanding, we are able to define three criterion for TADF in different molecules and these will be discussed.

Vibronic bands in the HOMO-LUMO excitation of linear polyyne molecules

NASA Astrophysics Data System (ADS)

Wakabayashi, Tomonari; Wada, Yoriko; Iwahara, Naoya; Sato, Tohru

2013-04-01

Hydrogen-capped linear carbon chain molecules, namely polyynes H(C≡C)nH (n>=2), give rise to three excited states in the HOMO-LUMO excitation. Electric dipole transition from the ground state is fully allowed to one of the three excited states, while forbidden for the other two low-lying excited states. In addition to the strong absorption bands in the UV for the allowed transition, the molecules exhibit weak absorption and emission bands in the near UV and visible wavelength regions. The weak features are the vibronic bands in the forbidden transition. In this article, symmetry considerations are presented for the optical transitions in the centrosymmetric linear polyyne molecule. The argument includes Herzberg-Teller expansion for the state mixing induced by nuclear displacements along the normal coordinate of the molecule, intensity borrowing from fully allowed transitions, and inducing vibrational modes excited in the vibronic transition. The vibronic coupling considered here includes off-diagonal matrix elements for second derivatives along the normal coordinate. The vibronic selection rule for the forbidden transition is derived and associated with the transition moment with respect to the molecular axis. Experimental approaches are proposed for the assignment of the observed vibronic bands.

Laser Spectroscopy of Ruthenium Containing Diatomic Molecules: RuH/D and RuP.

NASA Astrophysics Data System (ADS)

Adam, Allan G.; Konder, Ricarda M.; Nickerson, Nicole M.; Linton, Colan; Tokaryk, D. W.

2015-06-01

In the last few years, the Cheung group in Hong Kong and the Steimle group in Arizona have successfully studied several ruthenium containing diatomic molecules, RuX (X =C, O, N, B, using the laser-ablation molecular jet technique. Based on this success, the UNB spectroscopy group decided to try and find the optical signatures of other RuX molecules. Using CH_3OH and PH_3 as reactant gases, the RuH and RuP diatomic molecules have been detected in surveys of the 420 - 675 nm spectral region. RuD has also been made using fully deuterated methanol as a reactant. Dispersed fluorescence experiments have been performed to determine ground state vibrational frequencies and the presence of any low-lying electronic states. Rotationally resolved spectra for these molecules have also been taken and the analysis is proceeding. The most recent results will be presented. F. Wang et al., Journal of Chemical Physics 139, 174318 (2013). N. Wang et al., Journal of Physical Chemistry A 117, 13279 (2013). T. Steimle et al., Journal of Chemical Physics 119, 12965 (2003). N. Wang et al., Chemical Physics Letters 547, 21 (2012).

Effect of Solvent Dielectric Constant on the Formation of Large Flat Bilayer Stacks in a Lecithin/Hexadecanol Hydrogel.

PubMed

Nakagawa, Yasuharu; Nakazawa, Hiromitsu; Kato, Satoru

2016-07-12

We investigated the effect of dielectric properties of the aqueous medium on the novel type of hydrogel composed of a crude lecithin mixture (PC70) and hexadecanol (HD), in which charged sheet-like bilayers are kept far apart due to interbilayer repulsive interaction. We used dipropylene glycol (DPG) as a modifier of the dielectric properties and examined its effect on the hydrogel by synchrotron X-ray diffraction, differential scanning calorimetry (DSC), polarized optical microscopy, and freeze-fracture electron microscopy. We found that at a DPG weight fraction in the aqueous medium WDPG ≈ 0.4, the bilayer organization is transformed into unusually large flat bilayer stacks with a regular lamellar spacing of 6.25 nm and consequently disintegration of the hydrogel takes place. Semiquantitative calculation of the interbilayer interaction energy based on the Deyaguin-Landau-Verwey-Overbeek (DLVO) theory suggested that the reduction of the aqueous medium dielectric constant ε by DPG may lower the energy barrier preventing flat bilayers from coming closer together. We inferred that the size of the bilayer sheet increases because the reduction of ε promotes protonation of acidic lipids that work as edge-capping molecules.

Functionalized ZnO nanowires for microcantilever biosensors with enhanced binding capability.

PubMed

Stassi, Stefano; Chiadò, Alessandro; Cauda, Valentina; Palmara, Gianluca; Canavese, Giancarlo; Laurenti, Marco; Ricciardi, Carlo

2017-04-01

An efficient way to increase the binding capability of microcantilever biosensors is here demonstrated by growing zinc oxide nanowires (ZnO NWs) on their active surface. A comprehensive evaluation of the chemical compatibility of ZnO NWs brought to the definition of an innovative functionalization method able to guarantee the proper immobilization of biomolecules on the nanostructured surface. A noteworthy higher amount of grafted molecules was evidenced with colorimetric assays on ZnO NWs-coated devices, in comparison with functionalized and activated silicon flat samples. ZnO NWs grown on silicon microcantilever arrays and activated with the proposed immobilization strategy enhanced the sensor binding capability (and thus the dynamic range) of nearly 1 order of magnitude, with respect to the commonly employed flat functionalized silicon devices. Graphical Abstract An efficient way to increase the binding capability of microcantilever biosensors is represented by growing zinc oxide nanowires (ZnO NWs) on their active surface. ZnO NWs grown on silicon microcantilever arrays and activated with an innovative immobilization strategy enhanced the sensor binding capability of nearly 1 order of magnitude, with respect to the commonly employed flat functionalized silicon devices.

Preliminary report on the coal resources of the Dickenson area, Billings, Dunn, and Stark counties, North Dakota

USGS Publications Warehouse

Menge, Michael L.

1977-01-01

The Dickinson area is underlain by the coal-bearing Fort Union Formation (Paleocene). The Fort Union in this area contains nine potentially economic coal beds. Five of these beds are, either all or in part, shallow enough to be economically extracted by conventional strip-mining methods, while the remaining four deeper beds represent future possible strip-mining, in situ, or shaft-mining coal resources. The Fort Union coal beds in the Dickinson area are relatively flat lying (dips are less than 1??) and only slightly influenced by faulting and both depositional and post-depositional channeling. Topography, coal thickness, and minimum overburden all combine to give the Dickinson area an excellent future coal resource development potential.

Synthesis of new oligothiophene derivatives and their intercalation compounds: Orientation effects

USGS Publications Warehouse

Ibrahim, M.A.; Lee, B.-G.; Park, N.-G.; Pugh, J.R.; Eberl, D.D.; Frank, A.J.

1999-01-01

The orientation dependence of intercalated oligothiophene derivatives in vermiculite and metal disulfides MS2 (M = Mo, Ti and Zr) on the pendant group on the thiophene ring and the host material was studied by X-ray diffraction (XRD) and solid state nuclear magnetic resonance spectroscopy. Amino and nitro derivatives of bi-, ter- and quarter-thiophenes were synthesized for the first time. The amino-oligothiophenes were intercalated into vermiculite by an exchange reaction with previously intercalated octadecylammonium vermiculite and into MS2 by the intercalation-exfoliation technique. Analysis of the XRD data indicates that a monolayer of amino-oligothiophene orients perpendicularly to the silicate surface in vermiculite and lies flat in the van der Waals gap of MS2.

Water resources of the Two Rivers Watershed, Northwestern Minnesota

USGS Publications Warehouse

Maclay, R.W.; Winter, Thomas C.; Pike, G.M.

1967-01-01

It lies in parts of Kittson and Roseau counties and includes the drainage basins of the Two Rivers and Joe River. The flat lake plain which extends 15 to 20 miles east of the Red River of the North is extensively cultivated for small grains and sugar beets. The gently undulating till plain is cultivated largely for small grains and hay. The areas not under cultivation support a forest of poplar with some maple and oak. Oak is the predominate tree on the sandy ridges. The large peat areas are covered with brush and marsh grasslands. Outdoor recreational facilities in the watershed consist principally of the Lake Bronson Park, water-fowl hunting in the extensive marshlands, and deer and small game hunting in the forested areas.

A comprehensive study of extended tetrathiafulvalene cruciform molecules for molecular electronics: synthesis and electrical transport measurements.

PubMed

Parker, Christian R; Leary, Edmund; Frisenda, Riccardo; Wei, Zhongming; Jennum, Karsten S; Glibstrup, Emil; Abrahamsen, Peter Bæch; Santella, Marco; Christensen, Mikkel A; Della Pia, Eduardo Antonio; Li, Tao; Gonzalez, Maria Teresa; Jiang, Xingbin; Morsing, Thorbjørn J; Rubio-Bollinger, Gabino; Laursen, Bo W; Nørgaard, Kasper; van der Zant, Herre; Agrait, Nicolas; Nielsen, Mogens Brøndsted

2014-11-26

Cruciform-like molecules with two orthogonally placed π-conjugated systems have in recent years attracted significant interest for their potential use as molecular wires in molecular electronics. Here we present synthetic protocols for a large selection of cruciform molecules based on oligo(phenyleneethynylene) (OPE) and tetrathiafulvalene (TTF) scaffolds, end-capped with acetyl-protected thiolates as electrode anchoring groups. The molecules were subjected to a comprehensive study of their conducting properties as well as their photophysical and electrochemical properties in solution. The complex nature of the molecules and their possible binding in different configurations in junctions called for different techniques of conductance measurements: (1) conducting-probe atomic force microscopy (CP-AFM) measurements on self-assembled monolayers (SAMs), (2) mechanically controlled break-junction (MCBJ) measurements, and (3) scanning tunneling microscopy break-junction (STM-BJ) measurements. The CP-AFM measurements showed structure-property relationships from SAMs of series of OPE3 and OPE5 cruciform molecules; the conductance of the SAM increased with the number of dithiafulvene (DTF) units (0, 1, 2) along the wire, and it increased when substituting two arylethynyl end groups of the OPE3 backbone with two DTF units. The MCBJ and STM-BJ studies on single molecules both showed that DTFs decreased the junction formation probability, but, in contrast, no significant influence on the single-molecule conductance was observed. We suggest that the origins of the difference between SAM and single-molecule measurements lie in the nature of the molecule-electrode interface as well as in effects arising from molecular packing in the SAMs. This comprehensive study shows that for complex molecules care should be taken when directly comparing single-molecule measurements and measurements of SAMs and solid-state devices thereof.

Ultrafast dynamics and excited state spectra of open-chain carotenoids at room and low temperatures.

PubMed

Niedzwiedzki, Dariusz; Koscielecki, Jeremy F; Cong, Hong; Sullivan, James O; Gibson, George N; Birge, Robert R; Frank, Harry A

2007-05-31

Many of the spectroscopic features and photophysical properties of carotenoids are explained using a three-state model in which the strong visible absorption of the molecules is associated with an S0 (1(1)Ag-) --> S2 (1(1)Bu+) transition, and the lowest lying singlet state, S1 (2(1)Ag-), is a state into which absorption from the ground state is forbidden by symmetry. However, semiempirical and ab initio quantum calculations have suggested additional excited singlet states may lie either between or in the vicinity of S1 (2(1)Ag-) and S2 (1(1)Bu+), and some ultrafast spectroscopic studies have reported evidence for these states. One such state, denoted S*, has been implicated as an intermediate in the depopulation of S2 (1(1)Bu+) and as a pathway for the formation of carotenoid triplet states in light-harvesting complexes. In this work, we present the results of an ultrafast, time-resolved spectroscopic investigation of a series of open-chain carotenoids derived from photosynthetic bacteria and systematically increasing in their number of pi-electron carbon-carbon double bonds (n). The molecules are neurosporene (n = 9), spheroidene (n = 10), rhodopin glucoside (n = 11), rhodovibrin (n = 12), and spirilloxanthin (n = 13). The molecules were studied in acetone and CS2 solvents at room temperature. These experiments explore the effect of solvent polarity and polarizability on the spectroscopic and kinetic behavior of the molecules. The molecules were also studied in ether/isopentane/ethanol (EPA) glasses at 77 K, in which the spectral resolution is greatly enhanced. Analysis of the data using global fitting techniques has revealed the ultrafast dynamics of the excited states and spectral changes associated with their decay, including spectroscopic features not previously reported. The data are consistent with S* being identified with a twisted conformational structure, the yield of which is increased in molecules having longer pi-electron conjugations. In particular, for the longest molecule in the series, spirilloxanthin, the experiments and a detailed quantum computational analysis reveal the presence of two S* states associated with relaxed S1 (2(1)Ag-) conformations involving nearly planar 6-s-cis and 6-s-trans geometries. We propose that in polar solvents, the ground state of spirilloxanthin takes on a corkscrew conformation that generates a net solute dipole moment while decreasing the cavity formation energy. Upon excitation and relaxation into the S1 (2(1)Ag-) state, the polyene unravels and flattens into a more planar geometry with comparable populations of 6-s-trans and 6-s-cis conformations.

Ab Initio Study of Chemical Reactions of Cold SrF and CaF Molecules with Alkali-Metal and Alkaline-Earth-Metal Atoms: The Implications for Sympathetic Cooling.

PubMed

Kosicki, Maciej Bartosz; Kędziera, Dariusz; Żuchowski, Piotr Szymon

2017-06-01

We investigate the energetics of the atom exchange reaction in the SrF + alkali-metal atom and CaF + alkali-metal atom systems. Such reactions are possible only for collisions of SrF and CaF with the lithium atoms, while they are energetically forbidden for other alkali-metal atoms. Specifically, we focus on SrF interacting with Li, Rb, and Sr atoms and use ab initio methods to demonstrate that the SrF + Li and SrF + Sr reactions are barrierless. We present potential energy surfaces for the interaction of the SrF molecule with the Li, Rb, and Sr atoms in their energetically lowest-lying electronic spin states. The obtained potential energy surfaces are deep and exhibit profound interaction anisotropies. We predict that the collisions of SrF molecules in the rotational or Zeeman excited states most likely have a strong inelastic character. We discuss the prospects for the sympathetic cooling of SrF and CaF molecules using ultracold alkali-metal atoms.

(E)-2-[(2,4,6-Tri-meth-oxy-benzyl-idene)amino]-phenol.

PubMed

Kaewmanee, Narissara; Chantrapromma, Suchada; Boonnak, Nawong; Quah, Ching Kheng; Fun, Hoong-Kun

2014-01-01

There are two independent mol-ecules in the asymmetric unit of the title compound, C16H17NO4, with similar conformations but some differences in their bond angles. Each mol-ecule adopts a trans configuration with respect to the methyl-idene C=N bond and is twisted with a dihedral angle between the two substituted benzene rings of 80.52 (7)° in one mol-ecule and 83.53 (7)° in the other. All meth-oxy groups are approximately coplanar with the attached benzene rings, with Cmeth-yl-O-C-C torsion angles ranging from -6.7 (2) to 5.07 (19)°. In the crystal, independent mol-ecules are linked together by O-H⋯N and O-H⋯O hydrogen bonds and a π-π inter-action [centroid-centroid distance of 3.6030 (9) Å], forming a dimer. The dimers are further linked by weak C-H⋯O inter-actions and another π-π inter-action [centroid-centroid distance of 3.9452 (9) Å] into layers lying parallel to the ab plane.

Nanowire Electron Scattering Spectroscopy

NASA Technical Reports Server (NTRS)

Hunt, Brian; Bronikowsky, Michael; Wong, Eric; VonAllmen, Paul; Oyafuso, Fablano

2009-01-01

Nanowire electron scattering spectroscopy (NESS) has been proposed as the basis of a class of ultra-small, ultralow-power sensors that could be used to detect and identify chemical compounds present in extremely small quantities. State-of-the-art nanowire chemical sensors have already been demonstrated to be capable of detecting a variety of compounds in femtomolar quantities. However, to date, chemically specific sensing of molecules using these sensors has required the use of chemically functionalized nanowires with receptors tailored to individual molecules of interest. While potentially effective, this functionalization requires labor-intensive treatment of many nanowires to sense a broad spectrum of molecules. In contrast, NESS would eliminate the need for chemical functionalization of nanowires and would enable the use of the same sensor to detect and identify multiple compounds. NESS is analogous to Raman spectroscopy, the main difference being that in NESS, one would utilize inelastic scattering of electrons instead of photons to determine molecular vibrational energy levels. More specifically, in NESS, one would exploit inelastic scattering of electrons by low-lying vibrational quantum states of molecules attached to a nanowire or nanotube.

Constraints of subducted slab geometries on trench migration and subduction velocities: flat slabs and slab curtains in the mantle under Asia

NASA Astrophysics Data System (ADS)

Wu, J. E.; Suppe, J.; Renqi, L.; Lin, C.; Kanda, R. V.

2013-12-01

The past locations, shapes and polarity of subduction trenches provide first-order constraints for plate tectonic reconstructions. Analogue and numerical models of subduction zones suggest that relative subducting (Vs) and overriding (Vor) plate velocities may strongly influence final subducted slab geometries. Here we have mapped the 3D geometries of subducted slabs in the upper and lower mantle of Asia from global seismic tomography. We have incorporated these slabs into plate tectonic models, which allows us to infer the subducting and overriding plate velocities. We describe two distinct slab geometry styles, ';flat slabs' and ';slab curtains', and show their implications for paleo-trench positions and subduction geometries in plate tectonic reconstructions. When compared to analogue and numerical models, the mapped slab styles show similarities to modeled slabs that occupy very different locations within Vs:Vor parameter space. ';Flat slabs' include large swaths of sub-horizontal slabs in the lower mantle that underlie the well-known northward paths of India and Australia from Eastern Gondwana, viewed in a moving hotspot reference. At India the flat slabs account for a significant proportion of the predicted lost Ceno-Tethys Ocean since ~100 Ma, whereas at Australia they record the existence of a major 8000km by 2500-3000km ocean that existed at ~43 Ma between East Asia, the Pacific and Australia. Plate reconstructions incorporating the slab constraints imply these flat slab geometries were generated when continent overran oceanic lithosphere to produce rapid trench retreat, or in other words, when subducting and overriding velocities were equal (i.e. Vs ~ Vor). ';Slab curtains' include subvertical Pacific slabs near the Izu-Bonin and Marianas trenches that extend from the surface down to 1500 km in the lower mantle and are 400 to 500 km thick. Reconstructed slab lengths were assessed from tomographic volumes calculated at serial cross-sections. The ';slab curtain' geometry and restored slab lengths indicate a nearly stationary Pacific trench since ~43 Ma. In contrast to the flat slabs, here the reconstructed subduction zone had large subducting plate velocities relative to very small overriding plate velocities (i.e. Vs >> Vor). In addition to flat slabs and slab curtains, we also find other less widespread local subduction settings that lie at other locations in Vs:Vor parameter space or involved other processes. Slabs were mapped using Gocad software. Mapped slabs were restored to a spherical model Earth surface by two approaches: unfolding (i.e. piecewise flattening) to minimize shape and area distortions, and by evaluated mapped slab volumes. Gplates software was used to integrate the mapped slabs with plate tectonic reconstructions.

Skin friction and heat transfer correlations for high-speed low-density flow past a flat plate

NASA Technical Reports Server (NTRS)

Woronowicz, Michael S.; Baganoff, Donald

1991-01-01

The independent and dependent variables associated with drag and heat transfer to a flat plate at zero incidence in high-speed, rarefied flow are analyzed anew to reflect the importance of kinetic effects occurring near the plate surface on energy and momentum transfer, rather than following arguments normally used to describe continuum, higher density flowfields. A new parameter, the wall Knudsen number Knx,w, based on an estimate of the mean free path length of molecules having just interacted with the surface of the plate, is introduced and used to correlate published drag and heat transfer data. The new parameter is shown to provide better correlation than either the viscous interaction parameter X or the widely-used slip parameter Voo for drag and heat transfer data over a wide range of Mach numbers, Reynolds numbers, and plate-to-freestream stagnation temperature ratios.

Effect of Ultraviolet Light Irradiation on Structure and Electrochemical Properties of Iron Surface

NASA Astrophysics Data System (ADS)

Nanjo, Hiroshi; Deng, Huihua; Oconer, Irmin S.; Ishikawa, Ikuo; Suzuki, Toshishige M.

2005-01-01

The effect of ultraviolet light (UV) irradiation (254 nm, 0.8 mW/cm2) on air-formed oxide films and passivated films on iron was investigated by electrochemical methods and scanning tunneling microscopy (STM), in particular with respect to surface micro/nanostructures and the surface protective property. An as-deposited film appeared uniformly flat after UV irradiation for 2-4 h, which is associated with a decrease in current density. UV irradiation for 1-4 h assisted N-dodecylhydroxamic acid (DHA) molecules to strongly bond to the air-formed oxide film. UV irradiation for 1 h led to the formation of a flat terrace of atomic resolution on a surface passivated at 800 mV for 15 min. However, it was difficult to observe a terrace wider than 3 nm on the passive film irradiated for 4 h.

