Unusual structures of MgF5- superhalogen anion

NASA Astrophysics Data System (ADS)

Anusiewicz, Iwona; Skurski, Piotr

2007-05-01

The vertical electron detachment energies (VDE) of three MgF5- anions were calculated at the outer valence Green function level with the 6-311 + G(3df) basis sets. This species was found to form unusual geometrical structures each of which corresponds to an anionic state exhibiting superhalogen nature. The global minimum structure was described as a system in which two central magnesium atoms are linked via symmetrical triangle formed by three fluorine atoms. Extremely large electron binding energies of these anions (exceeding 8.5 eV in all cases) were predicted and discussed.

Vibrationally-resolved Photoelectron Spectroscopy of the Model GFP Chromophore Anion Revealing the Photoexcited S-1 State being both Vertically and Adiabatically Bound against the Photodetached D-0 Continuum

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

Deng, Shihu; Kong, Xiangyu; Zhang, GuanXin

2014-06-19

The first excited state of the model green fluorescence protein (GFP) chromophore anion (S1) and its energy level against the electron-detached neutral radical, D0 state are crucial in determining the photophysics and the photo-induced dynamics of GFP. Extensive experimental and theoretical studies, particularly several very recent gas phase investigations concluded that S1 is a bound state in the Franck-Condon vertical region with respect to D0. However, what remains unknown and challenging is if S1 is bound adiabatically, primarily due to lack of accurate experimental measurements, as well as due to close proximity in energy for these two states that evenmore » sophisticated high-level ab initio calculations can’t reliably predict. Here, we report a negative ion photoelectron spectroscopy study on the model GFP chromophore anion, the deprotonated p-hydroxybenzylidene-2,3-dimethylimidazolinone anion (HBDI–). Despite the considerable size and low symmetry of the molecule, well resolved vibrational structures were obtained with the 0–0 transition being the most intense peak. The adiabatic (ADE) and vertical detachment energy (VDE) therefore are determined, both to be 2.73 ± 0.01 eV, indicating the detached D0 state is 0.16 eV higher in energy than the photon excited S1 state. The accurate ADE and VDE values and the well-resolved photoelectron spectra reported here provide much needed, robust benchmarks for future theoretical investigations.« less

Density Functional Study of Structures and Electron Affinities of BrO4F/BrO4F−

PubMed Central

Gong, Liangfa; Xiong, Jieming; Wu, Xinmin; Qi, Chuansong; Li, Wei; Guo, Wenli

2009-01-01

The structures, electron affinities and bond dissociation energies of BrO4F/BrO4F− species have been investigated with five density functional theory (DFT) methods with DZP++ basis sets. The planar F-Br…O2…O2 complexes possess 3A′ electronic state for neutral molecule and 4A′ state for the corresponding anion. Three types of the neutral-anion energy separations are the adiabatic electron affinity (EAad), the vertical electron affinity (EAvert), and the vertical detachment energy (VDE). The EAad value predicted by B3LYP method is 4.52 eV. The bond dissociation energies De (BrO4F → BrO4-mF + Om) (m = 1–4) and De− (BrO4F− → BrO4-mF− + Om and BrO4F− → BrO4-mF + Om−) are predicted. The adiabatic electron affinities (EAad) were predicted to be 4.52 eV for F-Br…O2…O2 (3A′←4A′) (B3LYP method). PMID:19742128

Ab Initio Calculations of Singlet and Triplet Excited States of Chlorine Nitrate and Nitric Acid

NASA Technical Reports Server (NTRS)

Grana, Ana M.; Lee, Timothy J.; Head-Gordon, Martin; Langhoff, Stephen R. (Technical Monitor)

1994-01-01

Ab initio calculations of vertical excitations to singlet and triplet excited states of chlorine nitrate and nitric acid are reported. The nature of the electronic transitions are examined by decomposing the difference density into the sum of detachment and attachment densities. Counterparts for the three lowest singlet excited states of nitric acid survive relatively unperturbed in chlorine nitrate, while other low-lying singlet states of chlorine nitrate appear to be directly dissociative in the ClO chromophore. These results suggest an assignment of the two main peaks in the experimental chlorine nitrate absorption spectrum. In addition, triplet vertical excitations and the lowest optimized triplet geometries of both molecules are studied.

Kinetics of Sulfur Oxide, Sulfur Fluoride, and Sulfur Oxyfluoride Anions with Atomic Species at 298 and 500 K

DTIC Science & Technology

2007-02-01

TABLE 4: Energetics for the HS0 2 - Isomers Calculated Using G2 and G2(MP2) Theory, Including the Vertical Detachment Energy ( VDE ) of the Anion and...548.595 939 76.7 SIOSO- -548.582 037 -548.576 281 151.0 -548.570 411 -548.564 655 155.3 •11298K VDE 298K VDE G2 G2 G2(MP2) G2(MP2) (kJ mol-) (kJ mol-1) (kJ...However, as seen in Table 4, if neutral ( VDE ) values given in Table 4 derived from the neutral energies HS0 2 is produced via vertical electron

Negative ion photoelectron spectroscopy of solvated electron cluster anions, (H2O){/n -} and (NH3){/n -}

NASA Astrophysics Data System (ADS)

Lee, G. H.; Arnold, S. T.; Eaton, J. G.; Sarkas, H. W.; Bowen, K. H.; Ludewigt, C.; Haberland, H.

1991-03-01

The photodetachment spectra of (H2O){/n =2-69/-} and (NH3){/n =41-1100/-} have been recorded, and vertical detachment energies (VDEs) were obtained from the spectra. For both systems, the cluster anion VDEs increase smoothly with increasing sizes and most species plot linearly with n -1/3, extrapolating to a VDE ( n=∞) value which is very close to the photoelectric threshold energy for the corresponding condensed phase solvated electron system. The linear extrapolation of this data to the analogous condensed phase property suggests that these cluster anions are gas phase counterparts to solvated electrons, i.e. they are embryonic forms of hydrated and ammoniated electrons which mature with increasing cluster size toward condensed phase solvated electrons.

Solvation of excess electrons trapped in charge pockets on molecular surfaces

NASA Astrophysics Data System (ADS)

Jalbout, Abraham F.

This work considers the ability of hydrogen fluoride (HF) to solvate excess electrons located on cyclic hydrocarbon surfaces. The principle applied involves the formation of systems in which excess electrons can be stabilized not only on concentrated molecular surface charge pockets but also by HF. Recent studies have shown that OH groups can form stable hydrogen-bonded networks on one side of a hydrocarbon surface (i.e. cyclohexane sheets), at the same time, the hydrogen atoms on the opposite side of this surface form a pocket of positive charge can attract the excess electron. This density can be further stabilized by the addition of an HF molecule that can form an 'anion with an internally solvated electron' (AISE) state. These systems are shown to be stable with respect to vertical electron detachment (VDE).

Characterization of solvated electrons in hydrogen cyanide clusters: (HCN)n- (n=3, 4)

NASA Astrophysics Data System (ADS)

Wu, Di; Li, Ying; Li, Zhuo; Chen, Wei; Li, Zhi-Ru; Sun, Chia-Chung

2006-02-01

Theoretical studies of the solvated electrons (HCN)n- (n =3, 4) reveal a variety of electron trapping possibilities in the (HCN)n (n =3, 4) clusters. Two isomers for (HCN)3- and four isomers for (HCN)4- are obtained at the MP2/aug -cc-pVDZ+dBF (diffusive bond functions) level of theory. In view of vertical electron detachment energies (VDEs) at the CCSD(T) level, the excess electron always "prefers" locating in the center of the system, i.e., the isomer with higher coordination number shows larger VDE value. However, the most stable isomers of the solvated electron state (HCN)3- and (HCN)4- are found to be the linear C∞ν and D∞h structures, respectively, but not the fullyl symmetric structures which have the largest VDE values.

Coupled-cluster and explicitly correlated perturbation-theory calculations of the uracil anion.

PubMed

Bachorz, Rafał A; Klopper, Wim; Gutowski, Maciej

2007-02-28

A valence-type anion of the canonical tautomer of uracil has been characterized using explicitly correlated second-order Moller-Plesset perturbation theory (RI-MP2-R12) in conjunction with conventional coupled-cluster theory with single, double, and perturbative triple excitations. At this level of electron-correlation treatment and after inclusion of a zero-point vibrational energy correction, determined in the harmonic approximation at the RI-MP2 level of theory, the valence anion is adiabatically stable with respect to the neutral molecule by 40 meV. The anion is characterized by a vertical detachment energy of 0.60 eV. To obtain accurate estimates of the vertical and adiabatic electron binding energies, a scheme was applied in which electronic energy contributions from various levels of theory were added, each of them extrapolated to the corresponding basis-set limit. The MP2 basis-set limits were also evaluated using an explicitly correlated approach, and the results of these calculations are in agreement with the extrapolated values. A remarkable feature of the valence anionic state is that the adiabatic electron binding energy is positive but smaller than the adiabatic electron binding energy of the dipole-bound state.

Effect of Solvation on Electron Detachment and Excitation Energies of a Green Fluorescent Protein Chromophore Variant.

PubMed

Bose, Samik; Chakrabarty, Suman; Ghosh, Debashree

2016-05-19

Hybrid quantum mechanics/molecular mechanics (QM/MM) is applied to the fluorinated green fluorescent protein (GFP) chromophore (DFHBDI) in its deprotonated form to understand the solvatochromic shifts in its vertical detachment energy (VDE) and vertical excitation energy (VEE). This variant of the GFP chromophore becomes fluorescent in an RNA environment and has a wide range of applications in biomedical and biochemical fields. From microsolvation studies, we benchmark (with respect to full QM) the accuracy of our QM/MM calculations with effective fragment potential (EFP) as the MM method of choice. We show that while the solvatochromic shift in the VEE is minimal (0.1 eV blue shift) and its polarization component is only 0.03 eV, the effect of the solvent on the VDE is quite large (3.85 eV). We also show by accurate calculations on the solvatochromic shift of the VDE that polarization accounts for ∼0.23 eV and therefore cannot be neglected. The effect of the counterions on the VDE of the deprotonated chromophore in solvation is studied in detail, and a charge-smearing scheme is suggested for charged chromophores.

The existence and stability of the anions matching the MFk+2- formula (M = Li, Na, K, Be, Mg, Ca, B, Al, Ga)

NASA Astrophysics Data System (ADS)

Marchaj, Marzena; Freza, Sylwia; Skurski, Piotr

2013-02-01

The electronic stabilities of the MFk+2- anions (where M = Li, Na, K, Be, Mg, Ca, B, Al, Ga; and k is the maximal formal valence of atom M) were investigated at the OVGF/6-311 + G(3df) level. The vertical electron detachment energies (VDE) of the anions examined were found to be large (7.1-10.1 eV) albeit not significantly exceeding those for the corresponding MFk+1- superhalogen anions. Even though all the MFk+2- species studied were predicted to be both geometrically and electronically stable, some of them turned out to be thermodynamically unstable (i.e., susceptible to the F atom loss).

Homogenous stretching or detachment faulting? Which process is primarily extending the Aegean crust

NASA Astrophysics Data System (ADS)

Kumerics, C.; Ring, U.

2003-04-01

In extending orogens like the Aegean Sea of Greece and the Basin-and-Range province of the western United States, knowledge of rates of tectonic processes are important for understanding which process is primarily extending the crust. Platt et al. (1998) proposed that homogeneous stretching of the lithosphere (i.e. vertical ductile thinning associated with a subhorizontal foliation) at rates of 4-5 km Myr-1 is the dominant process that formed the Alboran Sea in the western Mediterranean. The Aegean Sea in the eastern Mediterranean is well-known for its low-angle normal faults (detachments) (Lister et al., 1984; Lister &Forster, 1996) suggesting that detachment faulting may have been the primary agent achieving ~>250 km (McKenzie, 1978) of extension since the Miocene. Ring et al. (2003) provided evidence for a very fast-slipping detachment on the islands of Syros and Tinos in the western Cyclades, which suggests that normal faulting was the dominant tectonic process that formed the Aegean Sea. However, most extensional detachments in the Aegean do not allow to quantify the amount of vertical ductile thinning associated with extension and therefore a full evaluation of the significance of vertical ductile thinning is not possible. On the Island of Ikaria in the eastern Aegean Sea, a subhorizontal extensional ductile shear zone is well exposed. We studied this shear zone in detail to quantify the amount of vertical ductile thinning associated with extension. Numerous studies have shown that natural shear zones usually deviate significantly from progressive simple shear and are characterized by pronounced shortening perpendicular to the shear zone. Numerous deformed pegmatitic veins in this shear zone on Ikaria allow the reconstruction of deformation and flow parameters (Passchier, 1990), which are necessary for quantifying the amount of vertical ductile thinning in the shear zone. Furthermore, a flow-path and finite-strain study in a syn-tectonic granite, which intruded into the shear zone, was carried out. Consistent results show that the mean kinematic vorticity number in the shear zone was close to 1, indicating that the bulk deformation path was close to simple shear. This in turn indicates that vertical ductile thinning was not important during extensional faulting. We conclude that detachment faulting was the primary agent that extended the Aegean crust.

Stabilization of very rare tautomers of uracil by an excess electron.

PubMed

Bachorz, Rafał A; Rak, Janusz; Gutowski, Maciej

2005-05-21

We characterized valence-type and dipole-bound anionic states of uracil using various electronic structure methods. We found that the most stable anion is related to neither the canonical 2,4-dioxo nor a rare imino-hydroxy tautomer. Instead, it is related to an imino-oxo tautomer, in which the N1H proton is transferred to the C5 atom. This valence anion is characterized by an electron vertical detachment energy (VDE) of 1267 meV and it is adiabatically stable with respect to the canonical neutral by 3.93 kcal mol(-1). It is also more stable by 2.32 and 5.10 kcal mol(-1) than the dipole-bound and valence anion, respectively, of the canonical tautomer. The VDE values for the former and the latter are 73 and 506 meV, respectively. Another, anionic, low-lying imino-oxo tautomer with a VDE of 2499 meV has a proton transferred from N3H to C5. It is less stable than the neutral canonical tautomer by 1.38 kcal mol(-1). The mechanism of formation of anionic tautomers with the carbon C5 protonated may involve intermolecular proton transfer or dissociative electron attachment to the canonical neutral tautomer followed by a barrier-free attachment of a hydrogen atom to C5. The six-member ring structure of anionic tautomers with carbon atoms protonated might be unstable upon an excess electron detachment. Indeed, the neutral systems resulting from electron detachment from anionic tautomers with carbon atoms protonated evolve along barrier-free decomposition pathways to a linear or a bicyclo structure, which might be viewed as lesions to RNA. Within the PCM hydration model, the low-lying valence anions become adiabatically bound with respect to the canonical neutral and the two most stable tautomers have carbon atoms protonated.

Electron detachment energies in high-symmetry alkali halide solvated-electron anions

NASA Astrophysics Data System (ADS)

Anusiewicz, Iwona; Berdys, Joanna; Simons, Jack; Skurski, Piotr

2003-07-01

We decompose the vertical electron detachment energies (VDEs) in solvated-electron clusters of alkali halides in terms of (i) an electrostatic contribution that correlates with the dipole moment (μ) of the individual alkali halide molecule and (ii) a relaxation component that is related to the polarizability (α) of the alkali halide molecule. Detailed numerical ab initio results for twelve species (MX)n- (M=Li,Na; X=F,Cl,Br; n=2,3) are used to construct an interpolation model that relates the clusters' VDEs to their μ and α values as well as a cluster size parameter r that we show is closely related to the alkali cation's ionic radius. The interpolation formula is then tested by applying it to predict the VDEs of four systems [i.e., (KF)2-, (KF)3-, (KCl)2-, and (KCl)3-] that were not used in determining the parameters of the model. The average difference between the model's predicted VDEs and the ab initio calculated electron binding energies is less than 4% (for the twelve species studied). It is concluded that one can easily estimate the VDE of a given high-symmetry solvated electron system by employing the model put forth here if the α, μ and cation ionic radii are known. Alternatively, if VDEs are measured for an alkali halide cluster and the α and μ values are known, one can estimate the r parameter, which, in turn, determines the "size" of the cluster anion.