Einstein coefficients and oscillator strengths for low lying state of CO molecules

NASA Astrophysics Data System (ADS)

Swer, S.; Syiemiong, A.; Ram, M.; Jha, A. K.; Saxena, A.

2018-04-01

Einstein Coefficients and Oscillator Strengths for different state of CO molecule have been calculated using LEROY'S LEVEL program and MOLCAS ab initio code. Using the wave function derived from Morse potential and transition dipole moment obtained from ab initio calculation, The potential energy functions were computed for these states using the spectroscopic constants. The Morse potential of these states and electronic transition dipole moment of the transition calculated in a recent ab initio study have been used in LEVEL program to produce transition dipole matrix element for a large number of bands. Einstein Coefficients have also been used to compute the radiative lifetimes of several vibrational levels and the calculated values are compared with other theoretical results and experimental values.

1,3-Bis(chloro-meth-yl)-2-methyl-5-nitro-benzene.

PubMed

Shao, Chang-Lun; Li, Chunyuan; Liu, Zhen; Wei, Mei-Yan; Wang, Chang-Yun

2008-03-20

The title compound, C(9)H(9)Cl(2)NO(2), is a natural product isolated from the endophytic fungus No. B77 of the mangrove tree from the South China Sea coast. In the crystal structure, the mol-ecules lie on twofold axes and form offset stacks through face-to-face π-π inter-actions. Adjacent mol-ecules in each stack are related by a centre of inversion and have an inter-planar separation of 3.53 (1) Å, with a centroid-centroid distance of 3.76 (1) Å. Between stacks, there are C-H⋯O inter-actions to the nitro groups and Cl⋯Cl contacts of 3.462 (1) Å.

Energetics and Dynamics of GaAs Epitaxial Growth via Quantum Wave Packet Studies

NASA Technical Reports Server (NTRS)

Dzegilenko, Fedor N.; Saini, Subhash (Technical Monitor)

1998-01-01

The dynamics of As(sub 2) molecule incorporation into the flat Ga-terminated GaAs(100) surface is studied computationally. The time-dependent Schrodinger equation is solved on a two-dimensional potential energy surface obtained using density functional theory calculations. The probabilities of trapping and subsequent dissociation of the molecular As(sub 2) bond are calculated as a function of beam translational energy and vibrational quantum number of As(sub 2).

Dynamic molecular structure retrieval from low-energy laser-induced electron diffraction spectra

NASA Astrophysics Data System (ADS)

Vu, Dinh-Duy T.; Phan, Ngoc-Loan T.; Hoang, Van-Hung; Le, Van-Hoang

2017-12-01

A recently developed quantitative rescattering theory showed that a laser-free elastic cross section can be separated from laser-induced electron diffraction (LIED) spectra. Based upon this idea, Blaga et al investigated the possibility of reconstructing molecular structure from LIED spectra (2012 Nature 483 7388). In the above study, an independent atoms model (IAM) was used to interpret high-energy electron-molecule collisions induced by a mid-infrared laser. Our research aims to extend the application range of this structural retrieval method to low-energy spectra induced by more common near-infrared laser sources. The IAM is insufficient in this case, so we switch to a more comprehensive model—the multiple scattering (MS) theory. From the original version concerning only neutral targets, we upgrade the model so that it is compatible with electron-ion collisions at low energy. With available LIED experiment data of CO2 and O2, the upgraded MS is shown to be greatly effective as a tool for molecular imaging from spectra induced by a near-infrared laser. The captured image is at about 2 fs after the ionization, shorter than the period 4-6 fs by using the mid-infrared laser in Blaga’s experiment.

Raman imaging of lipid bilayer membrane by surface enhanced Raman scattering

NASA Astrophysics Data System (ADS)

Mori, Motoaki; Abe, Shunsuke; Kondo, Takahiro; Saito, Yuika

2018-04-01

We investigated two-dimensional lipid bilayers by spectroscopic imaging with surface enhanced Raman spectroscopy (SERS). A DSPC lipid bilayer incubated on a glass substrate was coated with a thin layer of silver. Due to the strong electromagnetic enhancement of the silver film and the affinity to lipid molecules, the Raman spectrum of a single bilayer was obtained in a 1 s exposure time with 0.1 mW of incident laser power. In the C-H vibrational region of the spectra, which is sensitive to bilayer configurations, a randomly stacked area was dominated by the CH3 asymmetric-stretch mode, whereas flat areas including double bilayers showed typical SERS spectra. The spectral features of the randomly stacked area are explained by the existence of many free lipid molecules, which is supported by DFT calculations of paired DSPC molecules. Our method can be applied to reveal the local crystallinity of single lipid bilayers, which is difficult to assess by conventional Raman imaging.

Unravelling the molecular structure and packing of a planar molecule by combining nuclear magnetic resonance and scanning tunneling microscopy.

PubMed

Sáfar, Gustavo A M; Malachias, Angelo; Magalhães-Paniago, Rogério; Martins, Dayse C S; Idemori, Ynara M

2013-12-21

The determination of the molecular structure of a porphyrin is achieved by using nuclear magnetic resonance (NMR) and scanning tunneling microscopy (STM) techniques. Since macroscopic crystals cannot be obtained in this system, this combination of techniques is crucial to solve the molecular structure without the need for X-ray crystallography. For this purpose, previous knowledge of the flatness of the reagent molecules (a porphyrin and its functionalizing group, a naphthalimide) and the resulting molecular structure obtained by a force-field simulation are used. The exponents of the I-V curves obtained by scanning tunneling spectroscopy (STS) allow us to check whether the thickness of the film of molecules is greater than a monolayer, even when there is no direct access to the exposed surface of the metal substrate. Photoluminescence (PL), optical absorption, infrared (IR) reflectance and solubility tests are used to confirm the results obtained here with this NMR/STM/STS combination.

Adjusting the surface areal density of click-reactive azide groups by kinetic control of the azide substitution reaction on bromine-functional SAMs.

PubMed

Zhang, Shuo; Maidenberg, Yanir; Luo, Kai; Koberstein, Jeffrey T

2014-06-03

Azide-alkyne click chemistry has emerged as an important and versatile means for tethering a wide variety of guest molecules to virtually any substrate. In many of these applications, it is important to exercise control over the areal density of surface functional groups to achieve a desired areal density of the tethered guest molecule of interest. We demonstrate herein that the areal density of surface azide groups on flat germanium surfaces and nanoparticle substrates (silica and iron oxide) can be controlled kinetically by appropriately timed quenching of the S(N)2 substitution reaction of bromo-alkane-silane monolayers induced by the addition of sodium azide. The kinetics of the azide substitution reaction on monolayers formed on flat Ge substrates, determined by attenuated total reflection infrared spectroscopy (ATR-IR), are found to be identical to those for monolayers formed on both silica and iron oxide nanoparticles, the latter determined by transmission infrared spectroscopy. To validate the method, the percentages of surface bromine groups converted to azide groups after various reaction times were measured by quenching the S(N)2 reaction followed by analysis with ATR-IR (for Ge) and thermogravimetric analysis (after a subsequent click reaction with an alkyne-terminal polymer) for the nanoparticle substrates. The conversions found after quenching agree well with those expected from the standard kinetic curves. The latter result suggests that the kinetic method for the control of azide group areal density is a versatile means for functionalizing substrates with a prescribed areal density of azide groups for subsequent click reactions, and that the method is universal for any substrate, flat or nanoparticle, that can be modified with bromo-alkane-silane monolayers. Regardless of the surface geometry, we find that the azide substitution reaction is complete within 2-3 h, in sharp contrast to previous reports that indicate times of 48-60 h required for completion of the reaction.

Molecular self assembly and chiral recognition of copper octacyanophthalocyanine on Au(111): Interplay of intermolecular and molecule-substrate interactions.

NASA Astrophysics Data System (ADS)

Sk, Rejaul; Dhara, Barun; Miller, Joel; Deshpande, Aparna

Submolecular resolution scanning tunneling microscopy (STM) of copper octacyanophthalocyanine, CuPc(CN)8, at 77 K demonstrates that these achiral molecules form a two dimensional (2D) tetramer-based self-assembly upon evaporation onto an atomically flat Au(111) substrate. They assemble in two different structurally chiral configurations upon adsorption on Au(111). Scanning tunneling spectroscopy (STS),acquired at 77 K, unveils the HOMO and LUMO energy levels of this self-assembly. Voltage dependent STM images show that each molecule in both the structurally chiral configurations individually becomes chiral by breaking the mirror symmetry due to the enhanced intermolecular dipolar coupling interaction at the LUMO energy while the individual molecules remain achiral at the HOMO energy and within the HOMO-LUMO gap. At the LUMO energy, the handedness of the each chiral molecule is decided by the direction of the dipolar coupling interaction in the tetramer unit cell. This preference for LUMO energy indicates that this chirality is purely electronic in nature and it manifests on top of the organizational chirality that is present in the self-assembly independent of the orbital energy. Supported by IISER Pune and DAE-BRNS, India (Project No. 2011/20/37C/17/BRNS).

Concentration profiles of actin-binding molecules in lamellipodia

NASA Astrophysics Data System (ADS)

Falcke, Martin

2016-04-01

Motile cells form lamellipodia in the direction of motion, which are flat membrane protrusions containing an actin filament network. The network flows rearward relative to the leading edge of the lamellipodium due to actin polymerization at the front. Thus, actin binding molecules are subject to transport towards the rear of the cell in the bound state and diffuse freely in the unbound state. We analyze this reaction-diffusion-advection process with respect to the concentration profiles of these species and provide an analytic approximation for them. Network flow may cause a depletion zone of actin binding molecules close to the leading edge. The existence of such zone depends on the free molecule concentration in the cell body, on the ratio of the diffusion length to the distance bound molecules travel rearward with the flow before dissociating, and the ratio of the diffusion length to the width of the region with network flow and actin binding. Our calculations suggest the existence of depletion zones for the F-actin cross-linkers filamin and α-actinin in fish keratocytes (and other cell types), which is in line with the small elastic moduli of the F-actin network close to the leading edge found in measurements of the force motile cells are able to exert.

Electronic spectroscopy of HRe(CO) 5: a CASSCF/CASPT2 and TD-DFT study

NASA Astrophysics Data System (ADS)

Bossert, J.; Ben Amor, N.; Strich, A.; Daniel, C.

2001-07-01

The low-lying excited states of HRe(CO) 5 have been calculated at the CASSCF/CASPT2 and TD-DFT level of theory using relativistic effective core potentials (ECP) or ab initio model potentials (AIMP). The theoretical absorption spectrum is compared to the experimental one. Despite the similarity between the experimental absorption spectra of HMn(CO) 5 and HRe(CO) 5 in the UV/visible energy domain it is shown that the assignment differs significantly between the two molecules. The low-lying excited states of HRe(CO) 5 correspond to 5d→π *CO excitations whereas the spectrum of HMn(CO) 5 consists mainly of 3d→3d and 3d→ σ*Mn-H excitations. If the CASPT2 and TD-DFT results are quite comparable for the lowest excited states, the upper part assignment is more problematic with the TD-DFT method.

A cubic scaling algorithm for excited states calculations in particle-particle random phase approximation

NASA Astrophysics Data System (ADS)

Lu, Jianfeng; Yang, Haizhao

2017-07-01

The particle-particle random phase approximation (pp-RPA) has been shown to be capable of describing double, Rydberg, and charge transfer excitations, for which the conventional time-dependent density functional theory (TDDFT) might not be suitable. It is thus desirable to reduce the computational cost of pp-RPA so that it can be efficiently applied to larger molecules and even solids. This paper introduces an O (N3) algorithm, where N is the number of orbitals, based on an interpolative separable density fitting technique and the Jacobi-Davidson eigensolver to calculate a few low-lying excitations in the pp-RPA framework. The size of the pp-RPA matrix can also be reduced by keeping only a small portion of orbitals with orbital energy close to the Fermi energy. This reduced system leads to a smaller prefactor of the cubic scaling algorithm, while keeping the accuracy for the low-lying excitation energies.

Manson impact structure, Iowa: First geochemical results for drill core M-1

NASA Technical Reports Server (NTRS)

Koeberl, Christian; Anderson, Raymond R.; Hartung, Jack B.; Reimold, Wolf Uwe

1993-01-01

The Manson Impact Structure is a large complex impact crater centered ca. S km north of the town of Manson, Iowa. It is the largest intact impact structure recognized in the United States (35 km in diameter). Its Ar-40/Ar-39 age is indistinguishable from that of the Cretaceous-Tertiary (K-T) boundary. The Manson structure may be one element of the events at the K-T boundary. The crater is completely covered by Quaternary glacial sedimentary deposits that are normally underlain by Cretaceous clastic sediments and flat-lying carbonate sediments of Phanerozoic age, as well as Proterozoic red clastic, metamorphic, volcanic, and plutonic rock sequences. The study of a reflection seismic profile, provided by Amoco, was critical in interpreting the structure. In the 35 km diameter zone that marks the extension of the crater the normal rock sequence is disturbed due to the impact, and at the center of the structure granitic basement rocks are present that have been uplifted from about 4 km depth. Our studies consist of detailed petrological and geochemical characterization of all cores, with emphasis on a detailed description of all rock types found in the core samples and their relationship to target rocks. Geochemical data on samples from the Manson M-1 core are presented.

Manson impact structure, Iowa: First geochemical results for drill core M-1

NASA Astrophysics Data System (ADS)

Koeberl, Christian; Anderson, Raymond R.; Hartung, Jack B.; Reimold, Wolf Uwe

1993-03-01

The Manson Impact Structure is a large complex impact crater centered ca. S km north of the town of Manson, Iowa. It is the largest intact impact structure recognized in the United States (35 km in diameter). Its Ar-40/Ar-39 age is indistinguishable from that of the Cretaceous-Tertiary (K-T) boundary. The Manson structure may be one element of the events at the K-T boundary. The crater is completely covered by Quaternary glacial sedimentary deposits that are normally underlain by Cretaceous clastic sediments and flat-lying carbonate sediments of Phanerozoic age, as well as Proterozoic red clastic, metamorphic, volcanic, and plutonic rock sequences. The study of a reflection seismic profile, provided by Amoco, was critical in interpreting the structure. In the 35 km diameter zone that marks the extension of the crater the normal rock sequence is disturbed due to the impact, and at the center of the structure granitic basement rocks are present that have been uplifted from about 4 km depth. Our studies consist of detailed petrological and geochemical characterization of all cores, with emphasis on a detailed description of all rock types found in the core samples and their relationship to target rocks. Geochemical data on samples from the Manson M-1 core are presented.

A Closer Look at Holden Crater

NASA Image and Video Library

2017-03-15

Holden Crater in southern Margaritifer Terra displays a series of finely layered deposits on its floor. The layered deposits are especially well exposed in the southwestern section of the crater where erosion by water flowing through a breach in the crater rim created spectacular outcrops. In this location, the deposits appear beneath a cap of alluvial fan materials (tan to brown in this image). Within the deposits, individual layers are nearly flat-lying and can be traced for hundreds of meters to kilometers. Information from the CRISM instrument on the Mars Reconnaissance Orbiter suggests that at least some of these beds contain clays. By contrast, the beds in the overlying alluvial fan are less continuous and dip in varying directions, showing less evidence for clays. Collectively, the characteristics of the finely bedded deposits suggest they may have been deposited into a lake on the crater floor, perhaps fed by runoff related to formation of the overlying fans. The map is projected here at a scale of 25 centimeters (9.8 inches) per pixel. [The original image scale is 25.9 centimeters (10.2 inches) per pixel (with 1 x 1 binning); objects on the order of 78 centimeters (30.7 inches) across are resolved.] North is up. http://photojournal.jpl.nasa.gov/catalog/PIA21561

Assessment of shoreline vegetation in relation to use by molting black brant Branta bernicla nigricans on the Alaska Coastal Plain

USGS Publications Warehouse

Weller, Milton W.; Jensen, K.C.; Taylor, Eric J.; Miller, Mark W.; Bollinger, Karen S.; Derksen, Dirk V.; Esler, Daniel N.; Markon, Carl J.

1994-01-01

To evaluate the importance of large thaw lakes on the Alaska Coastal Plain for molting Pacific black brant Branta bernicla nigricans, distribution and life form of shoreline vegetation were assessed using several scales: satellite imagery, point-intercept transects, cover quadrats, and a parameter for water regime. Brant population and distribution estimates from aerial surveys were used to classify large lakes into high, moderate, and low use. Correlations between brant and abundance of their preferred feeding site - moss flats - were best demonstrated by satellite imagery. Intercepts and cover ratings were not correlated, presumably because these techniques were less efficient at assessing area. General observations suggested that the presence of islands, large ice floes, and possibly other physical attributes of the habitat, influenced brant distribution. This area is unique because of low-lying, drained-lake basins that have ideal combinations of moss flats and large water areas where brant seek protection disturbance is vital to the success of this declining species because alternate habitats may not be available elsewhere on the Coastal Plain. in water or on ice floes. Protection of the area from disturbance is vital to the success of this declining species because alternate habitats may not be available elsewhere on the Coastal Plain.

Geology and undiscovered resource assessment of the potash-bearing Central Asia Salt Basin, Turkmenistan, Uzbekistan, Tajikistan, and Afghanistan: Chapter AA in Global mineral resource assessment

USGS Publications Warehouse

Wynn, Jeff; Orris, Greta J.; Dunlap, Pamela; Cocker, Mark D.; Bliss, James D.

2016-03-23

Chapter 1 of this report provides an overview of the history of the CASB and summarizes evaporite potash deposition, halokinesis, and dissolution processes that have affected the current distribution of potash-bearing salt in the CASB. Chapter 2 describes the Gissar tract, an uplifted region that contains a mix of stratabound and halokinetic potash deposits and all of the discovered and exploited potash deposits of the CASB. Chapter 3 describes the Amu Darya tract, where evaporite deposits remain flat-lying and undeformed since their original deposition. Chapter 4 describes the highly deformed and compressed Afghan-Tajik tract and what is known of the deeply-buried Jurassic salt. Chapter 5 describes the spatial databases included with this report, which contain a collection of CASB potash information. Appendixes A and B summarize descriptive models for stratabound and halokinetic potash-bearing salt deposits, respectively. Appendix C summarizes the AGE method used to evaluate the Gissar and Amu Darya tracts. Appendixes D and E contain grade and thickness data for the Gissar and Amu Darya tracts. Appendix F provides the SYSTAT script used to estimate undiscovered K2 O in a CASB tract. Appendix G provides a potash glossary, and appendix H provides biographies of assessment participants.

Crew Earth Observations over Utah taken during Expedition 12

NASA Image and Video Library

2005-10-14

ISS012-E-05172 (14 October 2005) --- Navajo Mountain, Utah is featured in this image photographed by an Expedition 12 crewmember on the international space station. According to scientists, the Colorado Plateau of Arizona, Colorado, New Mexico, and Utah is characterized by mostly flat-lying sedimentary layers that record paleoclimate extremes ranging from oceans to widespread deserts over the last 1.8 billion years. Navajo Mountain is formed by a dome-shaped body of igneous rock (called a laccolith by geologists), one of several in southeast Utah that intrude and uplift the surrounding sedimentary layers of the Plateau. This oblique image highlights Navajo Mountain in the center of the image, surrounded by light red-brown Navajo Sandstone (also visible in canyons at bottom of image). Scientists believe the peak of Navajo Mountain, at approximately 3148 meters (10,388 feet) elevation, is comprised of uplifted Dakota Sandstone deposited during the Cretaceous Period. The establishment of Rainbow Bridge National Monument (1910), and the filling of Glen Canyon by Lake Powell in 1963 (upper right), have facilitated tourism and aesthetic appreciation of this previously remote region. Access to Navajo Mountain is still regulated by the sovereign Navajo Nation, and the process of permitting is required to hike in the region.

Smart vortex generator transformed by change in ambient temperature and aerodynamic force

NASA Astrophysics Data System (ADS)

Ikeda, Tadashige; Masuda, Shinya; Ueda, Tetsuhiko

2007-04-01

A Smart Vortex Generator (SVG) concept has been proposed, where the SVG is autonomously transformed between an upright vortex-generating position in take-off and landing and a flat drag-reducing position in a cruise. This SVG is made of a Shape Memory Alloy (SMA), which is in the austenite phase and memorizes the upright position at high temperatures of the take-off and landing. At low temperatures during ascent the SVG is transformed into a martensite phase, and it lies flat against a base structure due to external or/and internal forces. In this paper, we examine whether the SVG can be transformed into the drag-reducing position by an aerodynamic force. To this end, numerical simulations are carried out with a simple line element model. The aerodynamic force applied on the SVG is calculated by a commercial CFD program. Result reveals that this SVG can be transformed from the upright vortex-generating position into the drag-reducing position by just an airplane climbing, and vice versa, if the SMA applied to the SVG has the two-way shape memory effect. If the SMA has the one-way shape memory effect, it is necessary to reduce the stiffness of the SVG or/and use a counter spring.

Geologic map of the Van Buren South quadrangle, Carter County, Missouri

USGS Publications Warehouse

Weary, D.J.; Schindler, J.S.

2004-01-01

The bedrock exposed in the Van Buren South quadrangle, Missouri, comprises Late Cambrian and Early Ordovician aged dolomite, sandstone, and chert. The sedimentary rocks are nearly flat-lying except where they are adjacent to faults. The carbonate rocks are karstified and the area contains numerous sinkholes, springs, caves, and losing-streams. This map is one of several being produced under the U.S. Geological Survey National Cooperative Geologic Mapping Program to provide geologic data applicable to land-use problems in the Ozarks of south-central Missouri. Ongoing and potential industrial and agricultural development in the Ozarks region has presented issues of ground-water quality in karst areas. A National Park in this region (Ozark National Scenic Riverways, Missouri ) is concerned about the effects of activities in areas outside of their stewardship on the water resources that define the heart of this Park. This task applies geologic mapping and karst investigations to address issues surrounding competing land use in south-central Missouri. This task keeps geologists from the USGS associated with the park and allows the Parks to utilize USGS expertise and aid the NPS on how to effectively use geologic maps for Park management. For more information see: http://geology.er.usgs.gov/eespteam/Karst/index.html

Geologic map of the Low Wassie Quadrangle, Oregon and Shannon counties, Missouri

USGS Publications Warehouse

Weems, Robert E.

2002-01-01

The bedrock exposed in the Low Wassie Quadrangle, Missouri, comprises Late Cambrian and Early Ordovician aged dolomite, sandstone, and chert. The sedimentary rocks are nearly flat-lying except where they are adjacent to faults. The carbonates are karstified and the area contains numerous sinkholes, springs, caves, and losing-streams. This map is one of several being produced under the U.S. Geological Survey National Cooperative Geologic Mapping Program to provide geologic data applicable to land-use problems in the Ozarks of south-central Missouri. Ongoing and potential industrial and agricultural development in the Ozarks region has presented issues of ground-water quality in karst areas. A National Park in this region (Ozark National Scenic Riverways, Missouri ) is concerned about the effects of activities in areas outside of their stewardship on the water resources that define the heart of this Park. This task applies geologic mapping and karst investigations to address issues surrounding competing land use in south-central Missouri. This task keeps geologists from the USGS associated with the park and allows the Parks to utilize USGS expertise and aid the NPS on how to effectively use geologic maps for Park management. For more information see: http://geology.er.usgs.gov/eespteam/Karst/index.html.

Geologic map of the Winona Quadrangle, Shannon County, Missouri

USGS Publications Warehouse

Orndorff, R.C.; Harrison, R.W.

2001-01-01

The bedrock exposed in the Winona Quadrangle, Missouri, comprises Mesoproterozoic aged volcanic rocks overlain by Late Cambrian and Early Ordovician aged dolomite, sandstone, and chert. The sedimentary rocks are nearly flat-lying except where they drape around knobs of the volcanic rocks or where they are adjacent to faults. The carbonates are karstified and the area contains numerous sinkholes, springs, caves, and losing-streams. This map is one of several being produced under the U.S. Geological Survey National Cooperative Geologic Mapping Program to provide geologic data applicable to land-use problems in the Ozarks of south-central Missouri. Ongoing and potential industrial and agricultural development in the Ozarks region has presented issues of ground-water quality in karst areas. A National Park in this region (Ozark National Scenic Riverways, Missouri ) is concerned about the effects of activities in areas outside of their stewardship on the water resources that define the heart of this Park. This task applies geologic mapping and karst investigations to address issues surrounding competing land use in south-central Missouri. This task keeps geologists from the USGS associated with the park and allows the Parks to utilize USGS expertise and aid the NPS on how to effectively use geologic maps for Park management. For more information see: http://geology.er.usgs.gov/eespteam/Karst/index.html

Machine vision based quality inspection of flat glass products

NASA Astrophysics Data System (ADS)

Zauner, G.; Schagerl, M.

2014-03-01

This application paper presents a machine vision solution for the quality inspection of flat glass products. A contact image sensor (CIS) is used to generate digital images of the glass surfaces. The presented machine vision based quality inspection at the end of the production line aims to classify five different glass defect types. The defect images are usually characterized by very little `image structure', i.e. homogeneous regions without distinct image texture. Additionally, these defect images usually consist of only a few pixels. At the same time the appearance of certain defect classes can be very diverse (e.g. water drops). We used simple state-of-the-art image features like histogram-based features (std. deviation, curtosis, skewness), geometric features (form factor/elongation, eccentricity, Hu-moments) and texture features (grey level run length matrix, co-occurrence matrix) to extract defect information. The main contribution of this work now lies in the systematic evaluation of various machine learning algorithms to identify appropriate classification approaches for this specific class of images. In this way, the following machine learning algorithms were compared: decision tree (J48), random forest, JRip rules, naive Bayes, Support Vector Machine (multi class), neural network (multilayer perceptron) and k-Nearest Neighbour. We used a representative image database of 2300 defect images and applied cross validation for evaluation purposes.

Lipid-Mediated Clusters of Guest Molecules in Model Membranes and Their Dissolving in the Presence of Lipid Rafts.

PubMed

Kardash, Maria E; Dzuba, Sergei A

2017-05-25

The clustering of molecules is an important feature of plasma membrane organization. It is challenging to develop methods for quantifying membrane heterogeneities because of their transient nature and small size. Here, we obtained evidence that transient membrane heterogeneities can be frozen at cryogenic temperatures which allows the application of solid-state experimental techniques sensitive to the nanoscale distance range. We employed the pulsed version of electron paramagnetic resonance (EPR) spectroscopy, the electron spin echo (ESE) technique, for spin-labeled molecules in multilamellar lipid bilayers. ESE decays were refined for pure contribution of spin-spin magnetic dipole-dipolar interaction between the labels; these interactions manifest themselves at a nanometer distance range. The bilayers were prepared from different types of saturated and unsaturated lipids and cholesterol (Chol); in all cases, a small amount of guest spin-labeled substances 5-doxyl-stearic-acid (5-DSA) or 3β-doxyl-5α-cholestane (DChl) was added. The local concentration found of 5-DSA and DChl molecules was remarkably higher than the mean concentration in the bilayer, evidencing the formation of lipid-mediated clusters of these molecules. To our knowledge, formation of nanoscale clusters of guest amphiphilic molecules in biological membranes is a new phenomenon suggested only recently. Two-dimensional 5-DSA molecular clusters were found, whereas flat DChl molecules were found to be clustered into stacked one-dimensional structures. These clusters disappear when the Chol content is varied between the boundaries known for lipid raft formation at room temperatures. The room temperature EPR evidenced entrapping of DChl molecules in the rafts.

Collision Dynamics of Rydberg Atoms and Molecules at Ultralow Energies

DTIC Science & Technology

2005-12-31

body recombination between electrons, ions and neural gas atoms. We wish to study the interaction and collisions between two Rydberg atoms in the...transitions, Exact solutions of Stark mixing in atomic hydro- where Ekjn is the Levi - Civita antisymmetric symbol gen induced by the time-dependent...L and U do not close under commutation to form a Lie algebra because [Ui, Uj] = (-2g)iCijkLk, where cijk is the Levi - Civita antisymmetric symbol for

trans-Bis(azido-kappaN)bis(pyridine-2-carboxamide-kappa2N1,O2)nickel(II).

PubMed

Daković, Marijana; Popović, Zora

2007-11-01

In the title compound, [Ni(N(3))(2)(C(6)H(6)N(2)O)(2)], the Ni(II) atom lies on an inversion centre. The distorted octahedral nickel(II) coordination environment contains two planar trans-related N,O-chelating picolinamide ligands in one plane and two monodentate azide ligands perpendicular to this plane. Molecules are linked into a three-dimensional framework by N-H...N hydrogen bonds.

7-Meth­oxy­indan-1-one

PubMed Central

Chang, Yuan Jay; Chen, Kew-Yu

2012-01-01

In the title compound, C10H10O2, the 1-indanone unit is essentially planar (r.m.s. deviation = 0.028 Å). In the crystal, molecules are linked via C—H⋯O hydrogen bonds, forming layers lying parallel to the ab plane. This two-dimensional structure is stabilized by a weak C—H⋯π inter­action. A second weak C—H⋯π inter­action links the layers, forming a three-dimensional structure. PMID:23284398

Di-tert-butyl-bis(N-isopropyl-N-methyl-dithio-carbamato-κS,S')tin(IV).

PubMed

Muthalib, Amirah Faizah; Baba, Ibrahim; Samsudin, Mohd Wahid; Ng, Seik Weng

2010-03-03

The dithio-carbamate anions in the title compound, [Sn(C(4)H(9))(2)(C(5)H(10)NS(2))(2)], chelate to the Sn(IV) atom, which is six-coordinated in a skew-trapezoidal-bipyramidal geometry. The mol-ecule lies across a twofold rotation axis. The crystal studied was a non-merohedral twin, the ratio of the twin components being 0.82 (1):0.18 (1).

A Method for Increasing the Firepower of Virginia Class Cruisers.

DTIC Science & Technology

1982-04-01

Invited paper peented at the CHIS mesting an wthmatical Problms In feyaan’s Park PP 212 Integrals. Marseille. France. May 22-26, 1978) (Poi shed Mengel ...1978, 234-253) PD AD55 536 AD ADSS 33 PP 223 PP 213 Mengel . Marc, "Stochastic mechanics of moleajielon Molecule Mengel , Marc, "Fluctuations In...Strategic Naqivresents end PP 225 Military PFeteret), Chicago, Ill., Septmer 2, 1978). Mengel . Marc. -Oscillations, Fluctuations, end lie Hopt AD A056

Low-lying excited states by constrained DFT.

PubMed

Ramos, Pablo; Pavanello, Michele

2018-04-14

Exploiting the machinery of Constrained Density Functional Theory (CDFT), we propose a variational method for calculating low-lying excited states of molecular systems. We dub this method eXcited CDFT (XCDFT). Excited states are obtained by self-consistently constraining a user-defined population of electrons, N c , in the virtual space of a reference set of occupied orbitals. By imposing this population to be N c = 1.0, we computed the first excited state of 15 molecules from a test set. Our results show that XCDFT achieves an accuracy in the predicted excitation energy only slightly worse than linear-response time-dependent DFT (TDDFT), but without incurring into problems of variational collapse typical of the more commonly adopted ΔSCF method. In addition, we selected a few challenging processes to test the limits of applicability of XCDFT. We find that in contrast to TDDFT, XCDFT is capable of reproducing energy surfaces featuring conical intersections (azobenzene and H 3 ) with correct topology and correct overall energetics also away from the intersection. Venturing to condensed-phase systems, XCDFT reproduces the TDDFT solvatochromic shift of benzaldehyde when it is embedded by a cluster of water molecules. Thus, we find XCDFT to be a competitive method among single-reference methods for computations of excited states in terms of time to solution, rate of convergence, and accuracy of the result.

Spectroscopic Study and Astronomical Detection of Vibrationally Excited n-PROPYL Cyanide

NASA Astrophysics Data System (ADS)

Müller, Holger S. P.; Wehres, Nadine; Wilkins, Olivia H.; Lewen, Frank; Schlemmer, Stephan; Walters, Adam; Vicente, Rémi; Liu, Delong; Garrod, Robin T.; Belloche, Arnaud; Menten, Karl M.

2016-06-01

We have obtained ALMA data of Sagittarius (Sgr for short) B2(N) between 84.0 and 114.4 GHz in its Early Science Cycles 0 and 1. We have focused our analyses on the northern, secondary hot molecular core Sgr B2(N2) because of the smaller line widths. The survey led to the first detection of a branched alkyl compound, iso-propyl cyanide, i-C_3H_7CN, in space besides the ˜2.5 times more abundant straight chain isomer n-propyl cyanide, a molecule which we had detected in our IRAM 30 m survey. We suspected to be able to detect n-propyl cyanide in vibrationally excited states in our ALMA data. We have recorded laboratory rotational spectra of this molecule in three large frequency regions and identified several excited vibrational states. The analyses of these spectra have focused on the 36 to 70 GHz and 89 to 127 GHz regions and on the four lowest excited vibrational states of both the lower lying gauche- and the slightly higher lying anti-conformer for which rotational constants had been published. We will present results of our laboratory spectroscopic investigations and will report on the detection of these states toward Sgr B2(N2). A. Belloche et al., Science 345 (2014) 1584. A. Belloche et al., A&A 499 (2009) 215. E. Hirota, J. Chem. Phys. 37 (1962) 2918.

Flat and complex temperate reefs provide similar support for fish: Evidence for a unimodal species-habitat relationship.

PubMed

Paxton, Avery B; Pickering, Emily A; Adler, Alyssa M; Taylor, J Christopher; Peterson, Charles H

2017-01-01

Structural complexity, a form of habitat heterogeneity, influences the structure and function of ecological communities, generally supporting increased species density, richness, and diversity. Recent research, however, suggests the most complex habitats may not harbor the highest density of individuals and number of species, especially in areas with elevated human influence. Understanding nuances in relationships between habitat heterogeneity and ecological communities is warranted to guide habitat-focused conservation and management efforts. We conducted fish and structural habitat surveys of thirty warm-temperate reefs on the southeastern US continental shelf to quantify how structural complexity influences fish communities. We found that intermediate complexity maximizes fish abundance on natural and artificial reefs, as well as species richness on natural reefs, challenging the current paradigm that abundance and other fish community metrics increase with increasing complexity. Naturally occurring rocky reefs of flat and complex morphologies supported equivalent abundance, biomass, species richness, and community composition of fishes. For flat and complex morphologies of rocky reefs to receive equal consideration as essential fish habitat (EFH), special attention should be given to detecting pavement type rocky reefs because their ephemeral nature makes them difficult to detect with typical seafloor mapping methods. Artificial reefs of intermediate complexity also maximized fish abundance, but human-made structures composed of low-lying concrete and metal ships differed in community types, with less complex, concrete structures supporting lower numbers of fishes classified largely as demersal species and metal ships protruding into the water column harboring higher numbers of fishes, including more pelagic species. Results of this study are essential to the process of evaluating habitat function provided by different types and shapes of reefs on the seafloor so that all EFH across a wide range of habitat complexity may be accurately identified and properly managed.

A comparison of force fields and calculation methods for vibration intervals of isotopic H3(+) molecules

NASA Astrophysics Data System (ADS)

Carney, G. D.; Adler-Golden, S. M.; Lesseski, D. C.

1986-04-01

This paper reports (1) improved values for low-lying vibration intervals of H3(+), H2D(+), D2H(+), and D3(+) calculated using the variational method and Simons-Parr-Finlan (1973) representations of the Carney-Porter (1976) and Dykstra-Swope (1979) ab initio H3(+) potential energy surfaces, (2) quartic normal coordinate force fields for isotopic H3(+) molecules, (3) comparisons of variational and second-order perturbation theory, and (4) convergence properties of the Lai-Hagstrom internal coordinate vibrational Hamiltonian. Standard deviations between experimental and ab initio fundamental vibration intervals of H3(+), H2D(+), D2H(+), and D3(+) for these potential surfaces are 6.9 (Carney-Porter) and 1.2/cm (Dykstra-Swope). The standard deviations between perturbation theory and exact variational fundamentals are 5 and 10/cm for the respective surfaces. The internal coordinate Hamiltonian is found to be less efficient than the previously employed 't' coordinate Hamiltonian for these molecules, except in the case of H2D(+).

Visualizing the Role of Molecular Orbitals in Charge Transport through Individual Diarylethene Isomers

PubMed Central

2016-01-01

Diarylethene molecules are prototype molecular switches with their two isomeric forms exhibiting strikingly different conductance, while maintaining similar length. We employed low-temperature scanning tunneling microscopy (STM) to resolve the energy and the spatial extend of the molecular orbitals of the open and closed isomers when lying on a Au(111) surface. We find an intriguing difference in the extension of the respective HOMOs and a peculiar energy splitting of the formerly degenerate LUMO of the open isomer. We then lift the two isomers with the tip of the STM and measure the current through the individual molecules. By a simple analytical model of the transport, we show that the previously determined orbital characteristics are essential ingredients for the complete understanding of the transport properties. We also succeeded in switching the suspended molecules by the current, while switching the ones which are in direct contact to the surface occurs nonlocally with the help of the electric field of the tip. PMID:27775886

Origin of the Surface-Induced First Hyperpolarizability in the C60/SiO2 System: SCC-DFTB Insight.

PubMed

Nénon, Sébastien; Champagne, Benoît

2014-01-02

Using the self-consistent charge density functional tight binding (SCC-DFTB) method, C60 molecules physisorbed on an α-quartz slab are shown to display a first hyperpolarizability, whereas, owing to their symmetry, both the α-quartz slab and C60 molecule have no first hyperpolarizabilities. A larger first hyperpolarizability is achieved when the lowest-lying (five- or six-membered) ring is situated in between two hydroxyl rows, rather than on top, because this situation favors orbital overlaps and charge transfer. Further analysis has demonstrated that (i) the first hyperpolarizability originates from the MO overlap and field-induced charge transfers from the neighboring substrate/adsorbate moieties but not to geometric relaxation of the C60 molecules at the interface and that (ii) larger first hyperpolarizabilities are associated with low surface coverage and with small distances between C60 and the surface. This contribution is a clear illustration of the emergence of second-order nonlinear optical responses (first hyperpolarizability) as a result of breaking the centrosymmetry.

Spectroscopy of Cold LiCa Molecules Formed on Helium Nanodroplets

PubMed Central

2013-01-01

We report on the formation of mixed alkali–alkaline earth molecules (LiCa) on helium nanodroplets and present a comprehensive experimental and theoretical study of the ground and excited states of LiCa. Resonance enhanced multiphoton ionization time-of-flight (REMPI-TOF) spectroscopy and laser induced fluorescence (LIF) spectroscopy were used for the experimental investigation of LiCa from 15000 to 25500 cm–1. The 42Σ+ and 32Π states show a vibrational structure accompanied by distinct phonon wings, which allows us to determine molecular parameters as well as to study the interaction of the molecule with the helium droplet. Higher excited states (42Π, 52Σ+, 52Π, and 62Σ+) are not vibrationally resolved and vibronic transitions start to overlap. The experimental spectrum is well reproduced by high-level ab initio calculations. By using a multireference configuration interaction (MRCI) approach, we calculated the 19 lowest lying potential energy curves (PECs) of the LiCa molecule. On the basis of these calculations, we could identify previously unobserved transitions. Our results demonstrate that the helium droplet isolation approach is a powerful method for the characterization of tailor-made alkali–alkaline earth molecules. In this way, important contributions can be made to the search for optimal pathways toward the creation of ultracold alkali–alkaline earth ground state molecules from the corresponding atomic species. Furthermore, a test for PECs calculated by ab initio methods is provided. PMID:24028555

Nonsmooth modal analysis of a N-degree-of-freedom system undergoing a purely elastic impact law

NASA Astrophysics Data System (ADS)

Legrand, Mathias; Junca, Stéphane; Heng, Sokly

2017-04-01

The dynamics of a N-degree-of-freedom autonomous oscillator undergoing an energy-preserving impact law on one of its masses is investigated in the light of nonlinear modal analysis. The impacted rigid foundation provides a natural Poincaré section of the investigated system from which is formulated a smooth First Return Map well-defined away from the grazing trajectory. In order to focus on the impact-induced nonlinearity, the oscillator is assumed linear. Continuous one-parameter families of T-periodic orbits featuring one impact per period and lying on two-dimensional invariant manifolds in the state-space are shown to exist. The geometry of these piecewise-smooth manifolds is such that a linear "flat" portion (on which contact is not activated) is continuously attached to a purely nonlinear portion (on which contact is activated once per period) exhibiting a velocity discontinuity through a grazing orbit. These features explain the newly introduced terminology "Nonsmooth modal analysis". The stability of the periodic orbits lying on the invariant manifolds is also explored by calculating the eigenvalues of the linearized First Return Map. Internal resonances and multiple impacts per period are not addressed in this work. However, the pre-stressed case is succinctly described and extensions to multiple oscillators as well as self-contact are discussed.

Group theoretical quantization of isotropic loop cosmology

NASA Astrophysics Data System (ADS)

Livine, Etera R.; Martín-Benito, Mercedes

2012-06-01

We achieve a group theoretical quantization of the flat Friedmann-Robertson-Walker model coupled to a massless scalar field adopting the improved dynamics of loop quantum cosmology. Deparemetrizing the system using the scalar field as internal time, we first identify a complete set of phase space observables whose Poisson algebra is isomorphic to the su(1,1) Lie algebra. It is generated by the volume observable and the Hamiltonian. These observables describe faithfully the regularized phase space underlying the loop quantization: they account for the polymerization of the variable conjugate to the volume and for the existence of a kinematical nonvanishing minimum volume. Since the Hamiltonian is an element in the su(1,1) Lie algebra, the dynamics is now implemented as SU(1, 1) transformations. At the quantum level, the system is quantized as a timelike irreducible representation of the group SU(1, 1). These representations are labeled by a half-integer spin, which gives the minimal volume. They provide superselection sectors without quantization anomalies and no factor ordering ambiguity arises when representing the Hamiltonian. We then explicitly construct SU(1, 1) coherent states to study the quantum evolution. They not only provide semiclassical states but truly dynamical coherent states. Their use further clarifies the nature of the bounce that resolves the big bang singularity.