Anion Photoelectron Spectroscopy of the Homogenous 2-Hydroxypyridine Dimer Electron Induced Proton Transfer System

NASA Astrophysics Data System (ADS)

Vlk, Alexandra; Stokes, Sarah; Wang, Yi; Hicks, Zachary; Zhang, Xinxing; Blando, Nicolas; Frock, Andrew; Marquez, Sara; Bowen, Kit; Bowen Lab JHU Team

Anion photoelectron spectroscopic (PES) and density functional theory (DFT) studies on the dimer anion of (2-hydroxypyridine)2-are reported. The experimentally measured vertical detachment energy (VDE) of 1.21eV compares well with the theoretically predicted values. The 2-hydroxypyridine anionic dimer system was investigated because of its resemblance to the nitrogenous heterocyclic pyrimidine nucleobases. Experimental and theoretical results show electron induced proton transfer (EIPT) in both the lactim and lactam homogeneous dimers. Upon electron attachment, the anion can serve as the intermediate between the two neutral dimers. A possible double proton transfer process can occur from the neutral (2-hydroxypyridine)2 to (2-pyridone)2 through the dimer anion. This potentially suggests an electron catalyzed double proton transfer mechanism of tautomerization. Research supported by the NSF Grant No. CHE-1360692.

A Computational Study of Structure and Reactivity of N-Substitued-4-Piperidones Curcumin Analogues and Their Radical Anions.

PubMed

Martínez-Cifuentes, Maximiliano; Weiss-López, Boris; Araya-Maturana, Ramiro

2016-12-02

In this work, a computational study of a series of N -substitued-4-piperidones curcumin analogues is presented. The molecular structure of the neutral molecules and their radical anions, as well as their reactivity, are investigated. N -substituents include methyl and benzyl groups, while substituents on the aromatic rings cover electron-donor and electron-acceptor groups. Substitutions at the nitrogen atom do not significantly affect the geometry and frontier molecular orbitals (FMO) energies of these molecules. On the other hand, substituents on the aromatic rings modify the distribution of FMO. In addition, they influence the capability of these molecules to attach an additional electron, which was studied through adiabatic (AEA) and vertical electron affinities (VEA), as well as vertical detachment energy (VDE). To study electrophilic properties of these structures, local reactivity indices, such as Fukui ( f ⁺) and Parr ( P ⁺) functions, were calculated, and show the influence of the aromatic rings substituents on the reactivity of α,β-unsaturated ketones towards nucleophilic attack. This study has potential implications for the design of curcumin analogues based on a 4-piperidone core with desired reactivity.

Vertical Electron Detachment Energies for Octahedral Closed-Shell Multiply Charged Anions

DTIC Science & Technology

1994-04-22

however, at low theoretical levels, motivating us to extend the investigations to: a) higher levels of theory, b) analogous closed-shell singly- and...hundredths of an eV. This further supports our choice of SBKJ+diff as the basis set for the production runs. The SCF relaxation energies for F- and Cl...intensities for the product molecules ML 5(’)" (D3h) and ML 4 (n-2 )" 15 (Td) were determined at the SCF/SBKJ level and are reported in Table V

Numerical Optimization of the Thermal Field in Bridgman Detached Growth

NASA Technical Reports Server (NTRS)

Stelian, C.; Volz, M. P.; Derby, J. J.

2009-01-01

The global modeling of the thermal field in two vertical Bridgman-like crystal growth configurations, has been performed to get optimal thermal conditions for a successful detached growth of Ge and CdTe crystals. These computations are performed using the CrysMAS code and expand upon our previous analysis [1] that propose a new mechanism involving the thermal field and meniscus position to explain stable conditions for dewetted Bridgman growth. The analysis of the vertical Bridgman configuration with two heaters, used by Palosz et al. for the detached growth of Ge, shows, consistent with their results, that the large wetting angle of germanium on boron nitride surfaces was an important factor to promote a successful detached growth. Our computations predict that by initiating growth much higher into the hot zone of the furnace, the thermal conditions will be favorable for continued detachment even for systems that did not exhibit high contact angles. The computations performed for a vertical gradient freeze configuration with three heaters representative of that used for the detached growth of CdTe, show favorable thermal conditions for dewetting during the entirely growth run described. Improved thermal conditions are also predicted for coated silica crucibles when the solid-liquid interface advances higher into the hot zone during the solidification process. The second set of experiments on CdTe growth described elsewhere has shown the reattachment of the crystal to the crucible after few centimeters of dewetted growth. The thermal modeling of this configuration shows a second solidification front appearing at the top of the sample and approaching the middle line across the third heater. In these conditions, the crystal grows detached from the bottom, but will be attached to the crucible in the upper part because of the solidification without gap in this region. The solidification with two interfaces can be avoided when the top of the sample is positioned below the middle position of the third furnace.

On the unusual stability of valence anions of thymine based on very rare tautomers. A computational study

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

Mazurkiewicz, Kamil; Bachorz, Rafal; Gutowski, Maciej S.

2006-12-07

We characterized valence-type and dipole-bound anionic states of thymine using various electronic structure methods, with the most accurate results obtained at the CCSD(T)/aug-cc-pVDZ level of theory followed by extrapolations to complete basis set limits. We found that the most stable anion in the gas phase is related to neither the canonical 2,4-dioxo nor a rare imino-hydroxy tautomer. Instead, it is related to an imino-oxo tautomer, in which the N1H proton is transferred to the C5 atom. This valence anion is characterized by an electron vertical detachment energy (VDE) of 1251 meV and it is adiabatically stable with respect to themore » canonical neutral by 2.4 kcal/mol. It is also more stable than the dipole-bound and valence anion of the canonical tautomer. The latter is adiabatically unbound with respect to by 0.1 kcal/mol and this instability is smaller than the uncertainty of the computational model used. The VDE values for and are 55 and 457 meV, respectively. Another, anionic, low-lying imino-oxo tautomer with a VDE of 2458 meV has a proton transferred from N3H to C5. It is less stable than by 3.2 kcal/mol. The mechanism of formation of anionic tautomers with the carbons C5 or C6 protonated may involve intermolecular proton transfer or dissociative electron attachment to the canonical neutral tautomer followed by a barrier-free attachment of a hydrogen atom to C5. The six-member ring structure of anionic tautomers with carbon atoms protonated might be unstable upon an excess electron detachment. Indeed, the neutral systems resulting from electron detachment from and evolve, along barrier-free decomposition pathways, to a linear or a bicyclo structure, respectively, which might be viewed as lesions to DNA.« less

Electron attachment to DNA single strands: gas phase and aqueous solution.

PubMed

Gu, Jiande; Xie, Yaoming; Schaefer, Henry F

2007-01-01

The 2'-deoxyguanosine-3',5'-diphosphate, 2'-deoxyadenosine-3',5'-diphosphate, 2'-deoxycytidine-3',5'-diphosphate and 2'-deoxythymidine-3',5'-diphosphate systems are the smallest units of a DNA single strand. Exploring these comprehensive subunits with reliable density functional methods enables one to approach reasonable predictions of the properties of DNA single strands. With these models, DNA single strands are found to have a strong tendency to capture low-energy electrons. The vertical attachment energies (VEAs) predicted for 3',5'-dTDP (0.17 eV) and 3',5'-dGDP (0.14 eV) indicate that both the thymine-rich and the guanine-rich DNA single strands have the ability to capture electrons. The adiabatic electron affinities (AEAs) of the nucleotides considered here range from 0.22 to 0.52 eV and follow the order 3',5'-dTDP > 3',5'-dCDP > 3',5'-dGDP > 3',5'-dADP. A substantial increase in the AEA is observed compared to that of the corresponding nucleic acid bases and the corresponding nucleosides. Furthermore, aqueous solution simulations dramatically increase the electron attracting properties of the DNA single strands. The present investigation illustrates that in the gas phase, the excess electron is situated both on the nucleobase and on the phosphate moiety for DNA single strands. However, the distribution of the extra negative charge is uneven. The attached electron favors the base moiety for the pyrimidine, while it prefers the 3'-phosphate subunit for the purine DNA single strands. In contrast, the attached electron is tightly bound to the base fragment for the cytidine, thymidine and adenosine nucleotides, while it almost exclusively resides in the vicinity of the 3'-phosphate group for the guanosine nucleotides due to the solvent effects. The comparatively low vertical detachment energies (VDEs) predicted for 3',5'-dADP(-) (0.26 eV) and 3',5'-dGDP(-) (0.32 eV) indicate that electron detachment might compete with reactions having high activation barriers such as glycosidic bond breakage. However, the radical anions of the pyrimidine nucleotides with high VDE are expected to be electronically stable. Thus the base-centered radical anions of the pyrimidine nucleotides might be the possible intermediates for DNA single-strand breakage.

Quaternary low-angle slip on detachment faults in Death Valley, California

USGS Publications Warehouse

Hayman, N.W.; Knott, J.R.; Cowan, D.S.; Nemser, E.; Sarna-Wojcicki, A. M.