Stokes flow inside an evaporating liquid line for any contact angle

NASA Astrophysics Data System (ADS)

Petsi, A. J.; Burganos, V. N.

2008-09-01

Evaporation of droplets or liquid films lying on a substrate induces internal viscous flow, which affects the transport of suspended particles and, thus, the final deposit profile in numerous applications. In this work, the problem of Stokes flow inside a two-dimensional droplet, representing the cross section of an evaporating liquid line lying on a flat surface, is considered. The stream function formulation is adopted, leading to the biharmonic equation in bipolar coordinates. A solution in closed form is obtained for any contact angle in (0,π) and is, thus, valid for both hydrophilic and hydrophobic substrates. The solution can be used with any type of evaporation mechanism, including diffusion, convection, or kinetically controlled modes. Both pinned and depinned contact lines are considered. For the boundary conditions to be compatible at the contact lines, the Navier slip boundary condition is applied on the substrate. Numerical results are presented for kinetically and diffusion controlled evaporation. For pinned contact lines, the flow inside the evaporating liquid line is directed towards the edges, thus, promoting the coffee stain phenomenon. In the case of depinned contact lines and contact angle less than π/2 , the flow is directed towards the center of the droplet, whereas, for strongly hydrophobic substrates it is directed outwards.

Assessing the impacts of sea-level rise and precipitation change on the surficial aquifer in the low-lying coastal alluvial plains and barrier islands, east-central Florida (USA)

NASA Astrophysics Data System (ADS)

Xiao, Han; Wang, Dingbao; Hagen, Scott C.; Medeiros, Stephen C.; Hall, Carlton R.

2016-11-01

A three-dimensional variable-density groundwater flow and salinity transport model is implemented using the SEAWAT code to quantify the spatial variation of water-table depth and salinity of the surficial aquifer in Merritt Island and Cape Canaveral Island in east-central Florida (USA) under steady-state 2010 hydrologic and hydrogeologic conditions. The developed model is referred to as the `reference' model and calibrated against field-measured groundwater levels and a map of land use and land cover. Then, five prediction/projection models are developed based on modification of the boundary conditions of the calibrated `reference' model to quantify climate change impacts under various scenarios of sea-level rise and precipitation change projected to 2050. Model results indicate that west Merritt Island will encounter lowland inundation and saltwater intrusion due to its low elevation and flat topography, while climate change impacts on Cape Canaveral Island and east Merritt Island are not significant. The SEAWAT models developed for this study are useful and effective tools for water resources management, land use planning, and climate-change adaptation decision-making in these and other low-lying coastal alluvial plains and barrier island systems.

The National Nanotechnology Initiative. Research and Development Leading to a Revolution in Technology ad Industry. Supplement to the President’s 2009 Budget

DTIC Science & Technology

2008-09-30

About this document This document is a supplement to the President’s 2009 Budget Request submitted to Congress on February 4, 2008. It gives a ...Initiative (NNI), primarily from a programmatic and budgetary perspective. It is based on the NNI Strategic Plan released in December 2007 and reports...microscope image of C60 molecules on a flat silver surface. Additional technical and ordering information for the new NIST nanoparticle reference

Using Multiorder Time-Correlation Functions (TCFs) To Elucidate Biomolecular Reaction Pathways from Microsecond Single-Molecule Fluorescence Experiments.

PubMed

Phelps, Carey; Israels, Brett; Marsh, Morgan C; von Hippel, Peter H; Marcus, Andrew H

2016-12-29

Recent advances in single-molecule fluorescence imaging have made it possible to perform measurements on microsecond time scales. Such experiments have the potential to reveal detailed information about the conformational changes in biological macromolecules, including the reaction pathways and dynamics of the rearrangements involved in processes, such as sequence-specific DNA "breathing" and the assembly of protein-nucleic acid complexes. Because microsecond-resolved single-molecule trajectories often involve "sparse" data, that is, they contain relatively few data points per unit time, they cannot be easily analyzed using the standard protocols that were developed for single-molecule experiments carried out with tens-of-millisecond time resolution and high "data density." Here, we describe a generalized approach, based on time-correlation functions, to obtain kinetic information from microsecond-resolved single-molecule fluorescence measurements. This approach can be used to identify short-lived intermediates that lie on reaction pathways connecting relatively long-lived reactant and product states. As a concrete illustration of the potential of this methodology for analyzing specific macromolecular systems, we accompany the theoretical presentation with the description of a specific biologically relevant example drawn from studies of reaction mechanisms of the assembly of the single-stranded DNA binding protein of the T4 bacteriophage replication complex onto a model DNA replication fork.

The 2D Selfassembly of Benzimidazole and its Co-crystallization

NASA Astrophysics Data System (ADS)

Costa, Paulo; Teeter, Jacob; Kunkel, Donna; Sinitskii, Alexander; Enders, Axel

Benzimidazoles (BI) are organic molecules that form ferroelectric crystals. Key to their ferroelectric behavior are the switchable N . . . HN type bonds and how they couple to the electron system of the molecules. We attempted to crystallize BI on various metal surfaces and studied them using STM. We observed that on Au and Ag, BI joins into zipper chains characteristic of its bulk structure that can pack into a continuous 2D layer. Because the dipole of BI lies in the direction of its switchable hydrogen bond, these zippers should in principle have reversible polarizations that point along the direction they run. BI's crystallization is reminiscent to how croconic acid (CA) crystallizes in 2D using O . . . HO bonding, suggesting that these molecules may be able to co-crystallize through OH . . . N bonds. This would present the opportunity to modify BI's properties, such as the energy needed to switch a hydrogen from a donor to acceptor site. When co-deposited, CA and BI successfully combine into a co-crystal formed by building blocks consisting of 2 CA and 2 BI molecules. These findings demonstrate the usefulness of using STM as a preliminary check to verify if two molecules are compatible with each other without having to attempt crystallization with multiple solvents and mixing methods.

Elementary Reactions and Their Role in Gas-Phase Prebiotic Chemistry

PubMed Central

Balucani, Nadia

2009-01-01

The formation of complex organic molecules in a reactor filled with gaseous mixtures possibly reproducing the primitive terrestrial atmosphere and ocean demonstrated more than 50 years ago that inorganic synthesis of prebiotic molecules is possible, provided that some form of energy is provided to the system. After that groundbreaking experiment, gas-phase prebiotic molecules have been observed in a wide variety of extraterrestrial objects (including interstellar clouds, comets and planetary atmospheres) where the physical conditions vary widely. A thorough characterization of the chemical evolution of those objects relies on a multi-disciplinary approach: 1) observations allow us to identify the molecules and their number densities as they are nowadays; 2) the chemistry which lies behind their formation starting from atoms and simple molecules is accounted for by complex reaction networks; 3) for a realistic modeling of such networks, a number of experimental parameters are needed and, therefore, the relevant molecular processes should be fully characterized in laboratory experiments. A survey of the available literature reveals, however, that much information is still lacking if it is true that only a small percentage of the elementary reactions considered in the models have been characterized in laboratory experiments. New experimental approaches to characterize the relevant elementary reactions in laboratory are presented and the implications of the results are discussed. PMID:19564951

A scale-bridging modeling approach for anisotropic organic molecules at patterned semiconductor surfaces

NASA Astrophysics Data System (ADS)

Kleppmann, Nicola; Klapp, Sabine H. L.

2015-02-01

Hybrid systems consisting of organic molecules at inorganic semiconductor surfaces are gaining increasing importance as thin film devices for optoelectronics. The efficiency of such devices strongly depends on the collective behavior of the adsorbed molecules. In the present paper, we propose a novel, coarse-grained model addressing the condensed phases of a representative hybrid system, that is, para-sexiphenyl (6P) at zinc-oxide (ZnO). Within our model, intermolecular interactions are represented via a Gay-Berne potential (describing steric and van-der-Waals interactions) combined with the electrostatic potential between two linear quadrupoles. Similarly, the molecule-substrate interactions include a coupling between a linear molecular quadrupole to the electric field generated by the line charges characterizing ZnO(10-10). To validate our approach, we perform equilibrium Monte Carlo simulations, where the lateral positions are fixed to a 2D lattice, while the rotational degrees of freedom are continuous. We use these simulations to investigate orientational ordering in the condensed state. We reproduce various experimentally observed features such as the alignment of individual molecules with the line charges on the surface, the formation of a standing uniaxial phase with a herringbone structure, as well as the formation of a lying nematic phase.

Dissociative excitation of H2, HD, and D2 by electron impact

NASA Technical Reports Server (NTRS)

Carnahan, B. L.; Zipf, E. C.

1977-01-01

Time-of-flight techniques have been used to investigate the electron-impact dissociation of H2, HD, and D2 in order to determine the effect of isotopic mass variation in the target molecule on the dissociative excitation process. At incident electron energies near 100 eV, the time-of-flight spectrum produced from each molecule consists of atoms in the metastable 2s state and in high-lying long-lived Rydberg levels. The individual time-of-flight distributions, kinetic-energy spectra, and relative differential cross sections for these two species resulting from each molecule have been measured. The kinetic-energy spectrum of the Rydberg atoms produced from dissociative excitation of H2 was notably dissimilar in shape from the corresponding distributions produced from HD and D2. Also the 2s and Rydberg production cross sections differed between the three molecules. In the dissociation of the heteronuclear HD molecule, the ratio of fast H(2s) atoms to D(2s) atoms was about 1 to 1, while the same ratio comparing the Rydberg atoms was nearly 2 to 1. These differences indicate the influence of the mass variation on the position of the Franck-Condon region in the production of 2s atoms and on the competition between autoionization and dissociation in the formation of Rydberg fragments.

Selective on site separation and detection of molecules in diluted solutions with super-hydrophobic clusters of plasmonic nanoparticles.

PubMed

Gentile, Francesco; Coluccio, Maria Laura; Zaccaria, Remo Proietti; Francardi, Marco; Cojoc, Gheorghe; Perozziello, Gerardo; Raimondo, Raffaella; Candeloro, Patrizio; Di Fabrizio, Enzo

2014-07-21

Super-hydrophobic surfaces are bio-inspired interfaces with a superficial texture that, in its most common evolution, is formed by a periodic lattice of silicon micro-pillars. Similar surfaces reveal superior properties compared to conventional flat surfaces, including very low friction coefficients. In this work, we modified meso-porous silicon micro-pillars to incorporate networks of metal nano-particles into the porous matrix. In doing so, we obtained a multifunctional-hierarchical system in which (i) at a larger micrometric scale, the super-hydrophobic pillars bring the molecules dissolved in an ultralow-concentration droplet to the active sites of the device, (ii) at an intermediate meso-scale, the meso-porous silicon film adsorbs the low molecular weight content of the solution and, (iii) at a smaller nanometric scale, the aggregates of silver nano-particles would measure the target molecules with unprecedented sensitivity. In the results, we demonstrated how this scheme can be utilized to isolate and detect small molecules in a diluted solution in very low abundance ranges. The presented platform, coupled to Raman or other spectroscopy techniques, is a realistic candidate for the protein expression profiling of biological fluids.

Preparation of monolayers of [MnIII 6CrIII]3+ single-molecule magnets on HOPG, mica and silicon surfaces and characterization by means of non-contact AFM

NASA Astrophysics Data System (ADS)

Gryzia, Aaron; Predatsch, Hans; Brechling, Armin; Hoeke, Veronika; Krickemeyer, Erich; Derks, Christine; Neumann, Manfred; Glaser, Thorsten; Heinzmann, Ulrich

2011-08-01

We report on the characterization of various salts of [ Mn III 6 Cr III ] 3+ complexes prepared on substrates such as highly oriented pyrolytic graphite (HOPG), mica, SiO2, and Si3N4. [ Mn III 6 Cr III ] 3+ is a single-molecule magnet, i.e., a superparamagnetic molecule, with a blocking temperature around 2 K. The three positive charges of [ Mn III 6 Cr III ] 3+ were electrically neutralized by use of various anions such as tetraphenylborate (BPh4 -), lactate (C3H5O3 -), or perchlorate (ClO4 -). The molecule was prepared on the substrates out of solution using the droplet technique. The main subject of investigation was how the anions and substrates influence the emerging surface topology during and after the preparation. Regarding HOPG and SiO2, flat island-like and hemispheric-shaped structures were created. We observed a strong correlation between the electronic properties of the substrate and the analyzed structures, especially in the case of mica where we observed a gradient in the analyzed structures across the surface.

Optofluidic lens actuated by laser-induced solutocapillary forces

NASA Astrophysics Data System (ADS)

Malyuk, A. Yu.; Ivanova, N. A.

2017-06-01

We demonstrate an adaptive liquid lens controlled by laser-induced solutocapillary forces. The liquid droplet serving as a lens is formed in a thin layer of binary liquid mixture by surface tension driven flows caused by the thermal action of laser irradiation. The shape of droplet, its aperture and the focal length are reversibly changed without hysteresis by varying the intensity of the laser beam. The focal length variation range of the droplet-lens lies in between infinity (a flat layer) to 15 mm (a curved interface). The droplet-lens is capable to adjust the in-plane lateral position in response to a displacement of the laser beam. The proposed laser controlled droplet-lens will enable to develop smart liquid optical devices, which can imitate the accommodation reflex and pupillary light reflex of the eye.

Ab initio atomic recombination reaction energetics on model heat shield surfaces

NASA Technical Reports Server (NTRS)

Senese, Fredrick; Ake, Robert

1992-01-01

Ab initio quantum mechanical calculations on small hydration complexes involving the nitrate anion are reported. The self-consistent field method with accurate basis sets has been applied to compute completely optimized equilibrium geometries, vibrational frequencies, thermochemical parameters, and stable site labilities of complexes involving 1, 2, and 3 waters. The most stable geometries in the first hydration shell involve in-plane waters bridging pairs of nitrate oxygens with two equal and bent hydrogen bonds. A second extremely labile local minimum involves out-of-plane waters with a single hydrogen bond and lies about 2 kcal/mol higher. The potential in the region of the second minimum is extremely flat and qualitatively sensitive to changes in the basis set; it does not correspond to a true equilibrium structure.

Metric Theories of Gravity: Perturbations and Conservation Laws

NASA Astrophysics Data System (ADS)

Petrov, Alexander N.; Kopeikin, Sergei M.; Lompay, Robert R.; Tekin, Bayram

2017-04-01

By focusing on the mostly used variational methods, this monograph aspires to give a unified description and comparison of various ways of constructing conserved quantities for perturbations and to study symmetries in general relativity and modified theories of gravity. The main emphasis lies on the field-theoretical covariant formulation of perturbations, the canonical Noether approach and the Belinfante procedure of symmetrisation. The general formalism is applied to build the gauge-invariant cosmological perturbation theory, conserved currents and superpotentials to describe physically important solutions of gravity theories. Meticulous attention is given to the construction of conserved quantities in asymptotically-flat spacetimes as well as in asymptotically constant curvature spacetimes such as the Anti-de Sitter space. Significant part of the book can be used in graduate courses on conservation laws in general relativity.

Microneedle crystals of cyano-substituted thiophene/phenylene co-oligomer epitaxially grown on KCl surface

NASA Astrophysics Data System (ADS)

Torii, Kazuki; Dokiya, Shohei; Tanaka, Yosuke; Yoshinaga, Shohei; Yanagi, Hisao

2017-06-01

A cyno-substituted thiophene/phenylene co-oligomer (TPCO), 5,5‧-bis(4‧-cyanobiphenyl-4-yl)-2,2‧-bithiophene (BP2T-CN), is vapor-deposited on KCl (001) surface kept at 220 °C by the mask-shadowing method. Transmission electron microscopy and fluorescence microscopy reveal that the deposited BP2T-CN crystallizes in two types of morphologies: microneedles and thin film crystallites. In particular, the predominant microneedles epitaxially grow in four directions in the manner that the BP2T-CN molecules align along the [110]KCl or [-110]KCl. X-ray diffraction patterns indicate that the BP2T-CN molecules in the microneedle lie parallel while those in the thin film crystallite obliquely stand on the KCl surface.

Microgravity

NASA Image and Video Library

2004-04-15

The loss of productivity due to flu is staggering. Costs range as much as $20 billio a year. High mutation rates of the flu virus have hindered development of new drugs or vaccines. The secret lies in a small molecule which is attached to the host cell's surface. Each flu virus, no matter what strain, must remove this small molecule to escape the host cell to spread infection. Using data from space and earth grown crystals, researchers from the Center of Macromolecular Crystallography (CMC) are desining drugs to bind with this protein's active site. This lock and key fit reduces the spread of flu in the body by blocking its escape route. In collaboration with its corporate partner, the CMC has refined drug structure in preparation for clinical trials. Tested and approved relief is expected to reach drugstores by year 2004.

Intermolecular C-H···O, Cl···Cl and π-π interactions in the 2-dichloromethyl derivative of vitamin K3.

PubMed

Soave, Raffaella; Colombo, Pietro

2013-12-15

The title 1,4-naphthoquinone, 2-dichloromethyl-3-methyl-1,4-dihydronaphthalene-1,4-dione, C12H8Cl2O2, is a chlorinated derivative of vitamin K3, which is a synthetic compound also known as menadione. Molecules of (I) are planar and lie on a crystallographic mirror plane (Z' = 0.5) in the space group Pnma. They are connected to each other by C-H···O hydrogen bonds, forming two-dimensional layers parallel to the ac plane. In addition, Cl···Cl and π-π interactions link adjacent molecules in different layers, thus forming zigzag ribbons along the b axis, such that a three-dimensional architecture is generated.

Single-molecule protein sequencing through fingerprinting: computational assessment

NASA Astrophysics Data System (ADS)

Yao, Yao; Docter, Margreet; van Ginkel, Jetty; de Ridder, Dick; Joo, Chirlmin

2015-10-01

Proteins are vital in all biological systems as they constitute the main structural and functional components of cells. Recent advances in mass spectrometry have brought the promise of complete proteomics by helping draft the human proteome. Yet, this commonly used protein sequencing technique has fundamental limitations in sensitivity. Here we propose a method for single-molecule (SM) protein sequencing. A major challenge lies in the fact that proteins are composed of 20 different amino acids, which demands 20 molecular reporters. We computationally demonstrate that it suffices to measure only two types of amino acids to identify proteins and suggest an experimental scheme using SM fluorescence. When achieved, this highly sensitive approach will result in a paradigm shift in proteomics, with major impact in the biological and medical sciences.

Nucleation type instabilities in partially wetting nanoscale nematic liquid films

NASA Astrophysics Data System (ADS)

Lam, Michael; Cummings, Linda; Kondic, Lou

2016-11-01

Nucleation type instabilities are studied in nematic liquid crystal (NLC) films with thicknesses less than a micrometer. Within the framework of the long wave approximation, a 4th order nonlinear partial differential equation is proposed for the free surface height. Unlike simple fluids, NLC molecules have a dipole moment which induces an elastic response due to deformation in the bulk of the fluid. The model includes the balance between the bulk elasticity energy and the anchoring (boundary) energy at the substrate and free surface, and van der Waals' intermolecular forces, by means of a structural disjoining pressure. In this presentation, we focus on two-dimensional flow and present simulation results for a flat film with a localized perturbation. We are interested in the morphology of the dewetted film as a function of the initial film thickness. We will show that there exists a range of film thicknesses within the linearly unstable flat film regime where stability analysis does not explain the morphology of the dewetted film. Marginal stability criterion (MSC) is used to derive an analytical expression for the velocity at which a perturbation propagates into the unstable flat film. Finally, we discuss the degree to which MSC can be used to explain the observed morphology.

Earth Observations taken by the Expedition 14 crew

NASA Image and Video Library

2006-12-23

ISS014-E-10499 (23 Dec. 2006) --- Caravelas strandplain, Bahia Province, Brazil is featured in this image photographed by an Expedition 14 crewmember on the International Space Station. This view highlights a flat coastal landform known as a strandplain, or ancient shoreline. The image is dominated by numerous, fine parallel lines (trending diagonally from upper left to lower right), each of which is an ancient shoreline made up of sand transported from rivers to the north. The strandplain has been generated by these narrow shorelines accumulating against one another, line by line in their dozens or even hundreds, over thousands of years. The shorelines can be grouped into at least four packets depending on the crosscutting relationships - younger packets will cut into or stratigraphically overlay older packets. These relationships indicate that the youngest packet lies nearest the coast (furthest right) and the oldest packet lies north of the city of Caravelas (bottom). The Caravelas River flows into the Atlantic Ocean at the bottom of the view. Sediment from this river, and from the current shoreline, produces the light browns and dun colors visible offshore. On the day this image was taken the river water was relatively clear; clear water (gray) is visible flowing out of the main river mouth, and also off to one side to the south over a levee. The Caravelas airport appears near the middle of the view, and is built on one of the ancient shoreline packets. Caravelas itself, a fishing town of about 20,000 inhabitants, lies on an estuary and was once a flourishing whaling center--the prominent cape at top right is known as Ponta da Baleia (Whale Point).

Studies on the accessibility of deoxyribonucleic acid in deoxyribonucleoprotein to cationic molecules

PubMed Central

Itzhaki, Ruth F.

1971-01-01

The binding of deoxyribonucleoprotein to Toluidine Blue, to cetylpyridinium chloride and to polylysine of various molecular weights was studied to determine the percentage of free DNA phosphate groups in deoxyribonucleoprotein. Binding was measured by addition of these reagents to deoxyribonucleoprotein at a range of concentrations such that complete precipitation of the deoxyribonucleoprotein occurred. With Toluidine Blue the binding corresponded to about 48% of the DNA phosphates in deoxyribonucleoprotein. The dye did not cause appreciable displacement of protein from the DNA. With cetylpyridinium chloride the binding corresponded to about 41% of the DNA phosphates. With polylysine preparations of molecular weight 1250 and 7790 the binding values for deoxyribonucleoprotein were 46 and 38% respectively. The results suggest that the free phosphates lie in stretches sufficiently long to accommodate most of each polylysine molecule. With polylysine of molecular weight 62000 cross-linking of free stretches of DNA on different deoxyribonucleoprotein molecules probably occurs. It is concluded that although most of the free phosphates are probably `hidden' beneath covering histone, corresponding perhaps to runs of non-basic residues in the latter, they are surprisingly accessible to very large molecules. The relevance of this finding to the problem of gene repression is discussed. PMID:5166331

Ethane-1,1,2-trisphosphonic acid hemihydrate.

PubMed

Delain-Bioton, Lise; Lohier, Jean François; Villemin, Didier; Sopková-de Oliveira Santos, Jana; Hix, Gary; Jaffrès, Paul Alain

2008-02-01

Ethane-1,1,2-trisphosphonic acid crystallizes as a hemihydrate, C(2)H(9)O(9)P(3).0.5H(2)O, in which the water O atom lies on an inversion centre in the space group P2(1)/c. The acid component, which contains a short but noncentred O-H...O hydrogen bond, adopts a gauche conformation. The acid components are linked by an extensive series of O-H...O hydrogen bonds to form layers, which are linked into pairs by the water molecules.

Recent measurements concerning uranium hexafluoride-electron collision processes

NASA Technical Reports Server (NTRS)

Trajmar, S.; Chutjian, A.; Srivastava, S.; Williams, W.; Cartwright, D. C.

1976-01-01

Scattering of electrons by UF6 molecules was studied at impact energies ranging from 5 to 100 eV and momentum transfer, elastic and inelastic scattering cross sections were determined. The measurements also yielded spectroscopic information which made possible to extend the optical absorption cross sections from 2000 angstroms to 435 angstroms. It was found that UF6 is a very strong absorber in the vacuum UV region. No transitions were found to lie below the onset of the optically detected 3.0 eV feature.

2,2',5,5'-Tetra-methyl-1,1'-(hexane-1,6-di-yl)di-1H-pyrrole.

PubMed

Santos, Ana C; Ramos Silva, Manuela; Monsanto, Paula V; Matos Beja, Ana; Sobral, Abilio J F N

2009-06-17

The mol-ecule of the title compound, C(18)H(28)N(2), composed of two 2,5-dimethyl-pyrrole groups linked by a hexane chain, lies across a crystallographic inversion centre. The mean plane of the pyrrole ring is almost perpendicular to the mean plane of the central chain, making a dihedral angle of 89.09 (8)°. The crystal structure is stabilized by inter-molecular C-H⋯π inter-actions.

Dielectric relaxation measurement and analysis of restricted water structure in rice kernels

NASA Astrophysics Data System (ADS)

Yagihara, Shin; Oyama, Mikio; Inoue, Akio; Asano, Megumi; Sudo, Seiichi; Shinyashiki, Naoki

2007-04-01

Dielectric relaxation measurements were performed for rice kernels by time domain reflectometry (TDR) with flat-end coaxial electrodes. Difficulties in good contact between the surfaces of the electrodes and the kernels are eliminated by a TDR set-up with a sample holder for a kernel, and the water content could be evaluated from relaxation curves. Dielectric measurements were performed for rice kernels, rice flour and boiled rice with various water contents, and the water amount and dynamic behaviour of water molecules were explained from restricted dynamics of water molecules and also from the τ-β (relaxation time versus the relaxation-time distribution parameter of the Cole-Cole equation) diagram. In comparison with other aqueous systems, the dynamic structure of water in moist rice is more similar to aqueous dispersion systems than to aqueous solutions.

Driving force behind adsorption-induced protein unfolding: a time-resolved X-ray reflectivity study on lysozyme adsorbed at an air/water interface.

PubMed

Yano, Yohko F; Uruga, Tomoya; Tanida, Hajime; Toyokawa, Hidenori; Terada, Yasuko; Takagaki, Masafumi; Yamada, Hironari

2009-01-06

Time-resolved X-ray reflectivity measurements for lysozyme (LSZ) adsorbed at an air/water interface were performed to study the mechanism of adsorption-induced protein unfolding. The time dependence of the density profile at the air/water interface revealed that the molecular conformation changed significantly during adsorption. Taking into account previous work using Fourier transform infrared (FTIR) spectroscopy, we propose that the LSZ molecules initially adsorbed on the air/water interface have a flat unfolded structure, forming antiparallel beta-sheets as a result of hydrophobic interactions with the gas phase. In contrast, as adsorption continues, a second layer forms in which the molecules have a very loose structure having random coils as a result of hydrophilic interactions with the hydrophilic groups that protrude from the first layer.

Photoisomers of Azobenzene Star with a Flat Core: Theoretical Insights into Multiple States from DFT and MD Perspective.

PubMed

Koch, Markus; Saphiannikova, Marina; Santer, Svetlana; Guskova, Olga

2017-09-21

This study focuses on comparing physical properties of photoisomers of an azobenzene star with benzene-1,3,5-tricarboxamide core. Three azobenzene arms of the molecule undergo a reversible trans-cis isomerization upon UV-vis light illumination giving rise to multiple states from the planar all-trans one, via two mixed states to the kinked all-cis isomer. Employing density functional theory, we characterize the structural and photophysical properties of each state indicating a role the planar core plays in the coupling between azobenzene chromophores. To characterize the light-triggered switching of solvophilicity/solvophobicity of the star, the difference in solvation free energy is calculated for the transfer of an azobenzene star from its gas phase to implicit or explicit solvents. For the latter case, classical all-atom molecular dynamics simulations of aqueous solutions of azobenzene star are performed employing the polymer consistent force field to shed light on the thermodynamics of explicit hydration as a function of the isomerization state and on the structuring of water around the star. From the analysis of two contributions to the free energy of hydration, the nonpolar van der Waals and the electrostatic terms, it is concluded that isomerization specificity largely determines the polarity of the molecule and the solute-solvent electrostatic interactions. This convertible hydrophilicity/hydrophobicity together with readjustable occupied volume and the surface area accessible to water, affects the self-assembly/disassembly of the azobenzene star with a flat core triggered by light.

Juxtaposition of contrasting structural regimes across a portion of the Norumbega fault system in the northern Casco Bay region of Maine

NASA Astrophysics Data System (ADS)

West, D. P., Jr.; Hussey, A. M., II

2015-12-01

It has long been recognized that Paleozoic stratified rocks in some regions of central New England are dominated by relatively flat structural features (e.g., recumbent folds, shallow dipping foliation) while other areas are dominated by near vertical upright structures. The northern Casco Bay region of coastal Maine (Brunswick 7.5' quadrangle and adjacent areas) provides an excellent venue for studying the relationships between these two structural regimes as they are in close proximity due to juxtaposition by high angle faulting associated with the Norumbega fault system. Stratified rocks exposed west of the Flying Point fault in northern Casco Bay are dominated by moderately east dipping foliation (ave. = 025o, 37o), moderate northeast plunging mineral lineations, and recumbent to gently inclined minor folds. In stark contrast, immediately east of the Flying Point fault, stratified rocks are dominated by steep east dipping foliation (ave. = 014o, 73o), subhorizontal mineral lineations, and upright to steeply inclined minor folds. The structural differences correspond directly to differences in the thermal histories preserved in these rocks as revealed by earlier thermochronological studies. Rocks in the zone of upright structures east of the Flying Point fault were last subjected to high grade metamorphic conditions and granitic plutonism in the Late Devonian and were relatively cold (<300oC) by Late Carboniferous time. In contrast, flat lying rocks west of the Flying Point fault were over 500oC in the Early Permian and Permian pegmatites are common. Geochronological studies north of the study area have revealed that the two distinctly different structural styles are not the product of strain partitioning during the same deformational episode, but rather they represent two temporally and kinematically distinct deformational events. Swanson (1999), originally suggested flat structures west of the Flying Point fault are consistent with an episode of northwest directed thrusting and our findings are consistent with this interpretation. However, this flat phase of deformation significantly post-dates the older upright structures preserved to the east and thus models for the structural evolution of the region must integrate both the kinematic and temporal differences in this deformation.

Active Deformation in the Overriding Plate Associated with Temporal Changes of the Philippine Sea Plate Motion

NASA Astrophysics Data System (ADS)

Ishiyama, T.; Sato, H.; Van Horne, A.

2015-12-01

We present detailed geologic evidence linking changes over time in Philippine Sea plate (PHS) motion and intracontinental deformation in central and southwest (SW) Japan during the Pliocene and after. In the early Pliocene, subduction of the PHS plate under SW Japan restarted in a northerly direction after period of deceleration or cessation. Later, motion changed to a more westerly direction. Corresponding geological changes found in the overriding plate include unconformities in the forearc basins, changes in slip sense on faults, depocenter migration, re-organization of drainage systems and volcanism. Quaternary intraplate deformation is prominent north of the Median Tectonic Line (MTL) inactive segment, above a shallow flat slab. In contrast, less Quaternary tectonic activity is found north of the MTL active segment which lies over a steadily-slipping portion of the subducting slab that behaves as a less-deformed rigid block. Depocenters and active thrusting have migrated north/northwestward over the past 5 My above the shallow flat slab segment of the PHS. We reconstructed the Plio-Pleistocene migration history using Neogene stratigraphy and shallow seismic reflection profiles. We see shallow PHS slab contact with the lower continental crust in our deep seismic reflection profiles, which may explain its enhanced downward drag of the overriding plate and synchronous strong compression in the crust. We find evidence of more westerly PHS plate subduction since the middle Pleistocene in (1) unconformities in the Kumano forearc basin deposits in SW Japan, (2) drastic stream captures in Shikoku, and (3) concordant changes in fault slip sense from thrust to dextral slip along the MTL. Oblique subduction could have induced stronger horizontal stress in the overriding plate above the shallow flat slab which could account for the increasing geologic slip rate observed on active structures. During four repetitions of megathrust earthquake sequences since the 17th century, ca. 65 % of all intraplate M>6.5 earthquakes have been concentrated in the area above the PHS flat slab. This also suggests that mechanical interaction between the slab and the overriding plate plays an important role in intraplate seismicity over shorter timescales as well.

Geological and geographical investigations of an Apollo 9 photo anomaly near Point of Pines, Arizona

USGS Publications Warehouse

Bromfield, Calvin S.; Eaton, G.P.; Peterson, D.L.; Ratte, J.C.

1972-01-01

An infrared photograph of southeastern Arizona, taken during the Apollo 9 multispectral terrain photography experiment in 1969, reveals a ringlike feature, some 3-4 miles (5-6 kin) in diameter, on the Natanes Plateau, 35 miles (56 kin) north of the town of Safford. Because the feature occurs in an area of nearly flat lying Tertiary volcanic rocks, the possibilities of its being a small collapse caldera or an exposed circular intrusive body were considered. Geological and geophysical studies of the area were made to test these hypotheses. The local stratigraphic section consists of approximately 1,500 feet (457 m) of Oligocene and perhaps older volcanic rocks, resting on a moderately irregular basement surface carved from nearly flat lying trending Basin-and-Range faults define a broad horst within which two arcuate cross faults, with 300-600 feet (91-183 m) of displacement, bound a downdropped area. Deep erosion along these faults has created a polygonal network of canyons which constitutes the 'ring' seen on the photograph. A mild arching of the volcanic rocks within the ring is suggested by structure contours on the base of the youngest flows. A sharp 350-gamma positive aeromagnetic anomaly is centered within the ring. In its southwest quadrant the anomaly has an elongate extension that trends northwest along an adjoining Basin-and-Range fault. Associated with both is a subtle gravity low. The geophysical data thus suggest the presence of a small blind silicic pluton, possibly of middle Tertiary or younger age. Although it can be argued that the arcuate faults and mild arching of the volcanic pile are related to this postulated pluton, no evidence of hydrothermal alteration or thermal metamorphism of the country rocks was seen. Thus if a pluton is present and of postvolcanic age, it must have been emplaced as a relatively cool dry body; or alternatively, it is older than the surface volcanic rocks. In either instance, its magnetic expression contrasts with that of the known mineralized Laramide porphyry intrusive bodies of the region.

Ice growth from supercooled aqueous solutions of benzene, naphthalene, and phenanthrene.

PubMed

Liyana-Arachchi, Thilanga P; Valsaraj, Kalliat T; Hung, Francisco R

2012-08-23

Classical molecular dynamics (MD) were performed to investigate the growth of ice from supercooled aqueous solutions of benzene, naphthalene, or phenanthrene. The main objective of this study is to explore the fate of those aromatic molecules after freezing of the supercooled aqueous solutions, i.e., if these molecules become trapped inside the ice lattice or if they are displaced to the QLL or to the interface with air. Ice growth from supercooled aqueous solutions of benzene, naphthalene, or phenanthrene result in the formation of quasi-liquid layers (QLLs) at the air/ice interface that are thicker than those observed when pure supercooled water freezes. Naphthalene and phenanthrene molecules in the supercooled aqueous solutions are displaced to the air/ice interface during the freezing process at both 270 and 260 K; no incorporation of these aromatics into the ice lattice is observed throughout the freezing process. Similar trends were observed during freezing of supercooled aqueous solutions of benzene at 270 K. In contrast, a fraction of the benzene molecules become trapped inside the ice lattice during the freezing process at 260 K, with the rest of the benzene molecules being displaced to the air/ice interface. These results suggest that the size of the aromatic molecule in the supercooled aqueous solution is an important parameter in determining whether these molecules become trapped inside the ice crystals. Finally, we also report potential of mean force (PMF) calculations aimed at studying the adsorption of gas-phase benzene and phenanthrene on atmospheric air/ice interfaces. Our PMF calculations indicate the presence of deep free energy minima for both benzene and phenanthrene at the air/ice interface, with these molecules adopting a flat orientation at the air/ice interface.

Super-resolution imaging of multiple cells by optimized flat-field epi-illumination

NASA Astrophysics Data System (ADS)

Douglass, Kyle M.; Sieben, Christian; Archetti, Anna; Lambert, Ambroise; Manley, Suliana

2016-11-01

Biological processes are inherently multi-scale, and supramolecular complexes at the nanoscale determine changes at the cellular scale and beyond. Single-molecule localization microscopy (SMLM) techniques have been established as important tools for studying cellular features with resolutions of the order of around 10 nm. However, in their current form these modalities are limited by a highly constrained field of view (FOV) and field-dependent image resolution. Here, we develop a low-cost microlens array (MLA)-based epi-illumination system—flat illumination for field-independent imaging (FIFI)—that can efficiently and homogeneously perform simultaneous imaging of multiple cells with nanoscale resolution. The optical principle of FIFI, which is an extension of the Köhler integrator, is further elucidated and modelled with a new, free simulation package. We demonstrate FIFI's capabilities by imaging multiple COS-7 and bacteria cells in 100 × 100 μm2 SMLM images—more than quadrupling the size of a typical FOV and producing near-gigapixel-sized images of uniformly high quality.

Conformations of peptoids in nanosheets result from the interplay of backbone energetics and intermolecular interactions.

PubMed

Edison, John R; Spencer, Ryan K; Butterfoss, Glenn L; Hudson, Benjamin C; Hochbaum, Allon I; Paravastu, Anant K; Zuckermann, Ronald N; Whitelam, Stephen

2018-05-29

The conformations adopted by the molecular constituents of a supramolecular assembly influence its large-scale order. At the same time, the interactions made in assemblies by molecules can influence their conformations. Here we study this interplay in extended flat nanosheets made from nonnatural sequence-specific peptoid polymers. Nanosheets exist because individual polymers can be linear and untwisted, by virtue of polymer backbone elements adopting alternating rotational states whose twists oppose and cancel. Using molecular dynamics and quantum mechanical simulations, together with experimental data, we explore the design space of flat nanostructures built from peptoids. We show that several sets of peptoid backbone conformations are consistent with their being linear, but the specific combination observed in experiment is determined by a combination of backbone energetics and the interactions made within the nanosheet. Our results provide a molecular model of the peptoid nanosheet consistent with all available experimental data and show that its structure results from a combination of intra- and intermolecular interactions.

Dynamic effects in friction and adhesion through cooperative rupture and formation of supramolecular bonds.

PubMed

Blass, Johanna; Albrecht, Marcel; Bozna, Bianca L; Wenz, Gerhard; Bennewitz, Roland

2015-05-07

We introduce a molecular toolkit for studying the dynamics in friction and adhesion from the single molecule level to effects of multivalency. As experimental model system we use supramolecular bonds established by the inclusion of ditopic adamantane connector molecules into two surface-bound cyclodextrin molecules, attached to a tip of an atomic force microscope (AFM) and to a flat silicon surface. The rupture force of a single bond does not depend on the pulling rate, indicating that the fast complexation kinetics of adamantane and cyclodextrin are probed in thermal equilibrium. In contrast, the pull-off force for a group of supramolecular bonds depends on the unloading rate revealing a non-equilibrium situation, an effect discussed as the combined action of multivalency and cantilever inertia effects. Friction forces exhibit a stick-slip characteristic which is explained by the cooperative rupture of groups of host-guest bonds and their rebinding. No dependence of friction on the sliding velocity has been observed in the accessible range of velocities due to fast rebinding and the negligible delay of cantilever response in AFM lateral force measurements.

The fluorescence resonance energy transfer (FRET) gate: a time-resolved study.

PubMed

Xu, Qing-Hua; Wang, Shu; Korystov, Dmitry; Mikhailovsky, Alexander; Bazan, Guillermo C; Moses, Daniel; Heeger, Alan J

2005-01-18

The two-step energy-transfer process in a self-assembled complex comprising a cationic conjugated polymer (CCP) and a dsDNA is investigated by using pump-dump-emission spectroscopy and time-correlated single-photon counting; energy is transferred from the CCP to an ethidium bromide (EB) molecule intercalated into the dsDNA through a fluorescein molecule linked to one terminus of the DNA. Time-dependent anisotropy measurements indicate that the inefficient direct energy transfer from the CCP to the intercalated EB results from the near orthogonality of their transition moments. These measurements also show that the transition moment of the fluorescein spans a range of angular distributions and lies between that of the CCP and EB. Consequently, the fluorescein acts as a fluorescence resonance energy-transfer gate to relay the excitation energy from the CCP to the EB.

The fluorescence resonance energy transfer (FRET) gate: A time-resolved study

PubMed Central

Xu, Qing-Hua; Wang, Shu; Korystov, Dmitry; Mikhailovsky, Alexander; Bazan, Guillermo C.; Moses, Daniel; Heeger, Alan J.