2003-01-01

Detachment faults on the west flank of the Black Mountains (Nevada and California) dip 29??-36?? and cut subhorizontal layers of the 0.77 Ma Bishop ash. Steeply dipping normal faults confined to the hanging walls of the detachments offset layers of the 0.64 Ma Lava Creek B tephra and the base of 0.12-0.18 Ma Lake Manly gravel. These faults sole into and do not cut the low-angle detachments. Therefore the detachments accrued any measurable slip across the kinematically linked hanging-wall faults. An analysis of the orientations of hundreds of the hanging-wall faults shows that extension occurred at modest slip rates (<1 mm/yr) under a steep to vertically oriented maximum principal stress. The Black Mountain detachments are appropriately described as the basal detachments of near-critical Coulomb wedges. We infer that the formation of late Pleistocene and Holocene range-front fault scarps accompanied seismogenic slip on the detachments.

Electron photodetachment from gas phase peptide dianions. Relation with optical absorption properties.

PubMed

Joly, Laure; Antoine, Rodolphe; Broyer, Michel; Lemoine, Jérôme; Dugourd, Philippe

2008-02-07

Electron detachment from peptide dianions is studied as a function of the laser wavelength. The first step for the detachment is a resonant electronic excitation of the dianions. Electronic excitation spectra are reported for three peptides, including gramicidin. A comparative study of the detachment yield for 13 peptides was performed at 260 nm and at 220 nm. At 260 nm, the detachment yield is mainly driven by the sum of the absorption coefficients of the aromatic amino acids that are contained in the peptide. At 220 nm, no direct relation is observed between the electron photodetachement yields and the sum of absorption efficiencies. At this wavelength, the sequence and the structure of the peptide may have an influence on the photodetachment process.

Anion photoelectron imaging spectroscopy of glyoxal

NASA Astrophysics Data System (ADS)

Xue, Tian; Dixon, Andrew R.; Sanov, Andrei

2016-09-01

We report a photoelectron imaging study of the radical-anion of glyoxal. The 532 nm photoelectron spectrum provides the first direct spectroscopic determination of the adiabatic electron affinity of glyoxal, EA = 1.10 ± 0.02 eV. This assignment is supported by a Franck-Condon simulation of the experimental spectrum that successfully reproduces the observed spectral features. The vertical detachment energy of the radical-anion is determined as VDE = 1.30 ± 0.04 eV. The reported EA and VDE values are attributed to the most stable (C2h symmetry) isomers of the neutral and the anion.

Measurement of cell adhesion force by vertical forcible detachment using an arrowhead nanoneedle and atomic force microscopy

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

Ryu, Seunghwan; Hashizume, Yui; Mishima, Mari

Graphical abstract: - Highlights: • We developed a method to measure cell adhesion force by detaching cell using an arrowhead nanoneedle and AFM. • A nanofilm consisting of fibronectin and gelatin was formed on cell surface to reinforce the cell cortex. • By the nanofilm lamination, detachment efficiencies of strongly adherent cell lines were improved markedly. - Abstract: The properties of substrates and extracellular matrices (ECM) are important factors governing the functions and fates of mammalian adherent cells. For example, substrate stiffness often affects cell differentiation. At focal adhesions, clustered–integrin bindings link cells mechanically to the ECM. In order tomore » quantitate the affinity between cell and substrate, the cell adhesion force must be measured for single cells. In this study, forcible detachment of a single cell in the vertical direction using AFM was carried out, allowing breakage of the integrin–substrate bindings. An AFM tip was fabricated into an arrowhead shape to detach the cell from the substrate. Peak force observed in the recorded force curve during probe retraction was defined as the adhesion force, and was analyzed for various types of cells. Some of the cell types adhered so strongly that they could not be picked up because of plasma membrane breakage by the arrowhead probe. To address this problem, a technique to reinforce the cellular membrane with layer-by-layer nanofilms composed of fibronectin and gelatin helped to improve insertion efficiency and to prevent cell membrane rupture during the detachment process, allowing successful detachment of the cells. This method for detaching cells, involving cellular membrane reinforcement, may be beneficial for evaluating true cell adhesion forces in various cell types.« less

Superatoms as Building Blocks of New Materials

DTIC Science & Technology

2012-10-24

size regime. The adiabatic detachment energy (ADE) and vertical detachment energy ( VDE ) of Zn3O3 − and Zn3O4 − clusters were determined by anion...Zn3Om (m = 3,4,5) clusters, while the theoretical ADE and VDE values are compared with experimental results. The experimentally observed relative

Are polynuclear superhalogens without halogen atoms probable? A high-level ab initio case study on triple-bridged binuclear anions with cyanide ligands

NASA Astrophysics Data System (ADS)

Yin, Bing; Li, Teng; Li, Jin-Feng; Yu, Yang; Li, Jian-Li; Wen, Zhen-Yi; Jiang, Zhen-Yi

2014-03-01

The first theoretical exploration of superhalogen properties of polynuclear structures based on pseudohalogen ligand is reported here via a case study on eight triply-bridged [Mg2(CN)5]- clusters. From our high-level ab initio results, all these clusters are superhalogens due to their high vertical electron detachment energies (VDE), of which the largest value is 8.67 eV at coupled-cluster single double triple (CCSD(T)) level. Although outer valence Green's function results are consistent with CCSD(T) in most cases, it overestimates the VDEs of three anions dramatically by more than 1 eV. Therefore, the combined usage of several theoretical methods is important for the accuracy of purely theoretical prediction of superhalogen properties of new structures. Spatial distribution of the extra electron of high-VDE anions here indicates two features: remarkable aggregation on bridging CN units and non-negligible distribution on every CN unit. These two features lower the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to detachment of CN-1 were also investigated for these anions. The collection of these results indicates that polynuclear structures based on pseudohalogen ligand are promising candidates for new superhalogens with enhanced properties.

Are superhalogens without halogen ligand capable of transcending traditional halogen-based superhalogens? Ab initio case study of binuclear anions based on pseudohalogen ligand

NASA Astrophysics Data System (ADS)

Li, Jin-Feng; Sun, Yin-Yin; Bai, Hongcun; Li, Miao-Miao; Li, Jian-Li; Yin, Bing

2015-06-01

The superhalogen properties of polynuclear structures without halogen ligand are theoretically explored here for several [M2(CN)5]-1 (M = Ca, Be) clusters. At CCSD(T) level, these clusters have been confirmed to be superhalogens due to their high vertical electron detachment energies (VDE). The largest one is 9.70 eV for [Ca2(CN)5]-1 which is even higher than those of corresponding traditional structures based on fluorine or chlorine ligands. Therefore the superhalogens stronger than the traditional halogen-based structures could be realized by ligands other than halogen atoms. Compared with CCSD(T), outer valence Green's function (OVGF) method either overestimates or underestimates the VDEs for different structures while MP2 results are generally consistent in the aspect of relative values. The extra electrons of the highest VDE anions here aggregate on the bridging CN units with non-negligible distribution occurring on other CN units too. These two features lower both the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to the detachment of cyanide ligand were also investigated. The sum of these results identifies the potential of polynuclear structures with pseudohalogen ligand as suitable candidates with enhanced superhalogens properties.

Are polynuclear superhalogens without halogen atoms probable? A high-level ab initio case study on triple-bridged binuclear anions with cyanide ligands.

PubMed

Yin, Bing; Li, Teng; Li, Jin-Feng; Yu, Yang; Li, Jian-Li; Wen, Zhen-Yi; Jiang, Zhen-Yi

2014-03-07

The first theoretical exploration of superhalogen properties of polynuclear structures based on pseudohalogen ligand is reported here via a case study on eight triply-bridged [Mg2(CN)5](-) clusters. From our high-level ab initio results, all these clusters are superhalogens due to their high vertical electron detachment energies (VDE), of which the largest value is 8.67 eV at coupled-cluster single double triple (CCSD(T)) level. Although outer valence Green's function results are consistent with CCSD(T) in most cases, it overestimates the VDEs of three anions dramatically by more than 1 eV. Therefore, the combined usage of several theoretical methods is important for the accuracy of purely theoretical prediction of superhalogen properties of new structures. Spatial distribution of the extra electron of high-VDE anions here indicates two features: remarkable aggregation on bridging CN units and non-negligible distribution on every CN unit. These two features lower the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to detachment of CN(-1) were also investigated for these anions. The collection of these results indicates that polynuclear structures based on pseudohalogen ligand are promising candidates for new superhalogens with enhanced properties.

Photoelectron Spectroscopy of the Doubly-Charged Anions [MIVO(mnt)2]2- (M=Mo, W; mnt=S2C2(CN)22-): Access to the Ground and Excited States of the [MvO(mnt)2]-Anion

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

Waters, Tom; Wang, Xue B.; Yang, Xin

2004-04-21

Photodetachment photoelectron spectroscopy was used to investigate the electronic structure of the doubly charged complexes [MIVO(mnt)2]2- (M=Mo, W;mnt=1,2 dicyanoethenedithiolato). These dianions are stable in the gas phase and are minimal models for the active sites of the dimethyl sulfoxide reductase family of molybdenum enzymes and of related tungsten enzymes. Adiabatic and vertical electron binding energies for both species were measured, providing detailed information about molecular orbital energy levels of the parent dianions as well as the ground and excited states of the product anions [MvO(mnt)2]. Density functional theory calculations were used to assist assignment of the detachment features.

Superhalogen properties of hetero-binuclear anions MM‧F4- and MM″F5- (M = Li, Na, M‧ = Be, Mg, Ca; M″ = B, Al, Ga)

NASA Astrophysics Data System (ADS)

Yang, Hui; Li, Ying; He, Hui-Min; Tong, Jing; Wu, Di; Li, Zhi-Ru

2017-09-01

Hetero-binuclear superhalogen anions, namely MM‧F4- and MM″F5- (M = Li, Na; M‧ = Be, Mg, Ca; M″ = B, Al, Ga), have been theoretically characterized at the MP2(FULL)/6-311+G(3df) level. It is found that two central atoms can be linked by at most three fluorine ligands. The large vertical electron detachment energies (VDEs, 7.449-8.978 eV) verify the superhalogen identity of these anions. The VDEs of both MM‧F4- and MM″F5- decrease when the atomic size of M increases whereas increase with the size of M‧ and M″. Besides, the extra electron distribution also has effect on the VDEs of such superhalogen anions.

Electron attachment to DNA single strands: gas phase and aqueous solution

PubMed Central

Gu, Jiande; Xie, Yaoming; Schaefer, Henry F.

2007-01-01

The 2′-deoxyguanosine-3′,5′-diphosphate, 2′-deoxyadenosine-3′,5′-diphosphate, 2′-deoxycytidine-3′,5′-diphosphate and 2′-deoxythymidine-3′,5′-diphosphate systems are the smallest units of a DNA single strand. Exploring these comprehensive subunits with reliable density functional methods enables one to approach reasonable predictions of the properties of DNA single strands. With these models, DNA single strands are found to have a strong tendency to capture low-energy electrons. The vertical attachment energies (VEAs) predicted for 3′,5′-dTDP (0.17 eV) and 3′,5′-dGDP (0.14 eV) indicate that both the thymine-rich and the guanine-rich DNA single strands have the ability to capture electrons. The adiabatic electron affinities (AEAs) of the nucleotides considered here range from 0.22 to 0.52 eV and follow the order 3′,5′-dTDP > 3′,5′-dCDP > 3′,5′-dGDP > 3′,5′-dADP. A substantial increase in the AEA is observed compared to that of the corresponding nucleic acid bases and the corresponding nucleosides. Furthermore, aqueous solution simulations dramatically increase the electron attracting properties of the DNA single strands. The present investigation illustrates that in the gas phase, the excess electron is situated both on the nucleobase and on the phosphate moiety for DNA single strands. However, the distribution of the extra negative charge is uneven. The attached electron favors the base moiety for the pyrimidine, while it prefers the 3′-phosphate subunit for the purine DNA single strands. In contrast, the attached electron is tightly bound to the base fragment for the cytidine, thymidine and adenosine nucleotides, while it almost exclusively resides in the vicinity of the 3′-phosphate group for the guanosine nucleotides due to the solvent effects. The comparatively low vertical detachment energies (VDEs) predicted for 3′,5′-dADP− (0.26 eV) and 3′,5′-dGDP− (0.32 eV) indicate that electron detachment might compete with reactions having high activation barriers such as glycosidic bond breakage. However, the radical anions of the pyrimidine nucleotides with high VDE are expected to be electronically stable. Thus the base-centered radical anions of the pyrimidine nucleotides might be the possible intermediates for DNA single-strand breakage. PMID:17660189

Hexuronic Acid Stereochemistry Determination in Chondroitin Sulfate Glycosaminoglycan Oligosaccharides by Electron Detachment Dissociation

NASA Astrophysics Data System (ADS)

Leach, Franklin E.; Ly, Mellisa; Laremore, Tatiana N.; Wolff, Jeremy J.; Perlow, Jacob; Linhardt, Robert J.; Amster, I. Jonathan

2012-09-01

Electron detachment dissociation (EDD) has previously provided stereo-specific product ions that allow for the assignment of the acidic C-5stereochemistry in heparan sulfate glycosaminoglycans (GAGs), but application of the same methodology to an epimer pair in the chondroitin sulfate glycoform class does not provide the same result. A series of experiments have been conducted in which glycosaminoglycan precursor ions are independently activated by electron detachment dissociation (EDD), electron induced dissociation (EID), and negative electron transfer dissociation (NETD) to assign the stereochemistry in chondroitin sulfate (CS) epimers and investigate the mechanisms for product ion formation during EDD in CS glycoforms. This approach allows for the assignment of electronic excitation products formed by EID and detachment products to radical pathways in NETD, both of which occur simultaneously during EDD. The uronic acid stereochemistry in electron detachment spectra produces intensity differences when assigned glycosidic and cross-ring cleavages are compared. The variations in the intensities of the doubly deprotonated 0,2X3 and Y3 ions have been shown to be indicative of CS-A/DS composition during the CID of binary mixtures. These ions can provide insight into the uronic acid composition of binary mixtures in EDD, but the relative abundances, although reproducible, are low compared with those in a CID spectrum acquired on an ion trap. The application of principal component analysis (PCA) presents a multivariate approach to determining the uronic acid stereochemistry spectra of these GAGs by taking advantage of the reproducible peak distributions produced by electron detachment.

Measurement of He neutral temperature in detached plasmas using laser absorption spectroscopy

NASA Astrophysics Data System (ADS)

Aramaki, M.; Tsujihara, T.; Kajita, S.; Tanaka, H.; Ohno, N.

2018-01-01

The reduction of the heat load onto plasma-facing components by plasma detachment is an inevitable scheme in future nuclear fusion reactors. Since the control of the plasma and neutral temperatures is a key issue to the detached plasma generation, we have developed a laser absorption spectroscopy system for the metastable helium temperature measurements and used together with a previously developed laser Thomson scattering system for the electron temperature and density measurements. The thermal relaxation process between the neutral and the electron in the detached plasma generated in the linear plasma device, NAGDIS-II was studied. It is shown that the electron temperature gets close to the neutral temperature by increasing the electron density. On the other hand, the pressure dependence of electron and neutral temperatures shows the cooling effect by the neutrals. The possibility of the plasma fluctuation measurement using the fluctuation in the absorption signal is also shown.

Theoretical study of 'Mixed' ligands superhalogens: Cl-M-NO3 (M = Li, Na, K)

NASA Astrophysics Data System (ADS)

Zhao, Xinghua; Liu, Weihui; Wang, Jiesheng; Li, Chun; Yuan, Guang

2016-08-01

MCl2-, M(NO3)2-, and (Cl-M-NO3)- (M = Li, Na, K) species are systematically investigated using the density functional theory. In all the cases studied, the vertical detachment energies (VDEs) exceed the electron affinity of chlorine atom, leading to the conclusion that MCl2-, M(NO3)2- and (Cl-M-NO3)- are superhalogens. The VDEs of (Cl-M-NO3)- are between that of MCl2- and M(NO3)2-, showing that replacing one ligand with a larger electronegative ligand leads to the higher VDE. Superhalogens with suitable VDEs can be built by using different ligands.

Study of the dielectric breakdown properties of CO2-O2 mixtures by considering electron detachments from negative ions

NASA Astrophysics Data System (ADS)

Zhao, Hu; Tian, Zengyao; Deng, Yunkun; Li, Xingwen; Lin, Hui

2017-12-01

The dielectric breakdown properties of CO2-O2 mixtures at different O2 concentrations and gas pressures were studied in this paper, with electron detachments from negative ions taken into consideration. The influences of the electron detachment on the reduced effective ionization coefficients αeff/N, the critical reduced electric fields (E/N)cr, the critical electron temperature Tcr, the breakdown reduced electric fields (E/N)breakdown, and the breakdown electron temperature Tbreakdown were analyzed for the CO2-O2 mixture. Based on the results, it was found that an enhancement in αeff/N and a decrease in (E/N)cr and Tcr were caused by the electron detachment, which appeared to be more significant at relatively low E/N and low gas pressures. With the increase in the pd product, both (E/N)breakdown and Tbreakdown in the CO2-O2 mixture decreased first and then tended to be a constant at relatively high pd products.