2005-01-01

The two-step energy-transfer process in a self-assembled complex comprising a cationic conjugated polymer (CCP) and a dsDNA is investigated by using pump-dump-emission spectroscopy and time-correlated single-photon counting; energy is transferred from the CCP to an ethidium bromide (EB) molecule intercalated into the dsDNA through a fluorescein molecule linked to one terminus of the DNA. Time-dependent anisotropy measurements indicate that the inefficient direct energy transfer from the CCP to the intercalated EB results from the near orthogonality of their transition moments. These measurements also show that the transition moment of the fluorescein spans a range of angular distributions and lies between that of the CCP and EB. Consequently, the fluorescein acts as a fluorescence resonance energy-transfer gate to relay the excitation energy from the CCP to the EB. PMID:15642946

Millimeter-wave and Submillimeter-wave Spectra of Aminoacetonitrile in the Three Lowest Vibrational Excited States

DOE Office of Scientific and Technical Information (OSTI.GOV)

Esposti, Claudio Degli; Dore, Luca; Melosso, Mattia

It is important to study possible precursors of amino acids such as glycine to enable future searches in interstellar space. Aminoacetonitrile (NH{sub 2}CH{sub 2}CN) is one of the most feasible molecules for this purpose. This molecule was already detected toward Sgr B2(N). Aminoacetonitrile has a few low-lying vibrational excited states, and transitions within these states may be found in space. In this study, the pure-rotational transitions in the three lowest vibrational states in the 80–450 GHz range have been assigned and analyzed. It was found to be very important to include Coriolis coupling between the two lowest vibrational fundamentals, whilemore » the third one was unperturbed. The partition function was evaluated considering these new results.« less

Low-energy excitations of a Bose-Einstein condensate of rigid rotor molecules

NASA Astrophysics Data System (ADS)

Smith, Joseph; Jones, Evan; Rittenhouse, Seth; Wilson, Ryan; Peden, Brandon

2017-04-01

We investigate the properties of the ground state and low-lying excitations of an oblate Bose-Einstein condensate composed of rigid rotor molecules in the presence of an external polarizing electric field. We build in a quantum model of molecular polarizability by including the full manifold of rotational states. The interplay between spatial and microscopic degrees of freedom via feedback between the molecular polarizability and inter-molecular dipole-dipole interactions leads to a rich quasi-particle spectrum. Under large applied fields, we reproduce the well-understood density-wave rotonization that appears in a fully polarized dipolar BEC, but under smaller applied fields, we predict the emergence of a spin wave instability and possible new stable ground state phases. We gratefully acknowledge support from the National Science Foundation under Grant No. PHYS-1516421.

Interstate vibronic coupling constants between electronic excited states for complex molecules

NASA Astrophysics Data System (ADS)

Fumanal, Maria; Plasser, Felix; Mai, Sebastian; Daniel, Chantal; Gindensperger, Etienne

2018-03-01

In the construction of diabatic vibronic Hamiltonians for quantum dynamics in the excited-state manifold of molecules, the coupling constants are often extracted solely from information on the excited-state energies. Here, a new protocol is applied to get access to the interstate vibronic coupling constants at the time-dependent density functional theory level through the overlap integrals between excited-state adiabatic auxiliary wavefunctions. We discuss the advantages of such method and its potential for future applications to address complex systems, in particular, those where multiple electronic states are energetically closely lying and interact. We apply the protocol to the study of prototype rhenium carbonyl complexes [Re(CO)3(N,N)(L)]n+ for which non-adiabatic quantum dynamics within the linear vibronic coupling model and including spin-orbit coupling have been reported recently.

3-Dimensional Protein Structure of Influenza

NASA Technical Reports Server (NTRS)

2004-01-01

The loss of productivity due to flu is staggering. Costs range as much as $20 billio a year. High mutation rates of the flu virus have hindered development of new drugs or vaccines. The secret lies in a small molecule which is attached to the host cell's surface. Each flu virus, no matter what strain, must remove this small molecule to escape the host cell to spread infection. Using data from space and earth grown crystals, researchers from the Center of Macromolecular Crystallography (CMC) are desining drugs to bind with this protein's active site. This lock and key fit reduces the spread of flu in the body by blocking its escape route. In collaboration with its corporate partner, the CMC has refined drug structure in preparation for clinical trials. Tested and approved relief is expected to reach drugstores by year 2004.

Ab initio multireference study of the BN molecule

NASA Technical Reports Server (NTRS)

Martin, J. M. L.; Lee, Timothy J.; Scuseria, Gustavo E.; Taylor, Peter R.

1992-01-01

The lowest 1Sigma(+) and 3Pi states of the BN molecule are studied using multireference configuration interaction (MRCI) and averaged coupled-pair functional (ACPF) methods and large atomic natural orbital (ANO) basis sets, as well as several coupled cluster methods. Our calculations strongly support a 3Pi ground state, but the a1Sigma(+) state lies only 381 +/- 100/cm higher. The a1Sigma(+) state wave function exhibits strong multireference character and, consequently, the predictions of the perturbationally-based single-reference CCSD(T) coupled cluster method are not as reliable in this case as the multireference results. The theoretical predictions for the spectroscopic constants of BN are in good agreement with experiment for the Chi3Pi state, but strongly suggest a misassignment of the fundamental vibrational frequency for the a1Sigma(+) state.

Symbolic derivation of high-order Rayleigh-Schroedinger perturbation energies using computer algebra: Application to vibrational-rotational analysis of diatomic molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Herbert, John M.

1997-01-01

Rayleigh-Schroedinger perturbation theory is an effective and popular tool for describing low-lying vibrational and rotational states of molecules. This method, in conjunction with ab initio techniques for computation of electronic potential energy surfaces, can be used to calculate first-principles molecular vibrational-rotational energies to successive orders of approximation. Because of mathematical complexities, however, such perturbation calculations are rarely extended beyond the second order of approximation, although recent work by Herbert has provided a formula for the nth-order energy correction. This report extends that work and furnishes the remaining theoretical details (including a general formula for the Rayleigh-Schroedinger expansion coefficients) necessary formore » calculation of energy corrections to arbitrary order. The commercial computer algebra software Mathematica is employed to perform the prohibitively tedious symbolic manipulations necessary for derivation of generalized energy formulae in terms of universal constants, molecular constants, and quantum numbers. As a pedagogical example, a Hamiltonian operator tailored specifically to diatomic molecules is derived, and the perturbation formulae obtained from this Hamiltonian are evaluated for a number of such molecules. This work provides a foundation for future analyses of polyatomic molecules, since it demonstrates that arbitrary-order perturbation theory can successfully be applied with the aid of commercially available computer algebra software.« less

n-Alkane adsorption to polar silica surfaces.

PubMed

Brindza, Michael R; Ding, Feng; Fourkas, John T; Walker, Robert A

2010-03-21

The structures of medium-length n-alkane species (C(8)-C(11)) adsorbed to a hydrophilic silica/vapor interface were examined using vibrational sum frequency spectroscopy. Experiments sampling out-of-plane orientation show a clear pattern in vibrational band intensities that implies chains having primarily all-trans conformations lying flat along the interface. Further analysis shows that the methylene groups of the alkane chains have their local symmetry axes directed into and away from the surface. Spectra acquired under different polarization conditions interlock to reinforce this picture of interfacial structure and organization. Variation in signal intensities with chain length suggests that correlation between adsorbed monomers weakens with increasing chain length. This result stands in contrast with alkane behavior at neat liquid/vapor interfaces where longer length alkanes show considerably more surface induced ordering than short chain alkanes.

Microfabricated instrument for tissue biopsy and analysis

DOEpatents

Krulevitch, Peter A.; Lee, Abraham P.; Northrup, M. Allen; Benett, William J.

2001-01-01

A microfabricated biopsy/histology instrument which has several advantages over the conventional procedures, including minimal specimen handling, smooth cutting edges with atomic sharpness capable of slicing very thin specimens (approximately 2 .mu.m or greater), micro-liter volumes of chemicals for treating the specimens, low cost, disposable, fabrication process which renders sterile parts, and ease of use. The cutter is a "cheese-grater" style design comprising a block or substrate of silicon and which uses anisotropic etching of the silicon to form extremely sharp and precise cutting edges. As a specimen is cut, it passes through the silicon cutter and lies flat on a piece of glass which is bonded to the cutter. Microchannels are etched into the glass or silicon substrates for delivering small volumes of chemicals for treating the specimen. After treatment, the specimens can be examined through the glass substrate.

Near-horizon BMS symmetries as fluid symmetries

NASA Astrophysics Data System (ADS)

Penna, Robert F.

2017-10-01

The Bondi-van der Burg-Metzner-Sachs (BMS) group is the asymptotic symmetry group of asymptotically flat gravity. Recently, Donnay et al. have derived an analogous symmetry group acting on black hole event horizons. For a certain choice of boundary conditions, it is a semidirect product of Diff( S 2), the smooth diffeomorphisms of the twosphere, acting on C ∞( S 2), the smooth functions on the two-sphere. We observe that the same group appears in fluid dynamics as symmetries of the compressible Euler equations. We relate these two realizations of Diff( S 2) ⋉ C ∞( S 2) using the black hole membrane paradigm. We show that the Lie-Poisson brackets of membrane paradigm fluid charges reproduce the near-horizon BMS algebra. The perspective presented here may be useful for understanding the BMS algebra at null infinity.

Lifetimes and energetics of the first electronically excited states of NaH2O from time-resolved photoelectron imaging

NASA Astrophysics Data System (ADS)

Gartmann, Thomas E.; Yoder, Bruce L.; Chasovskikh, Egor; Signorell, Ruth

2017-09-01

The energetics and lifetimes of the first electronically excited states (;3p-states;) of NaH2O and NaD2O have been measured by pump-probe (740/780 and 400 nm) photoelectron imaging. The photoelectron spectra of NaH2O show two bands at an electron kinetic energy of 0.14 and 0.38 eV, respectively. We assign the former to excitation via the two energetically close lying ;pπ-states; with flat potential curves in the intermolecular degrees of freedom, and the latter to the excitation via the ;pσ-state; characterized by significantly steeper potential curves. The relaxation of all ;p-states; follows a double exponential decay with a lifetime around 110 ps for the dominant fast component.

Real-time investigation of protein unfolding at an air–water interface at the 1 s time scale

PubMed Central

Yano, Yohko F.; Arakawa, Etsuo; Voegeli, Wolfgang; Matsushita, Tadashi

2013-01-01

Protein unfolding at an air–water interface has been demonstrated such that the X-ray reflectivity can be measured with an acquisition time of 1 s using a recently developed simultaneous multiple-angle–wavelength-dispersive X-ray reflectometer. This has enabled the electron density profile of the adsorbed protein molecules to be obtained in real time. A globular protein, lysozyme, adsorbed at the air–water interface is found to unfold into a flat shape within 1 s. PMID:24121352

Soil Erodibility Parameters Under Various Cropping Systems of Maize

NASA Astrophysics Data System (ADS)

van Dijk, P. M.; van der Zijp, M.; Kwaad, F. J. P. M.

1996-08-01

For four years, runoff and soil loss from seven cropping systems of fodder maize have been measured on experimental plots under natural and simulated rainfall. Besides runoff and soil loss, several variables have also been measured, including rainfall kinetic energy, degree of slaking, surface roughness, aggregate stability, soil moisture content, crop cover, shear strength and topsoil porosity. These variables explain a large part of the variance in measured runoff, soil loss and splash erosion under the various cropping systems. The following conclusions were drawn from the erosion measurements on the experimental plots (these conclusions apply to the spatial level at which the measurements were carried out). (1) Soil tillage after maize harvest strongly reduced surface runoff and soil loss during the winter; sowing of winter rye further reduced winter erosion, though the difference with a merely tilled soil is small. (2) During spring and the growing season, soil loss is reduced strongly if the soil surface is partly covered by plant residues; the presence of plant residue on the surface appeared to be essential in achieving erosion reduction in summer. (3) Soil loss reductions were much higher than runoff reductions; significant runoff reduction is only achieved by the straw system having flat-lying, non-fixed plant residue on the soil surface; the other systems, though effective in reducing soil loss, were not effective in reducing runoff.

Hyperspectral mapping of alteration assemblages within a hydrothermal vug at the Haughton impact structure, Canada

NASA Astrophysics Data System (ADS)

Greenberger, Rebecca N.; Mustard, John F.; Osinski, Gordon R.; Tornabene, Livio L.; Pontefract, Alexandra J.; Marion, Cassandra L.; Flemming, Roberta L.; Wilson, Janette H.; Cloutis, Edward A.

2016-12-01

Meteorite impacts on Earth and Mars can generate hydrothermal systems that alter the primary mineralogies of rocks and provide suitable environments for microbial colonization. We investigate a calcite-marcasite-bearing vug at the 23 km diameter Haughton impact structure, Devon Island, Nunavut, Canada, using imaging spectroscopy of the outcrop in the field (0.65-1.1 μm) and samples in the laboratory (0.4-2.5 μm), point spectroscopy (0.35-2.5 μm), major element chemistry, and X-ray diffraction analyses. The mineral assemblages mapped at the outcrop include marcasite; marcasite with minor gypsum and jarosite; fibroferrite and copiapite with minor gypsum and melanterite; gypsum, Fe3+ oxides, and jarosite; and calcite, gypsum, clay, microcline, and quartz. Hyperspectral mapping of alteration phases shows spatial patterns that illuminate changes in alteration conditions and formation of specific mineral phases. Marcasite formed from the postimpact hydrothermal system under reducing conditions, while subsequent weathering oxidized the marcasite at low temperatures and water/rock ratios. The acidic fluids resulting from the oxidation collected on flat-lying portions of the outcrop, precipitating fibroferrite + copiapite. That assemblage then likely dissolved, and the changing chemistry and pH resulting from interaction with the calcite-rich host rock formed gypsum-bearing red coatings. These results have implications for understanding water-rock interactions and habitabilities at this site and on Mars.

Submarine landslides in Arctic sedimentation: Canada Basin

USGS Publications Warehouse

Mosher, David C.; Shimeld, John; Hutchinson, Deborah R.; Lebedova-Ivanova, N; Chapman, C.

2016-01-01

Canada Basin of the Arctic Ocean is the least studied ocean basin in the World. Marine seismic field programs were conducted over the past 6 years using Canadian and American icebreakers. These expeditions acquired more than 14,000 line-km of multibeam bathymetric and multi-channel seismic reflection data over abyssal plain, continental rise and slope regions of Canada Basin; areas where little or no seismic reflection data existed previously. Canada Basin is a turbidite-filled basin with flat-lying reflections correlateable over 100s of km. For the upper half of the sedimentary succession, evidence of sedimentary processes other than turbidity current deposition is rare. The Canadian Archipelago and Beaufort Sea margins host stacked mass transport deposits from which many of these turbidites appear to derive. The stratigraphic succession of the MacKenzie River fan is dominated by mass transport deposits; one such complex is in excess of 132,000 km2 in area and underlies much of the southern abyssal plain. The modern seafloor is also scarred with escarpments and mass failure deposits; evidence that submarine landsliding is an ongoing process. In its latest phase of development, Canada Basin is geomorphologically confined with stable oceanographic structure, resulting in restricted depositional/reworking processes. The sedimentary record, therefore, underscores the significance of mass-transport processes in providing sediments to oceanic abyssal plains as few other basins are able to do.

A palaeomagnetic and 40Ar/39Ar study of late precambrian sills in the SW part of the Amazonian craton: Amazonia in the Rodinia reconstruction

NASA Astrophysics Data System (ADS)

Elming, S.-Å.; D'Agrella-Filho, M. S.; Page, L. M.; Tohver, E.; Trindade, R. I. F.; Pacca, I. I. G.; Geraldes, M. C.; Teixeira, W.

2009-07-01

A new key palaeomagnetic pole (Plat. = 64.3°S, Plon. = 271.0°E, N = 14, A95 = 9.2° Q = 5) is calculated from a primary magnetization isolated in early Neoproterozoic Aguapei basic sills and dykes hosted by 1.3-1.0 Ga sedimentary rocks from the southwestern part of the Amazon craton. The characteristic remanence carried by stable, pseudo-single domain titanomagnetite shows two antipodal polarities that pass a reversals test. Magnetic anisotropy for most sites shows fabric orientations that are typical of sills, with horizontal magnetic foliations concordant to the flat-lying bedding of the host sedimentary rocks. 40Ar/39Ar analyses for one of the sills reveal a well-defined plateau age at 981 +/- 2 Myr. A tectonic reconstruction for Amazonia relative Laurentia based on this new pole `is consistent with' a position of the present northwestern part of Amazonia attached with eastern Laurentia close to Greenland at ca. 981 Ma. On basis of palaeomagnetic and geological data, we propose a scenario where Amazonia moved northeastwards along the present southeast coast of Laurentia from ca. 1200 to 980 Ma. By 980 Ma, Amazonia is placed alongside Laurentia and Baltica, in a position similar to other reconstructions of Rodinia but with a significantly different orientation.

Pentacene on Au(1 1 1), Ag(1 1 1) and Cu(1 1 1): From physisorption to chemisorption.

PubMed

Lu, Meng-Chao; Wang, Rong-Bin; Yang, Ao; Duhm, Steffen

2016-03-09

We measured the electronic and the molecular surface structure of pentacene deposited on the (1 1 1)-surfaces of coinage metals by means of ultraviolet photoelectron spectroscopy (UPS) and low-energy electron diffraction (LEED). Pentacene is almost flat-lying in monolayers on all three substrates and highly ordered on Au(1 1 1) and on Cu(1 1 1). On Ag(1 1 1), however, weak chemisorption leads to almost disordered monolayers, both, at room temperature and at 78 K. On Cu(1 1 1) pentacene is strongly chemisorbed and the lowest unoccupied molecular orbital becomes observable in UPS by a charge transfer from the substrate. On Ag(1 1 1) and Cu(1 1 1) multilayers adopt a tilted orientation and a high degree of crystallinity. On Au(1 1 1), most likely, also in multilayers the molecular short and long axes are parallel to the substrate, leading to a distinctively different electronic structure than on Ag(1 1 1) and Cu(1 1 1). Overall, it could be demonstrated that the substrate not only determines the geometric and electronic characteristics of molecular monolayer films but also plays a crucial role for multilayer film growth.

Facies analysis and sequence stratigraphy of neoproterozoic Platform deposits in Adrar of Mauritania, Taoudeni basin, West Africa

NASA Astrophysics Data System (ADS)

Benan, C. A. A.; Deynoux, M.

The Neoproterozoic and Palaeozoic Taoudeni basin forms the flat-lying and unmetamorphosed sedimentary cover of the West African Craton. In the western part of this basin, the Char Group and the lower part of the Atar Group make up a 400-m-thick Neoproterozoic siliciclastic succession which rests on the Palaeoproterozoic metamorphic and granitic basement. Five erosional bounding surfaces of regional extent have been identified in this succession. These surfaces separate five stratigraphic units with lithofacies associations ranging from fluvial to coastal and fluvial-, tide-, or wave-dominated shallow marine deposits. Owing to their regional extent and their position within the succession, the erosive bounding surfaces correspond to relative sea-level falls, and accordingly the five stratigraphic units they bound represent allocyclic transgressive-regressive depositional sequences (S1-S5). Changes in the nature of the deposits forming the transgressive-regressive cycles reflect landward or seaward shifts of the stacked sequences. These successive relative sea-level changes are related to the reactivation of basement faults and tilting during rifting of the Pan-Afro-Brasiliano supercontinent 1000 m.y. ago. The stromatolite bearing carbonate-shale sequences which form the rest of the Atar Group mark the onset of a quiet period of homogeneous subsidence contemporaneous with the Pan-African I oceanization 800-700 m.y. ago.

Geologic map of the Alley Spring quadrangle, Shannon County, Missouri

USGS Publications Warehouse

Weary, David J.; Orndorff, Randall C.

2012-01-01

The Alley Spring 7.5-minute quadrangle is located in south-central Missouri within the Salem Plateau region of the Ozark Plateaus physiographic province. About 1,990 feet (ft) of flat-lying to gently dipping Lower Paleozoic sedimentary rocks, mostly dolomite, chert, sandstone, and orthoquartzite, overlie Mesoproterozoic volcanic rocks. A small exposure of the volcanic rocks exists near the eastern edge of the quadrangle. Unconsolidated residuum, colluvium, terrace deposits, and alluvium overlie the sedimentary rocks. Karst features, such as sinkholes, caves, and springs, have formed in the carbonate rocks. Many streams are spring fed. Alley Spring, the largest karst spring in the quadrangle, has an average discharge of 81 million gallons per day. The topography is a dissected karst plain with elevation ranging from 630 ft where the Jacks Fork River exits the quadrangle to more than 1,140 ft at numerous places in the northern half of the quadrangle. The most prominent physiographic feature is the valley of the Jacks Fork River. Most of the land in the quadrangle is privately owned and used primarily for grazing cattle and horses and growing timber. A large minority of the land within the quadrangle is publicly owned, either by the Missouri State Forests or by the Ozark National Scenic Riverways of the National Park Service. Geologic mapping for this investigation was conducted in 2003 and 2004.

Geology of the Stegall Mountain 7.5-minute quadrangle, Shannon and Carter Counties, south-central Missouri

USGS Publications Warehouse

Harrison, Richard W.; Orndorff, Randall C.; Weary, David J.