Toward the detection of the triatomic negative ion SPN-: Spectroscopy and potential energy surfaces

NASA Astrophysics Data System (ADS)

Trabelsi, Tarek; Hochlaf, Majdi; Francisco, Joseph S.

2018-04-01

High level theoretical calculations using coupled-cluster theory were performed to provide an accurate description of the electronic structure, spectroscopic properties, and stability of the triatomic negative ion comprising S, N, and P. The adiabatic electron affinities (AEAs) and vertical detachment energies (VDEs) of PNS, SPN, PSN, and cyc-PSN were calculated. The predicted AEA and VDE of the linear SPN isomer are large: 2.24 and 3.04 eV, respectively. The potential energy surfaces (PESs) of the lowest-lying electronic states of the SPN- isomer along the PN and SP bond lengths and bond angle were mapped. A set of spectroscopic parameters for SPN-, PNS-, and PSN- in their electronic ground states is obtained from the 3D PESs to help detect these species in the gas phase. The electronic excited state SPN-(12A″) is predicted to be stable with a long lifetime calculated to be 189.7 μs. The formation of SPN- in its electronic ground state through the bimolecular collision between S- + PN and N + PS- is also discussed.

Stabilization of very rare tautomers of 1-methylcytosine by an excess electron.

PubMed

Harańczyk, Maciej; Rak, Janusz; Gutowski, Maciej

2005-12-22

We characterized valence anionic states of 1-methylcytosine using various electronic structure methods. We found that the most stable valence anion is related to neither the canonical amino-oxo nor a rare imino-oxo tautomer, in which a proton is transferred from the N4 to N3 atom. Instead, it is related to an imino-oxo tautomer, in which the C5 atom is protonated. This anion is characterized by an electron vertical detachment energy (VDE) of 2.12 eV and it is more stable than the anion based on the canonical tautomer by 1.0 kcal/mol. The latter is characterized by a VDE of 0.31 eV. Another unusual low-lying imino-oxo tautomer with a VDE of 3.60 eV has the C6 atom protonated and is 3.6 kcal/mol less stable than the anion of the canonical tautomer. All these anionic states are adiabatically unbound with respect to the canonical amino-oxo neutral, with the instability of 5.8 kcal/mol for the most stable valence anion. The mechanism of formation of anionic tautomers with carbon atoms protonated may involve intermolecular proton transfer or dissociative electron attachment to the canonical neutral tautomer followed by a barrier-free attachment of a hydrogen atom to the C5 or C6 atom. The six-member ring structure of anionic tautomers with carbon atoms protonated is unstable upon an excess electron detachment. Indeed the neutral systems collapse without a barrier to a linear or a bicyclo structure, which might be viewed as lesions to DNA or RNA. Within the PCM hydration model, the anions become adiabatically bound with respect to the corresponding neutrals, and the two most stable tautomers have a carbon atom protonated.

Are superhalogens without halogen ligand capable of transcending traditional halogen-based superhalogens? Ab initio case study of binuclear anions based on pseudohalogen ligand

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

Li, Jin-Feng; Sun, Yin-Yin; Li, Miao-Miao

2015-06-15

The superhalogen properties of polynuclear structures without halogen ligand are theoretically explored here for several [M{sub 2}(CN){sub 5}]{sup −1} (M =  Ca, Be) clusters. At CCSD(T) level, these clusters have been confirmed to be superhalogens due to their high vertical electron detachment energies (VDE). The largest one is 9.70 eV for [Ca{sub 2}(CN){sub 5}]{sup −1} which is even higher than those of corresponding traditional structures based on fluorine or chlorine ligands. Therefore the superhalogens stronger than the traditional halogen-based structures could be realized by ligands other than halogen atoms. Compared with CCSD(T), outer valence Green’s function (OVGF) method either overestimatesmore » or underestimates the VDEs for different structures while MP2 results are generally consistent in the aspect of relative values. The extra electrons of the highest VDE anions here aggregate on the bridging CN units with non-negligible distribution occurring on other CN units too. These two features lower both the potential and kinetic energies of the extra electron respectively and thus lead to high VDE. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to the detachment of cyanide ligand were also investigated. The sum of these results identifies the potential of polynuclear structures with pseudohalogen ligand as suitable candidates with enhanced superhalogens properties.« less

Electrophilic properties of common MALDI matrix molecules

NASA Astrophysics Data System (ADS)

Lippa, T. P.; Eustis, S. N.; Wang, D.; Bowen, K. H.

2007-11-01

The negative ion photoelectron spectra of the following MALDI matrix molecules have been measured: 3-carboxypyridine (nicotinic acid), 2,5-dihydroxybenzoic acid (DHB), 3,5-dimethoxy-4-hydroxycinnamic acid (sinapinic acid), 2,6-dihydroxyacetophenone (DHAP), 3-(4-hydroxy-3-methoxyphenyl)-2-propenoic acid (ferulic acid), 3-hydroxy-2-pyridinecarboxylic acid (3HPA), and 2,6-pyridinedicarboxylic acid (dipicolinic acid). Adiabatic electron affinities and vertical detachment energies were extracted from these spectra and reported. In addition, electron affinities were calculated for DHAP, ferulic acid, dipicolinic acid and sinapinic acid. Photoelectron spectra were also measured for the dimer anions of DHB and nicotinic acid and for the fragment anion in which alpha-cyano-cinnamic acid had lost a CO2 unit. Together, these results augment the database of presently available electrophilic data on common matrix molecules along with some of their dimers and fragments.

Salt structures and vertical axis rotations; a case study in the Barbastro-Balaguer anticline, Southern Pyrenees.

NASA Astrophysics Data System (ADS)

Pueyo, Emilio L.; Oliván, Carlota; Soto, Ruth; Rodríguez-Pintó, Adriana; Santolaria, Pablo; Luzón, Aránzazu; Casas, Antonio M.; Ayala, Conxi

2017-04-01

Vertical axis rotations are common in all deformation settings. At larger scales, for example in fold and thrust belts, they are usually related to differential shortening along strike and this may be caused by a number of reasons (interplay of plate boundaries, sedimentary wedges, detachment level distribution, etc.). At smaller scales, local stress fields, interference of non-coaxial deformation phases, development of non-cylindrical structures, etc. may play an important role to accommodate significant magnitudes of rotation. Apart from their implication in the truly 4D understanding of geological structures, the occurrence of vertical axis rotation usually precludes the application of most 3D restoration techniques and thus, increases the uncertainty in any 3D reconstruction. Salt structures may form in different geological settings, but focusing on compressive regimes, very little is known about the relation between their geometry and kinematics and their ability to accommodate vertical axis rotations (i.e. local or regional lateral gradients of shortening). The Barbastro-Balaguer anticline (BBA) is the southernmost structure of the Central Pyrenees. It is a large detachment fold spreading more than 150 km along the front. In contrast to most frontal Pyrenean structures, the BBA is detached in Priabonian evaporites and was folded during Oligocene times as witnessed by well exposed growth strata. Along strike changes in the fold axis trend may reach 50°, an overall the anticline displays a convex shape towards the foreland (south). A residual Bouguer anomaly map based on a densely sampled gravimetric surveying (10.000 stations) has helped delineating a heterogeneous distribution of the Eocene detachment level in the subsurface. In this contribution we explore the interplay between vertical axis rotations, detachment level distribution and the fold geometry (structural trend and style based on hundreds of data). Seventy paleomagnetic sites evenly and densely distributed along the structure have been analyzed for this purpose. About 600 standard specimens have been thermally demagnetized in the Paleomagnetic Laboratory of the Burgos University (ASC TD48DC thermal demagnetizer and 2G superconducting magnetometer). Data processing has been carried out with the VPD program, applying standard PCA and virtual direction analyses. The ChRM directions passes the fold test and display two polarities, pointing to the primary character of the magnetization (key factor for the 3D restoration). This large dataset allows us to draw a robust network of rotation magnitudes along strike the western sector of the BBA that are key to understand its kinematics together to the aforementioned factors. We also pretend to use this network of vertical axis rotations to restore in 3D this salt structure.