2002-01-01

The bedrock exposed in the Stegall Mountain Quadrangle, Missouri, comprises Mesoproterozoic aged volcanic rocks overlain by Late Cambrian and Early Ordovician aged dolomite, sandstone, and chert. The sedimentary rocks are nearly flat-lying except where they drape around knobs of the volcanic rocks or where they are adjacent to faults. The carbonates are karstified and the area contains numerous sinkholes, springs, caves, and losing-streams. This map is one of several being produced under the U.S. Geological Survey National Cooperative Geologic Mapping Program to provide geologic data applicable to land-use problems in the Ozarks of south-central Missouri. Ongoing and potential industrial and agricultural development in the Ozarks region has presented issues of ground-water quality in karst areas. A National Park in this region (Ozark National Scenic Riverways, Missouri ) is concerned about the effects of activities in areas outside of their stewardship on the water resources that define the heart of this Park. This task applies geologic mapping and karst investigations to address issues surrounding competing land use in south-central Missouri. This task keeps geologists from the USGS associated with the park and allows the Parks to utilize USGS expertise and aid the NPS on how to effectively use geologic maps for Park management. For more information see: http://geology.er.usgs.gov/eespteam/Karst/index.html

Verification of the modified model of drying process of a polymer liquid film on a flat substrate by experiment (3) - using organic solvent

NASA Astrophysics Data System (ADS)

Kagami, Hiroyuki

2007-05-01

We have proposed and modified a model of drying process of polymer solution coated on a flat substrate for flat polymer film fabrication and have presented the fruits through Photomask Japan 2002, 2003, 2004, Smart Materials, Nano-, and Micro-Smart Systems 2006 and so on. And for example numerical simulation of the model qualitatively reappears a typical thickness profile of the polymer film formed after drying, that is, the profile that the edge of the film is thicker and just the region next to the edge's bump is thinner. Then we have clarified dependence of distribution of polymer molecules on a flat substrate on a various parameters based on analysis of many numerical simulations. Then we did a few kinds of experiments so as to verify the modified model and reported the results of them through Photomask Japan 2005 and 2006. We could observe some results supporting the modified model. But we could not observe a characteristic region of a valley next to the edge's bump of a polymer film after drying. After some trial of various improved experiments we reached the conclusion that the characteristic region didn't appear by reason that water which vaporized slower than organic solvent was used as solvent. Then, in this study, we adopted organic solvent instead of water as solvent for experiments. As a result, that the characteristic region as mentioned above could be seen and we could verify the model more accurately. In this paper, we present verification of the model through above improved experiments for verification using organic solvent.

Conformational and functional similarities between glutaredoxin and thioredoxins.

PubMed Central

Eklund, H; Cambillau, C; Sjöberg, B M; Holmgren, A; Jörnvall, H; Höög, J O; Brändén, C I

1984-01-01

The tertiary structures of thioredoxin from Escherichia coli and bacteriophage T4 have been compared and aligned giving a common fold of 68 C alpha atoms with a root mean square difference of 2.6 A. The amino acid sequence of glutaredoxin has been aligned to those of the thioredoxins assuming that glutaredoxin has the same common fold. A model of the glutaredoxin molecule was built on a vector display using this alignment and the T4 thioredoxin tertiary structure. By comparison of the model with those of the thioredoxins, we have identified a molecular surface area on one side of the redox-active S-S bridge which we suggest is the binding area of these molecules for redox interactions with other proteins. This area comprises residues 33-34, 75-76 and 91-93 in E. coli thioredoxin; 15-16, 65-66 and 76-78 in T4 thioredoxin and 12-13, 59-60 and 69-71 in glutaredoxin. In all three molecules, this part of the surface is flat and hydrophobic. Charged groups are completely absent. In contrast, there is a cluster of charged groups on the other side of the S-S bridge which we suggest participates in the mechanisms of the redox reactions. In particular, a lysine residue close to an aromatic ring is conserved in all molecules. PMID:6378624

Sugar-binding sites on the surface of the carbohydrate-binding module of CBH I from Trichoderma reesei.

PubMed

Tavagnacco, Letizia; Mason, Philip E; Schnupf, Udo; Pitici, Felicia; Zhong, Linghao; Himmel, Michael E; Crowley, Michael; Cesàro, Attilio; Brady, John W

2011-05-01

Molecular dynamics simulations were carried out for a system consisting of the carbohydrate-binding module (CBM) of the cellulase CBH I from Trichoderma reesei (Hypocrea jecorina) in a concentrated solution of β-D-glucopyranose, to determine whether there is any tendency for the sugar molecules to bind to the CBM. In spite of the general tendency of glucose to behave as an osmolyte, a marked tendency for the sugar molecules to bind to the protein was observed. However, the glucose molecules tended to bind only to specific sites on the protein. As expected, the hydrophobic face of the sugar molecules, comprising the axial H1, H3, and H5 aliphatic protons, tended to adhere to the flat faces of the three tyrosine side chains on the planar binding surface of the CBM. However, a significant tendency to bind to a groove-like feature on the upper surface of the CBM was also observed. These results would not be inconsistent with a model of the mechanism for this globular domain in which the cellodextrin chain being removed from the surface of crystalline cellulose passes over the upper surface of the CBM, presumably then available for hydrolysis in the active site tunnel of this processive cellulase. Copyright © 2011 Elsevier Ltd. All rights reserved.

High-spatial-resolution mapping of catalytic reactions on single particles

DOE PAGES

Wu, Chung-Yeh; Wolf, William J.; Levartovsky, Yehonatan; ...

2017-01-26

We report the critical role in surface reactions and heterogeneous catalysis of metal atoms with low coordination numbers, such as found at atomic steps and surface defects, is firmly established. But despite the growing availability of tools that enable detailed in situ characterization, so far it has not been possible to document this role directly. Surface properties can be mapped with high spatial resolution, and catalytic conversion can be tracked with a clear chemical signature; however, the combination of the two, which would enable high-spatial-resolution detection of reactions on catalytic surfaces, has rarely been achieved. Single-molecule fluorescence spectroscopy has beenmore » used to image and characterize single turnover sites at catalytic surfaces, but is restricted to reactions that generate highly fluorescing product molecules. Herein the chemical conversion of N-heterocyclic carbene molecules attached to catalytic particles is mapped using synchrotron-radiation-based infrared nanospectroscopy with a spatial resolution of 25 nanometres, which enabled particle regions that differ in reactivity to be distinguished. Lastly, these observations demonstrate that, compared to the flat regions on top of the particles, the peripheries of the particles-which contain metal atoms with low coordination numbers-are more active in catalysing oxidation and reduction of chemically active groups in surface-anchored N-heterocyclic carbene molecules.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wu, Chung-Yeh; Wolf, William J.; Levartovsky, Yehonatan

We report the critical role in surface reactions and heterogeneous catalysis of metal atoms with low coordination numbers, such as found at atomic steps and surface defects, is firmly established. But despite the growing availability of tools that enable detailed in situ characterization, so far it has not been possible to document this role directly. Surface properties can be mapped with high spatial resolution, and catalytic conversion can be tracked with a clear chemical signature; however, the combination of the two, which would enable high-spatial-resolution detection of reactions on catalytic surfaces, has rarely been achieved. Single-molecule fluorescence spectroscopy has beenmore » used to image and characterize single turnover sites at catalytic surfaces, but is restricted to reactions that generate highly fluorescing product molecules. Herein the chemical conversion of N-heterocyclic carbene molecules attached to catalytic particles is mapped using synchrotron-radiation-based infrared nanospectroscopy with a spatial resolution of 25 nanometres, which enabled particle regions that differ in reactivity to be distinguished. Lastly, these observations demonstrate that, compared to the flat regions on top of the particles, the peripheries of the particles-which contain metal atoms with low coordination numbers-are more active in catalysing oxidation and reduction of chemically active groups in surface-anchored N-heterocyclic carbene molecules.« less

Mono- and Polyhydrated Sulfates in Tithonium Chasma

NASA Technical Reports Server (NTRS)

2008-01-01

This image of sulfate-containing deposits in Tithonium Chasma was taken by the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) at 1538 UTC (11:38 a.m. EDT) on August 31, 2007 near 5.22 degrees south latitude, 270.48 degrees east longitude. CRISM's image was taken in 544 colors covering 0.36-3.92 micrometers, and shows features as small as 40 meters (132 feet) across. The region covered is just over 10 kilometers (6.2 miles) wide at its narrowest point.

Tithonium Chasma lies at the western end of the Valles Marineris canyon system. It extends approximately east-west for roughly 810 kilometers (503 miles), varies in width from approximately 10 to 110 kilometers (6 to 68 miles), and cuts into the Martian surface to a maximum depth of roughly 6 kilometers (4 miles).

The top panel in the montage above shows the location of the CRISM image on a mosaic taken by the Mars Odyssey spacecraft's Thermal Emission Imaging System (THEMIS). The CRISM data covers an area centered on a ridge of erosion-resistant rock.

The center left image, an infrared false color image, reveals banded, light-colored material draped on the ridge. The center right image unveils the mineralogical composition of the area, with yellow representing monohydrated sulfates (sulfates with one water molecule incorporated into each molecule of the mineral) and purple polyhydrated sulfates (sulfates with multiple waters per mineral molecule).

The lower two images are renderings of data draped over topography with 7 times vertical exaggeration. These images provide a view of the topography and reveal how the sulfate deposits both cover and flank the ridge. Brighter, monohydrated sulfate (yellow) deposits revealed in the lower right image lies along the ridge's northwest side and fall off into a small valley or depression, while darker polyhydrated sulfates (purple) lie along the ridge's northeast flank. A deposit of both mono- and polyhydrated sulfates spanning the ridge near its crest also appears to be coarsely banded.

CRISM is one of six science instruments on NASA's Mars Reconnaissance Orbiter. Led by The Johns Hopkins University Applied Physics Laboratory, Laurel, Md., the CRISM team includes expertise from universities, government agencies and small businesses in the United States and abroad. NASA's Jet Propulsion Laboratory, a division of the California Institute of Technology in Pasadena, manages the Mars Reconnaissance Orbiter and the Mars Science Laboratory for NASA's Science Mission Directorate, Washington. Lockheed Martin Space Systems, Denver, built the orbiter.

Millimeter-wave spectroscopy of hydantoin, a possible precursor of glycine

NASA Astrophysics Data System (ADS)

Ozeki, Hiroyuki; Miyahara, Rio; Ihara, Hiroto; Todaka, Satoshi; Kobayashi, Kaori; Ohishi, Masatoshi

2017-04-01

Context. Hydantoin (Imidazolidine-2, 4-dione, C3H4N2O2) is a five-membered heterocyclic compound that is known to arise from prebiotic molecules such as glycolic acid and urea, and to give the simplest amino acid, glycine, by hydrolysis under acidic condition. The gas chromatography combined with the mass spectrometry of carbonaceous chondrites lead to the detection of this molecule as well as several kinds of amino acids. Aims: The lack of spectroscopic information, especially on the rotational constants, has prevented us from conducting a search for hydantoin in interstellar space. If a rotational temperature of 100 K is assumed as the kinetic temperature of a star-forming region, the spectral intensity is expected to be at its maximum in the millimeter-wave region. Laboratory spectroscopy of hydantoin in the millimeter-wave region is the most important in providing accurate rest frequencies to be used for astronomical research. Methods: Pure rotational spectra of hydantoin were observed in the millimeter-wave region using the frequency modulated microwave spectrometer at Toho University. Solid hydantoin was heated to around 150 °C to provide appropriate vapor pressure. Quantum chemical calculations suggest that the permanent dipole moment of this molecule lies almost along the b-molecular axis, so that spectral search for b-type R-branch transition has been conducted. Results: Rotational and centrifugal distortion constants up to the fourth order for the ground vibrational state of hydantoin were accurately determined by measuring 161 b-type transitions in the frequency range between 90 and 370 GHz. In addition, we succeeded in assigning 230 satellite lines, which were attributed to the two vibrationally excited states. The spectral intensity ratio of these lines indicates that these states correspond to the low-lying (approximately 150 cm-1 above the ground state) vibrational modes. Conclusions: The frequency catalog of hydantoin in the millimeter-wave range was created for the ground state and for the two low-lying excited states, and are ideal for a future astronomical research. The 1σ frequency accuracy is lower than 100 kHz for the lines with upper-state energy below 200 cm-1, corresponding to a velocity resolution of 0.1 km s-1 at 300 GHz The spectral line list of hydantoin is available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/600/A44

DOE Office of Scientific and Technical Information (OSTI.GOV)

Herman, Michael F.; Currier, Robert P.; Peery, Travis B.

Intermolecular coupling of dipole moments is studied for a model system consisting of two diatomic molecules (AB monomers) arranged co-linearly and which can form non-covalently bound dimers. The dipolar coupling is a function of the bond length in each molecule as well as of the distance between the centers-of-mass of the two molecules. The calculations show that intermolecular coupling of the vibrations results in an isotope-dependent modification of the AB-AB intermolecular potential. This in turn alters the energies of the low-lying bound states of the dimers, producing isotope-dependent changes in the AB-AB dimer partition function. Explicit inclusion of intermolecular vibrationalmore » coupling then changes the predicted gas-dimer isotopic fractionation. In addition, a mass dependence in the intermolecular potential can also result in changes in the number of bound dimer states in an equilibrium mixture. This in turn leads to a significant dimer population shift in the model monomer-dimer equilibrium system considered here. Finally, the results suggest that intermolecular coupling terms should be considered when probing the origins of isotopic fractionation.« less

A test of the significance of intermolecular vibrational coupling in isotopic fractionation

DOE PAGES

Herman, Michael F.; Currier, Robert P.; Peery, Travis B.; ...

2017-07-15

Intermolecular coupling of dipole moments is studied for a model system consisting of two diatomic molecules (AB monomers) arranged co-linearly and which can form non-covalently bound dimers. The dipolar coupling is a function of the bond length in each molecule as well as of the distance between the centers-of-mass of the two molecules. The calculations show that intermolecular coupling of the vibrations results in an isotope-dependent modification of the AB-AB intermolecular potential. This in turn alters the energies of the low-lying bound states of the dimers, producing isotope-dependent changes in the AB-AB dimer partition function. Explicit inclusion of intermolecular vibrationalmore » coupling then changes the predicted gas-dimer isotopic fractionation. In addition, a mass dependence in the intermolecular potential can also result in changes in the number of bound dimer states in an equilibrium mixture. This in turn leads to a significant dimer population shift in the model monomer-dimer equilibrium system considered here. Finally, the results suggest that intermolecular coupling terms should be considered when probing the origins of isotopic fractionation.« less

FAST TRACK COMMUNICATION: Conformation dependence of molecular conductance: chemistry versus geometry

NASA Astrophysics Data System (ADS)

Finch, Christopher M.; Sirichantaropass, Skon; Bailey, Steven W.; Grace, Iain M.; García-Suárez, Víctor M.; Lambert, Colin J.

2008-01-01

Recent experiments by Venkataraman et al (2006 Nature 442 904) on a series of molecular wires with varying chemical compositions revealed a linear dependence of the conductance on cos2 θ, where θ is the angle of twist between neighbouring aromatic rings. To investigate whether or not this dependence has a more general applicability, we present a first-principles theoretical study of the transport properties of this family of molecules as a function of the chemical composition, conformation and the contact atom and geometry. If the Fermi energy EF lies within the HOMO-LUMO (highest occupied molecular orbital-lowest unoccupied molecular orbital) gap, then we reproduce the above experimental results. More generally, however, if EF is located within either the LUMO or the HOMO states, the presence of resonances destroys the linear dependence of the conductance on cos2 θ and gives rise to non-monotonic behaviour associated with the level structure of the different molecules. Our results suggest that the above experiments provide a novel method for extracting spectroscopic information about molecules contacted to electrodes.

Microwave spectroscopy of 2-(trifluoromethyl)pyridine⋯water complex: Molecular structure and hydrogen bond

NASA Astrophysics Data System (ADS)

Li, Xiaolong; Zheng, Yang; Gou, Qian; Feng, Gang; Xia, Zhining

2018-01-01

In order to explore the -CF3 substitution effect on the complexation of pyridine, we investigated the 2-(trifluoromethyl)pyridine⋯water complex by using pulsed jet Fourier transform microwave spectroscopy complemented with quantum chemical calculations. Experimental assignment and ab initio calculations confirmed that the observed complex is stabilized through N⋯H-O and O⋯H-C hydrogen bonds forming a five-membered ring structure. The bonding distance in N⋯H-O is determined to be 2.027(2) Å, whilst that in O⋯H-C interaction is 2.728(2) Å. The quantum theory of atoms in molecules analysis indicates that the interaction energy of N⋯H-O hydrogen bond is ˜22 kJ mol-1 and that for O⋯H-C hydrogen bond is ˜5 kJ mol-1. The water molecule lies almost in the plane of the aromatic ring in the complex. The -CF3 substitution to pyridine quenches the tunneling splitting path of the internal motion of water molecule.

Electronic transitions of tantalum monofluoride

NASA Astrophysics Data System (ADS)

Ng, K. F.; Zou, Wenli; Liu, Wenjian; Cheung, A. S.-C.

2017-03-01

The electronic transition spectrum of the tantalum monofluoride (TaF) molecule in the spectral region between 448 and 560 nm has been studied using the technique of laser-ablation/reaction free jet expansion and laser induced fluorescence spectroscopy. The TaF molecule was produced by reacting laser-ablated tantalum atoms with sulfur hexafluoride gas seeded in argon. Twenty-two vibrational bands with resolved rotational structure have been recorded and analyzed, which were organized into seven electronic transitions. The X3Σ-(0+) state has been identified to be the ground state and the determined equilibrium bond length, re, and vibrational frequency, ωe, are 1.8184 Å and 700.1 cm-1, respectively. The low-lying Λ-S states and Ω sub-states of TaF were also theoretically studied at the MRCISD+Q level of theory with spin-orbit coupling. The Ω = 0+ and 2 sub-states from the -3Σ and 3Φ state have been found to be the ground and the first excited states, respectively, which agrees well with our experimental determinations. This work represents the first experimental investigation of the molecular structure of the TaF molecule.

Anharmonic Infrared Spectroscopy through the Fourier Transform of Time Correlation Function Formalism in ONETEP.

PubMed

Vitale, Valerio; Dziedzic, Jacek; Dubois, Simon M-M; Fangohr, Hans; Skylaris, Chris-Kriton

2015-07-14

Density functional theory molecular dynamics (DFT-MD) provides an efficient framework for accurately computing several types of spectra. The major benefit of DFT-MD approaches lies in the ability to naturally take into account the effects of temperature and anharmonicity, without having to introduce any ad hoc or a posteriori corrections. Consequently, computational spectroscopy based on DFT-MD approaches plays a pivotal role in the understanding and assignment of experimental peaks and bands at finite temperature, particularly in the case of floppy molecules. Linear-scaling DFT methods can be used to study large and complex systems, such as peptides, DNA strands, amorphous solids, and molecules in solution. Here, we present the implementation of DFT-MD IR spectroscopy in the ONETEP linear-scaling code. In addition, two methods for partitioning the dipole moment within the ONETEP framework are presented. Dipole moment partitioning allows us to compute spectra of molecules in solution, which fully include the effects of the solvent, while at the same time removing the solvent contribution from the spectra.

Peptide adsorption on the hydrophobic surface: A free energy perspective

NASA Astrophysics Data System (ADS)

Sheng, Yuebiao; Wang, Wei; Chen, P.

2011-05-01

Protein adsorption is a very attractive topic which relates to many novel applications in biomaterials, biotechnology and nanotechnology. Ionic complementary peptides are a group of novel nano-biomaterials with many biomedical applications. In this work, molecular dynamics simulations of the ionic-complementary peptide EAK16-II on a hydrophobic graphite surface were performed under neutral, acidic and basic solution conditions. Adsorption free energy contour maps were obtained by analyzing the dynamical trajectories. Hydrophobic interactions were found to govern the adsorption of the first peptide molecule, and both hydrophobic and electrostatic interactions contributed to the adsorption of the second peptide molecule. Especially under acidic and basic solution conditions, interplay existed among chain-chain hydrophobic, chain-surface hydrophobic and chain-chain electrostatic interactions during the adsorption of the second peptide molecule. Non-charged residues were found to lie on the graphite surface, while charged residue side-chains oriented towards the solution after the peptide deposited on the surface. These results provide a basis for understanding peptide adsorption on the hydrophobic surface under different solution conditions, which is useful for novel applications such as bioactive implant devices and drug delivery material design.

Vacuum ultraviolet spectroscopy of the lowest-lying electronic state in subcritical and supercritical water

NASA Astrophysics Data System (ADS)

Marin, Timothy W.; Janik, Ireneusz; Bartels, David M.; Chipman, Daniel M.

2017-05-01

The nature and extent of hydrogen bonding in water has been scrutinized for decades, including how it manifests in optical properties. Here we report vacuum ultraviolet absorption spectra for the lowest-lying electronic state of subcritical and supercritical water. For subcritical water, the spectrum redshifts considerably with increasing temperature, demonstrating the gradual breakdown of the hydrogen-bond network. Tuning the density at 381 °C gives insight into the extent of hydrogen bonding in supercritical water. The known gas-phase spectrum, including its vibronic structure, is duplicated in the low-density limit. With increasing density, the spectrum blueshifts and the vibronic structure is quenched as the water monomer becomes electronically perturbed. Fits to the supercritical water spectra demonstrate consistency with dimer/trimer fractions calculated from the water virial equation of state and equilibrium constants. Using the known water dimer interaction potential, we estimate the critical distance between molecules (ca. 4.5 Å) needed to explain the vibronic structure quenching.