An Assessment of Molten Metal Detachment Hazards for Electron Beam Welding in the Space Environment: Analysis and Test Results

NASA Technical Reports Server (NTRS)

Nunes, A. C., Jr.; Russell, C.; Bhat, B.; Fragomeni, J. M.

1998-01-01

Conditions under which molten metal detachments might occur in a space welding environment are analyzed. A weld pool detachment parameter specifying conditions for pool detachment by impact is derived and corroborated by experimental evidence. Impact detachment for the pool is unlikely. Impact detachment for a drop of metal on the end of the weld wire may be possible under extreme conditions. Other potential causes of molten metal detachment considered, vaporization pressure forces and wire flickout from the pool, did not appear to present significant detachment threats.

Numerical experiment to estimate the validity of negative ion diagnostic using photo-detachment combined with Langmuir probing

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

Oudini, N.; Sirse, N.; Ellingboe, A. R.

2015-07-15

This paper presents a critical assessment of the theory of photo-detachment diagnostic method used to probe the negative ion density and electronegativity α = n{sub -}/n{sub e}. In this method, a laser pulse is used to photo-detach all negative ions located within the electropositive channel (laser spot region). The negative ion density is estimated based on the assumption that the increase of the current collected by an electrostatic probe biased positively to the plasma is a result of only the creation of photo-detached electrons. In parallel, the background electron density and temperature are considered as constants during this diagnostics. While the numericalmore » experiments performed here show that the background electron density and temperature increase due to the formation of an electrostatic potential barrier around the electropositive channel. The time scale of potential barrier rise is about 2 ns, which is comparable to the time required to completely photo-detach the negative ions in the electropositive channel (∼3 ns). We find that neglecting the effect of the potential barrier on the background plasma leads to an erroneous determination of the negative ion density. Moreover, the background electron velocity distribution function within the electropositive channel is not Maxwellian. This is due to the acceleration of these electrons through the electrostatic potential barrier. In this work, the validity of the photo-detachment diagnostic assumptions is questioned and our results illustrate the weakness of these assumptions.« less

An Assessment of Molten Metal Detachment Hazards During Electron Beam Welding in Space

NASA Technical Reports Server (NTRS)

Fragomeni, James M.; Nunes, Arthur C., Jr.

1998-01-01

The safety issue has been raised with regards to potential molten metal detachments from the weld pool and cold filler wire during electron beam welding in space. This investigation was undertaken to evaluate if molten metal could detach and come in contact with astronauts and burn through the fabric of the astronauts' Extravehicular Mobility Unit (EMU) during electron beam welding in space. Molten metal detachments from either the weld/cut substrate or weld wire could present harm to a astronaut if the detachment was to burn through the fabric of the EMU. Theoretical models were developed to predict the possibility and size of the molten metal detachment hazards during the electron beam welding exercises at Low Earth Orbit (LEO). The primary molten metal detachment concerns were those cases of molten metal separation from the metal surface due to metal cutting, weld pool splashing, entrainment and release of molten metal due to filler wire snap-out from the weld puddle, and molten metal accumulation and release from the end of the weld wire. Some possible ways of obtaining molten metal drop detachments would include an impulse force, or bump, to the weld sample, cut surface, or filler wire. Theoretical models were developed for these detachment concerns from principles of impact and kinetic energies, surface tension, drop geometry, surface energies, and particle dynamics. The surface tension represents the force opposing the liquid metal drop from detaching whereas the weight of the liquid metal droplet represents a force that is tending to detach the molten metal drop. Theoretical calculations have indicated that only a small amount of energy is required to detach a liquid metal drop; however, much of the energy of an impact is absorbed in the sample or weld plate before it reaches the metal drop on the cut edge or surface. The tendency for detachment is directly proportional to the weld pool radius and metal density and inversely proportional to the surface tension of the liquid metal. For a detachment the initial kinetic energy of the weld pool with respect to the plate has to exceed the energy to form the extra surface required for the detachment of the pool. The difficulty is in transferring the energy from the point of impact through the plate and sample to the cut edge. It is likely that not all of the kinetic energy is available for detaching the pool; some may be sequestered in weld pool oscillations. The coefficient of restitution for the collision will be lower than one if irreversible deformation, for example plastic flow deformation, takes place during the collision. Thus determining the amount of energy from an impact that actually reaches the molten metal droplet is critical. Various molten metal detachment scenarios were tested experimentally in an enclosed vacuum chamber using the Ukrainian Universal Hand Tool, an electron beam welder designed for space welding. The experimental testing was performed in a 4 ft. X 4 ft. vacuum chamber at Marshall Space Flight Center, evacuated to vacuum levels of at least 50 microTorr, and also some welding garment material was utilized to observe the effect of the molten metal detachments on the material. A "carillon" apparatus consisting of four pendulum hammer strikers, each weighing approximately 3.65 lbs, raised to predetermined specific heights was used to apply an impact force to the weld sample/plate during electron beam welding and cutting exercises. The strikers were released by switching on an electric motor to rotate a pin holding wires retaining the strikers at desired heights. The specimens were suspended so as to be free to respond to the blows with a sudden velocity increment. The specimens were mounted on a hinged plate for minimizing effective mass with the option to fasten it down so as to raise its effective mass closer to that anticipated for an actual space welding scenario. Measurements were made of the impact energy and the horizontal fling distances of the detached metal drops. It was not particularly easy to generate the detachments for this experiment. This document presents the details of the theoretical modeling effort and a summary of the experimental effort to measure molten metal drop detachments from terrestrial electron beam welding in the enclosed vacuum chamber. The results of the experimental effort have shown that molten metal detachments can occur from the sample/weld plate only if a sufficiently large impact force is applied to the weld plate. A "weld pool detachment parameter" was determined to indicate whether detachment would occur. Detachment can be either full or partial (dripping), Partial detachment means that the weld pool detached from one side of the liquid-solid boundary so as to leave a hole at the puddle site but remained attached over part of the liquid-solid boundary and dripped down the plate with no fully detached material detected. Full detachment, however, does not necessarily mean that the whole pool fully detached; in some cases only a smaller portion of the pool detached, the remainder dripping down the plate. The weld pool detachment parameter according to theory and according to the empirical data allows a determination of whether full detachments might occur. Theoretical calculations indicated titanium alloy would be the most difficult from which to detach molten metal droplets followed by stainless steel and then by aluminum. The experimental results were for the most part consistent with the theoretical analysis and predictions. The above theory is applicable to other situations as desired for assessing the potential for molten metal detachments.

Periodicity, Electronic Structures, and Bonding of Gold Tetrahalides [AuX4](-) (X = F, CI, Br, I, At, Uus)

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

Li, Wan-Lu; Li, Yong; Xu, Congqiao

2015-12-07

Systematic theoretical and experimental investigations have been performed to understand the periodicity and electronic structures of trivalent-gold halides using gold tetrahalides [AuX4]⁻ anions (X = F, Cl, Br, I, At, Uus). The [AuX4]⁻ (X = Cl, Br, I) anions were produced in gas phase and their negative-ion photoelectron spectra were obtained, which exhibited rich and well-resolved spectral peaks. We calculated the adiabatic as well as vertical electron detachment energies using density functional methods with scalar and spin-orbit coupling relativistic effects. The simulated photoelectron spectra based on these calculations are in good agreement with the experimental spectra. Our results show thatmore » the trivalent Au(III) oxidation state becomes progressively less stable while Au(I) is preferred when the halides become heavier along the Period Table. This trend reveals that the oxidation state of metals in complexes can be manipulated through ligand design« less

The anionic (9-methyladenine)-(1-methylthymine) base pair solvated by formic acid. A computational and photoelectron spectroscopy study.

PubMed

Storoniak, Piotr; Mazurkiewicz, Kamil; Haranczyk, Maciej; Gutowski, Maciej; Rak, Janusz; Eustis, Soren N; Ko, Yeon Jae; Wang, Haopeng; Bowen, Kit H

2010-09-02

The photoelectron spectrum for (1-methylthymine)-(9-methyladenine)...(formic acid) (1MT-9MA...FA) anions with the maximum at ca. 1.87 eV was recorded with 2.54 eV photons and interpreted through the quantum-chemical modeling carried out at the B3LYP/6-31+G(d,p) level. The relative free energies of the anions and their calculated vertical detachment energies suggest that only seven anionic structures contribute to the observed PES signal. We demonstrate that electron binding to the (1MT-9MA...FA) complex can trigger intermolecular proton transfer from formic acid, leading to the strong stabilization of the resulting radical anion. The SOMO distribution indicates that an excess electron may localize not only on the pyrimidine but also on the purine moiety. The biological context of DNA-environment interactions concerning the formation of single-strand breaks induced by excess electrons has been briefly discussed.