Sigma- versus Pi-Dimerization Modes of Triangulene.

PubMed

Mou, Zhongyu; Kertesz, Miklos

2018-04-20

We show that the diradicaloid triangulene, a graphene nano-flake molecule, can aggregate in a variety of dimerization modes. We found by density functional theory modeling a number of triangulene dimers including six doubly bonded σ-dimers in addition to the previously reported six pancake bonded π-dimer isomers. The σ-dimers display a wide range of stabilities: the interaction energy of the most stable σ-dimer is -25.17 kcal mol -1 . Besides the doubly bonded σ-dimers with closed shell ground states, we also found an open-shell singly σ-bonded diradicaloid dimer. We found an interesting isomerization route between a doubly bonded σ-dimer, a singly bonded σ-dimer with a low-lying triplet state and two π-bonded dimers with low-lying quintet states. Derivatives of triangulene, trioxo-triangulenes (TOTs) have been previously characterized experimentally. Here, we show the reasons why so far only the π-dimer but not the σ-dimer was experimentally observed for all TOTs. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Vacuum ultraviolet spectroscopy of the lowest-lying electronic state in subcritical and supercritical water

DOE PAGES

Marin, Timothy W.; Janik, Ireneusz; Bartels, David M.; ...

2017-05-17

The nature and extent of hydrogen bonding in water has been scrutinized for decades, including how it manifests in optical properties. Here we report vacuum ultraviolet absorption spectra for the lowest-lying electronic state of subcritical and supercritical water. For subcritical water, the spectrum redshifts considerably with increasing temperature, demonstrating the gradual breakdown of the hydrogen-bond network. Tuning the density at 381°C gives insight into the extent of hydrogen bonding in supercritical water. The known gas-phase spectrum, including its vibronic structure, is duplicated in the low-density limit. With increasing density, the spectrum blueshifts and the vibronic structure is quenched as themore » water monomer becomes electronically perturbed. Fits to the supercritical water spectra demonstrate consistency with dimer/trimer fractions calculated from the water virial equation of state and equilibrium constants. As a result, using the known water dimer interaction potential, we estimate the critical distance between molecules (ca. 4.5 Å) needed to explain the vibronic structure quenching.« less

Nonadiabatic Photo-Process Involving the πσ* State in Intramolecular Charge Transfer: a Concerted Spectroscopic and Computational Study 4-(DIMETHYLAMINO)BENZETHYNE and 4-(DIMETHYLAMINO)BENZONITRILE.

NASA Astrophysics Data System (ADS)

Fujiwara, Takashige; Segarra-Martí, Javier; Coto, Pedro B.

2014-06-01

The ubiquitous nature of the low-lying πσ* state in the photo-excited aromatic molecules or biomolecules is widely recognized to play an important role in nonadiabatic photo-process such as photodissociation or intramolecular charge transfer (ICT). For instance, the O--H elimination channel in phenol is attributed to the state-cross of the repulsive πσ* state that exhibits a conical intersection with the lowest bright ππ* state and with the ground state, leading to ultrafast electronic deactivation. A similar decay pathway has been found in the ICT formation of 4-(dialkylamino)benzonitriles in a polar environment, where an initially photoexcited Frank-Condon state bifurcates in the presence of a dark intermediate πσ* state that crosses the fluorescent ππ* state, followed by a conical intersection with the twisted intramolecular charge transfer (TICT) state. We proposed such a two-fold decay mechanism that πσ*-state highly mediates intramolecular charge transfer in 4-(dialkylamino)benzonitriles, which is supported from both our high-level ab initio calculations and ultrafast laser spectroscopies in the previous study. 4-(Dimethylamino)benzethyne (DMABE) is isoelectronic with 4-(dimethylamino)benzonitrile (DMABN), and the electronic structures and electronic spectra of the two molecules bear very close resemblance. However, DMABN does show the ICT formation in a polar environment, whereas DMABE does not. To probe the photophysical differences among the low-lying excited-state configurations, we performed concerted time-resolved laser spectroscopies and high level ab initio multireference perturbation theory quantum-chemical (CASPT2//CASSCF) computations on the two molecules. In this paper we demonstrate the importance of the bound excited-state of a πσ* configuration that induce highly πσ*-state mediated intramolecular charge transfer in 4-(dialkylamino)benzonitriles.

Doping graphene films via chemically mediated charge transfer.

PubMed

Ishikawa, Ryousuke; Bando, Masashi; Morimoto, Yoshitaka; Sandhu, Adarsh

2011-01-31

Transparent conductive films (TCFs) are critical components of a myriad of technologies including flat panel displays, light-emitting diodes, and solar cells. Graphene-based TCFs have attracted a lot of attention because of their high electrical conductivity, transparency, and low cost. Carrier doping of graphene would potentially improve the properties of graphene-based TCFs for practical industrial applications. However, controlling the carrier type and concentration of dopants in graphene films is challenging, especially for the synthesis of p-type films. In this article, a new method for doping graphene using the conjugated organic molecule, tetracyanoquinodimethane (TCNQ), is described. Notably, TCNQ is well known as a powerful electron accepter and is expected to favor electron transfer from graphene into TCNQ molecules, thereby leading to p-type doping of graphene films. Small amounts of TCNQ drastically improved the resistivity without degradation of optical transparency. Our carrier doping method based on charge transfer has a huge potential for graphene-based TCFs.

Multicolor emission from large-area porous thin films constructed of nanowires of small organic molecules

NASA Astrophysics Data System (ADS)

Wang, Zhe-Chen; Xiao, Wen-Chang; Ding, Xun-Lei; Ma, Yan-Ping; Xue, Wei; He, Sheng-Gui

2008-12-01

We describe a facile low-temperature physical vapor deposition approach to fabricate porous network thin films constructed of nanowires of small organic molecules on a large area. Supermolecular assemblies of pyrene nanowires based on a combination of van der Waals forces and π-π stacking tend to hierarchically self-assemble to form uniform porous films using our techniques. The morphology of the films is studied and we also study several reasons influencing the process of assembly such as evaporation temperature, deposition temperature, and different kinds of substrate. The deposition temperature is determined to be the main reason for hierarchical aggregation. Typically prepared films exhibit unique optical properties, that is, multicolor red-green-blue emissions. This novel method can be applied to other organic molecular systems and may be potentially used to place nanoscaled building blocks directly on solid surfaces for fabricating large-area nanostructure-based flat screens.

Finite-Temperature Hydrogen Adsorption/Desorption Thermodynamics Driven by Soft Vibration Modes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Woo, Sung-Jae; Lee, Eui-Sup; Yoon, Mina

2013-01-01

It is widely accepted that room-temperature hydrogen storage on nanostructured or porous materials requires enhanced dihydrogen adsorption. In this work we reveal that room-temperature hydrogen storage is possible not only by the enhanced adsorption, but also by making use of the vibrational free energy from soft vibration modes. These modes exist for example in the case of metallo-porphyrin-incorporated graphenes (M-PIGs) with out-of-plane ( buckled ) metal centers. There, the in-plane potential surfaces are flat because of multiple-orbital-coupling between hydrogen molecules and the buckled-metal centers. This study investigates the finite-temperature adsorption/desorption thermodynamics of hydrogen molecules adsorbed on M-PIGs by employing first-principlesmore » total energy and vibrational spectrum calculations. Our results suggest that the current design strategy for room-temperature hydrogen storage materials should be modified by explicitly taking finite-temperature vibration thermodynamics into account.« less

An investigation of isomerization pathways of epoxysaccharides

NASA Astrophysics Data System (ADS)

Andrianov, V. M.; Kirillova, S. G.; Zhbankov, R. G.

1997-07-01

Direct and reverse interconversion pathways of six epoxysaccharide molecules, namely, three molecules with epoxypyranose rings: methyl 2,3-anhydro-2,3,4-trideoxy- β- D-lyxohexopyranoside, methyl 2,3-anhydro-4-deoxy- α- D, L-ribo- and - α- D, L-lyxohexopyranosides and three molecules with epoxypyranose rings: methyl 2,6-di- O-acetyl-3,4-anhydro- α- D, L-( 6,6- 2H2) derivatives of talopyranoside and galactopyranoside, and methyl 3,4-anhydro- α- D, L-allopyranoside were simulated by the Wiberg and Boyd method. This made it possible to determine all stationary and intermediate forms in which anhydropyranose rings can exist. Calculations of barrier heights for interconversion and energies of global minima have shown that conformations revealed in X-ray studies are more favorable. Most of the local minima found lie in the vicinity of the boat (B) forms, the other minima correspond to conformations possessing symmetry elements of the skew-boat (S) and twist (T) forms. The interconversion pathways of the molecules investigated are presented on the Cremer-Pople diagram. We studied the effect of various structural factors on the character of conformational transformations, heights of transition barriers, the form of the ground state, and the energy of stationary forms, and their number and location on the Cremer-Pople diagram.

One-step formation of straight nanostripes from a mammal lipid-oleamide directly on highly oriented pyrolytic graphite.

PubMed

Zhang, Renjie; Möhwald, Helmuth; Kurth, Dirk G

2009-02-17

Hierarchical nanostructures are obtained directly on highly oriented pyrolytic graphite (HOPG) by spin coating of dilute chloroform solution of 9-Z-octadecenamide (oleamide), a natural lipid with cis-CdC- conformation, existing in the cerebrospinal fluid of mammal animals and being an additive for medical use and food packaging. Straight separated nanostripes with a length of 70-300 nm exist in the topmost layer and compact nanostripes in the bottom layer contacting HOPG. Compact nanostripes have a periodicity spacing of 3.8 nm, indicating H-bonding between two rows of oleamide molecules. The orientation of the hierarchical nanostructures differs by n60 degrees+/-8 degrees (n=1 or 2), reflecting the epitaxial ordering along theHOPGsubstrate. The nanostripes are stable against annealing.Amolecular packing scheme for the nanostructures is proposed, where the -C=C bond angle in oleamide is 120 degrees and the plane of the carbon skeleton lies parallel to the HOPG substrate. Nanostripes in the topmost layer are formed from separated rows of oleamide molecules, due to the short-range surface potential of the substrate. The scheme involves direct influence ofHOPGon the orientation of oleamide molecules to form nanostripes without any purposely added saturated alkanes and H-bonds between amide groups in adjacent two rows of oleamide molecules.

Short-Lived Electronically-Excited Diatomic Molecules Cooled via Supersonic Expansion from a Plasma Microjet

NASA Astrophysics Data System (ADS)

Houlahan, Thomas J., Jr.; Su, Rui; Eden, Gary

2014-06-01

Using a pulsed plasma microjet to generate short-lived, electronically-excited diatomic molecules, and subsequently ejecting them into vacuum to cool via supersonic expansion, we are able to monitor the cooling of molecules having radiative lifetimes as low as 16 ns. Specifically, we report on the rotational cooling of He_2 molecules in the d^3Σ_u^+, e^3Π_g, and f^3Σ_u^+ states, which have lifetimes of 25 ns, 67 ns, and 16 ns, respectively. The plasma microjet is driven with a 2.6 kV, 140 ns high-voltage pulse (risetime of 20 ns) which, when combined with a high-speed optical imaging system, allows the nonequilibrium rotational distribution for these molecular states to be monitored as they cool from 1200 K to below 250 K with spatial and temporal resolutions of below 10 μm and 10 ns, respectively. The spatial and temporal resolution afforded by this system also allows the observation of excitation transfer between the f^3Σ_u^+ state and the lower lying d^3Σ_u^+ and e^3Π_g states. The extension of this method to other electronically excited diatomics with excitation energies >5 eV will also be discussed.

Di-μ-cyanido-tetra-cyanido(5,5,7,12,12,14-hexa-methyl-1,4,8,11-tetra-aza-cyclo-tetra-decane)[N-(quinolin-8-yl)quinoline-2-carboxamidato]diiron(III)nickel(II) 2.07-hydrate.

PubMed

Yang, Yuqi; Zhou, Hongbo; Shen, Xiaoping

2013-05-01

The asymmetric unit of the title complex, [Fe2Ni(C19H12N3O)2(CN)6(C16H36N4)]·2.07H2O, contains one [Fe(qcq)(CN)3](-) anion, half a [Ni(teta)](2+) cation and two partially occupied inter-stitial water mol-ecules [qcq(-) is the N-(quinolin-8-yl)quinoline-2-carboxamidate anion and teta is 5,5,7,12,12,14-hexa-methyl-1,4,8,11-tetra-aza-cyclo-tetra-deca-ne]. In the complex mol-ecule, two [Fe(qcq)(CN)3](-) anions additionally coordinate the central [Ni(teta)](2+) cation through cyanide groups in a trans mode, resulting in a trinuclear structure with the Ni(2+) cation lying on an inversion centre. The two inter-stitial water mol-ecules are partially occupied, with occupancy factors of 0.528 (10) and 0.506 (9). O-H⋯O and O-H⋯N hydrogen bonding involving the two lattice water molecules and the carbonyl function and a teta N atom in an adjacent cluster leads to the formation of layers extending parallel to (010).

A systematic benchmark of the ab initio Bethe-Salpeter equation approach for low-lying optical excitations of small organic molecules

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bruneval, Fabien; Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720; Department of Physics, University of California, Berkeley, California 94720

2015-06-28

The predictive power of the ab initio Bethe-Salpeter equation (BSE) approach, rigorously based on many-body Green’s function theory but incorporating information from density functional theory, has already been demonstrated for the optical gaps and spectra of solid-state systems. Interest in photoactive hybrid organic/inorganic systems has recently increased and so has the use of the BSE for computing neutral excitations of organic molecules. However, no systematic benchmarks of the BSE for neutral electronic excitations of organic molecules exist. Here, we study the performance of the BSE for the 28 small molecules in Thiel’s widely used time-dependent density functional theory benchmark setmore » [Schreiber et al., J. Chem. Phys. 128, 134110 (2008)]. We observe that the BSE produces results that depend critically on the mean-field starting point employed in the perturbative approach. We find that this starting point dependence is mainly introduced through the quasiparticle energies obtained at the intermediate GW step and that with a judicious choice of starting mean-field, singlet excitation energies obtained from BSE are in excellent quantitative agreement with higher-level wavefunction methods. The quality of the triplet excitations is slightly less satisfactory.« less

One and two hydrogen molecules in the large cage of the structure II clathrate hydrate: quantum translation-rotation dynamics close to the cage wall.

PubMed

Sebastianelli, Francesco; Xu, Minzhong; Kanan, Dalal K; Bacić, Zlatko

2007-07-19

We have performed a rigorous theoretical study of the quantum translation-rotation (T-R) dynamics of one and two H2 and D2 molecules confined inside the large hexakaidecahedral (5(12)6(4)) cage of the sII clathrate hydrate. For a single encapsulated H2 and D2 molecule, accurate quantum five-dimensional calculations of the T-R energy levels and wave functions are performed that include explicitly, as fully coupled, all three translational and the two rotational degrees of freedom of the hydrogen molecule, while the cage is taken to be rigid. In addition, the ground-state properties, energetics, and spatial distribution of one and two p-H2 and o-D2 molecules in the large cage are calculated rigorously using the diffusion Monte Carlo method. These calculations reveal that the low-energy T-R dynamics of hydrogen molecules in the large cage are qualitatively different from that inside the small cage, studied by us recently. This is caused by the following: (i) The large cage has a cavity whose diameter is about twice that of the small cage for the hydrogen molecule. (ii) In the small cage, the potential energy surface (PES) for H2 is essentially flat in the central region, while in the large cage the PES has a prominent maximum at the cage center, whose height exceeds the T-R zero-point energy of H2/D2. As a result, the guest molecule is excluded from the central part of the large cage, its wave function localized around the off-center global minimum. Peculiar quantum dynamics of the hydrogen molecule squeezed between the central maximum and the cage wall manifests in the excited T-R states whose energies and wave functions differ greatly from those for the small cage. Moreover, they are sensitive to the variations in the hydrogen-bonding topology, which modulate the corrugation of the cage wall.

N-tert-Butyl-N'-(5,7-dimethyl-1,8-naphthyridin-2-yl)urea.

PubMed

Lüning, U; Kühl, C; Bolte, M

2001-08-01

The title compound, C(15)H(20)N(4)O, has been synthesized as an AADD recognition unit for quadruple hydrogen bonds. All non-H atoms of the molecule apart from two methyl groups of the tert-butyl group lie in a common plane. An intramolecular hydrogen bond is formed connecting two N atoms. In the solid state, the title compound crystallizes as a centrosymmetric dimer connected by N-H...O=C interactions with an N...O distance of 2.824 (2) A.

The photodissociation lifetimes of the OH and OD radicals in comets

NASA Technical Reports Server (NTRS)

Singh, P. D.; Van Dishoeck, E. F.; Dalgarno, A.

1983-01-01

The photodissociation rates of OH and OD molecules due to absorption of solar radiation in the X(2)Pi-A(2)Sigma(+) electronic transition are calculated to lie between 3.5 and 6.7 x 10 to the -6th/sec for OH for heliocentric velocities between -60 and +60 km/sec and at about 4.7 x 10 to the -7th/sec for OD at 1 AU from the sun. The corresponding lifetimes, which are upper bounds to the actual lifetimes, are generally consistent with the observational cometary data.

(E)-2-Meth-oxy-9-(2-meth-oxy-9H-xanthen-9-yl-idene)-9H-xanthene.

PubMed

Tian, Xiang-Yu; Song, Qin-Hua

2013-01-01

The title compound, C28H20O4, was synthesized by a bimolecular Zn-HCl reduction in glacial acetic acid using the meth-oxy-substituted xanthone as a starting material. The crystal structure shows that the 2,2'-meth-oxy-bixanthenyl-idene unit is an E-type conformation anti-folded conformer. The mol-ecule lies on an inversion center. The meth-oxy group is almost coplanar with the attached benzene ring, with a C-O-C-C torsion angle of 179.38 (14)°.

Photoionisation of molecular wavepackets - the NaK( C1Σ +) case

NASA Astrophysics Data System (ADS)

Andersson, Renée; Kadi, Malin; Davidsson, Jan; Hansson, Tony

2002-01-01

The ultrafast photoionisation dynamics of NaK molecules in the C(3) 1Σ + state is investigated by pump-probe spectroscopy. The results are consistent with decreasing electronic transition dipole moment for photoionisation of the C state with increasing internuclear separation, due to increasing Na +K - ion pair character of the C state at the outer turning point of the wavepacket trajectory. Effects of a possible low-lying superexcited state cannot be ruled out, though, and in general future studies on ultrafast photoionisation processes need to address in more detail such effects.

Potential energy surfaces of the ground and low-lying states of HCCS and NCS: CASSCF, MRCI and CCSD(T) studies

NASA Astrophysics Data System (ADS)

Li, Yumin; Iwata, Suehiro

1997-07-01

For astronomically interesting molecules, HCCS and NCS, the equilibrium geometries and potential energy curves of three states (X 2Π, A 2Π and B 2Σ+) as well as vertical excitation energies are studied using complete active space SCF (CASSCF), multi-reference configuration interaction (MRCI) and coupled cluster (CCSD(T)) methods with cc-pVTZ basis sets. The difference and similarity in the three states of HCCS and NCS are illustrated. The results obtained are in good agreement with available experimental data.

1-Azaniumylcyclobutane-1-carboxylate monohydrate

NASA Technical Reports Server (NTRS)

Butcher, Ray J.; Brewer, Greg; Burton, Aaron S.; Dworkin, Jason

2014-01-01

In the title compound, C5H9NO2H2O, the amino acid is in the usual zwitterionic form involving the carboxylate group. The cyclobutane backbone of the amino acid is disordered over two conformations, with occupancies of 0.882 (7) and0.118 (7). In the crystal, NH O and OH O hydrogen bonds link the zwitterions [with the water molecule involved as both acceptor (with the NH3+) and donor (through a single carboxylate O from two different aminocyclobutane carboxylatemoities)], resulting in a two-dimensional layered structure lying parallel to (100).

Molecularly Imprinted Membranes

PubMed Central

Trotta, Francesco; Biasizzo, Miriam; Caldera, Fabrizio

2012-01-01

Although the roots of molecularly imprinted polymers lie in the beginning of 1930s in the past century, they have had an exponential growth only 40–50 years later by the works of Wulff and especially by Mosbach. More recently, it was also proved that molecular imprinted membranes (i.e., polymer thin films) that show recognition properties at molecular level of the template molecule are used in their formation. Different procedures and potential application in separation processes and catalysis are reported. The influences of different parameters on the discrimination abilities are also discussed. PMID:24958291