Equilibrium geometries, electronic and magnetic properties of small AunNi- (n = 1-9) clusters

NASA Astrophysics Data System (ADS)

Tang, Cui-Ming; Chen, Xiao-Xu; Yang, Xiang-Dong

2014-05-01

Geometrical, electronic and magnetic properties of small AunNi- (n = 1-9) clusters have been investigated based on density functional theory (DFT) at PW91P86 level. An extensive structural search shows that the relative stable structures of AunNi- (n = 1-9) clusters adopt 2D structure for n = 1-5, 7 and 3D structure for n = 6, 8-9. And the substitution of a Ni atom for an Au atom in the Au-n+1 cluster obviously changes the structure of the host cluster. Moreover, an odd-even alternation phenomenon has been found for HOMO-LUMO energy gaps, indicating that the relative stable structures of the AunNi- clusters with odd-numbered gold atoms have a higher relative stability. Finally, the natural population analysis (NPA) and the vertical detachment energies (VDE) are studied, respectively. The theoretical values of VDE are reported for the first time to our best knowledge.

Nano-jewellery: C5Au12--a gold-plated diamond at molecular level.

PubMed

Naumkin, F

2006-06-07

A mixed carbon-metal cluster is designed by combining the tetrahedral C(5) radical (with a central atom-the skeleton of the C(5)H(12) molecule) and the spherical Au(12) layer (the external atomic shell of the Au(13) cluster). The C(5)Au(12) cluster and its negative and positive ionic derivatives, C(5)Au(12)(+/-), are investigated ab initio (DFT) in terms of optimized structures and relative energies of a few spin-states, for the icosahedral-like and octahedral-like isomers. The cluster is predicted to be generally more stable in its octahedral shape (similar to C(5)H(12)) which prevails for the negative ion and may compete with the icosahedral shape for the neutral system and positive ion. Adiabatic ionization energies (AIE) and electron affinities (AEA) of C(5)Au(12), vertical electron-detachment (VDE) energies of C(5)Au(12)(-), and vertical ionization and electron-attachment energies (VIE, VEA) of C(5)Au(12) are calculated as well, and compared with those for the corresponding isomers of the Au(13) cluster. The AIE and VIE values are found to be close for the two systems, while the AEA and VDE values are significantly reduced for the radical-based species. A simple fragment-based model is proposed for the decomposition of the total interaction into carbon-gold and gold-gold components.

An Assessment of Molten Metal Detachment Hazards During Electron Beam Welding in Space

NASA Technical Reports Server (NTRS)

Fragomeni, James M.; Nunes, Arthur C., Jr.

1998-01-01

The safety issue has been raised with regards to potential molten metal detachments from the weld pool and cold filler wire during electron beam welding in space. This investigation was undertaken to evaluate if molten metal could detach and come in contact with astronauts and burn through the fabric of the astronauts' Extravehicular Mobility Unit (EMU) during electron beam welding in space. Molten metal detachments from either the weld/cut substrate or weld wire could present harm to a astronaut if the detachment was to burn through the fabric of the EMU. Theoretical models were developed to predict the possibility and size of the molten metal detachment hazards during the electron beam welding exercises at Low Earth Orbit (LEO). The primary molten metal detachment concerns were those cases of molten metal separation from the metal surface due to metal cutting, weld pool splashing, entrainment and release of molten metal due to filler wire snap-out from the weld puddle, and molten metal accumulation and release from the end of the weld wire. Some possible ways of obtaining molten metal drop detachments would include an impulse force, or bump, to the weld sample, cut surface, or filler wire. Theoretical models were developed for these detachment concerns from principles of impact and kinetic energies, surface tension, drop geometry, surface energies, and particle dynamics. The surface tension represents the force opposing the liquid metal drop from detaching whereas the weight of the liquid metal droplet represents a force that is tending to detach the molten metal drop. Theoretical calculations have indicated that only a small amount of energy is required to detach a liquid metal drop; however, much of the energy of an impact is absorbed in the sample or weld plate before it reaches the metal drop on the cut edge or surface. The tendency for detachment is directly proportional to the weld pool radius and metal density and inversely proportional to the surface tension of the liquid metal. For a detachment the initial kinetic energy of the weld pool with respect to the plate has to exceed the energy to form the extra surface required for the detachment of the pool. The difficulty is in transferring the energy from the point of impact through the plate and sample to the cut edge. It is likely that not all of the kinetic energy is available for detaching the pool; some may be sequestered in weld pool oscillations. The coefficient of restitution for the collision will be lower than one if irreversible deformation, for example plastic flow deformation, takes place during the collision. Thus determining the amount of energy from an impact that actually reaches the molten metal droplet is critical. Various molten metal detachment scenarios were tested experimentally in an enclosed vacuum chamber using the Ukrainian Universal Hand Tool, an electron beam welder designed for space welding. The experimental testing was performed in a 4 ft. X 4 ft. vacuum chamber at Marshall Space Flight Center, evacuated to vacuum levels of at least 50 microTorr, and also some welding garment material was utilized to observe the effect of the molten metal detachments on the material. A "carillon" apparatus consisting of four pendulum hammer strikers, each weighing approximately 3.65 lbs, raised to predetermined specific heights was used to apply an impact force to the weld sample/plate during electron beam welding and cutting exercises. The strikers were released by switching on an electric motor to rotate a pin holding wires retaining the strikers at desired heights. The specimens were suspended so as to be free to respond to the blows with a sudden velocity increment. The specimens were mounted on a hinged plate for minimizing effective mass with the option to fasten it down so as to raise its effective mass closer to that anticipated for an actual space welding scenario. Measurements were made of the impact energy and the horizontal fling distances of the detached metal drops. It was not particularly easy to generate the detachments fo

Anomalous property of Ag(BO2)2 hyperhalogen: does spin-orbit coupling matter?

PubMed

Chen, Hui; Kong, Xiang-Yu; Zheng, Weijun; Yao, Jiannian; Kandalam, Anil K; Jena, Puru

2013-10-07

Hyperhalogens were recently identified as a new class of highly electronagative species which are composed of metals and superhalogens. In this work, high-level theoretical calculations and photoelectron spectroscopy experiments are systematically conducted to investigate a series of coinage-metal-containing hyperhalogen anions, Cu(BO(2))(2)(-), Ag(BO(2))(2)(-), and Au(BO(2))(2)(-). The vertical electron detachment energy (VDE) of Ag(BO(2))(2)(-) is anomalously higher than those of Au(BO(2))(2)(-) and Cu(BO(2))(2)(-). In quantitative agreement with the experiment, high-level ab initio calculations reveal that spin-orbit coupling (SOC) lowers the VDE of Au(BO(2))(2)(-) significantly. The sizable magnitude of about 0.5 eV of SOC effect on the VDE of Au(BO(2))(2)(-) demonstrates that SOC plays an important role in the electronic structure of gold hyperhalogens. This study represents a new paradigm for relativistic electronic structure calculations for the one-electron-removal process of ionic Au(I)L(2) complexes, which is characterized by a substantial SOC effect. Copyright © 2013 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim.

Computational and photoelectron spectroscopic study of the dipole-bound anions, indole(H2O)1,2 (.).

PubMed

Buytendyk, A M; Buonaugurio, A M; Xu, S-J; Nilles, J M; Bowen, K H; Kirnosov, N; Adamowicz, L

2016-07-14

We report our joint computational and anion photoelectron spectroscopic study of indole-water cluster anions, indole(H2O)1,2 (-). The photoelectron spectra of both cluster anions show the characteristics of dipole-bound anions, and this is confirmed by our theoretical computations. The experimentally determined vertical electron detachment (VDE) energies for indole(H2O)1 (-) and indole(H2O)2 (-) are 144 meV and 251 meV, respectively. The corresponding theoretically determined VDE values for indole(H2O)1 (-) and indole(H2O)2 (-) are 124 meV and 255 meV, respectively. The vibrational features in the photoelectron spectra of these cluster anions are assigned as the vibrations of the water molecule.

Computational and photoelectron spectroscopic study of the dipole-bound anions, indole(H2O)1,2-

NASA Astrophysics Data System (ADS)

Buytendyk, A. M.; Buonaugurio, A. M.; Xu, S.-J.; Nilles, J. M.; Bowen, K. H.; Kirnosov, N.; Adamowicz, L.

2016-07-01

We report our joint computational and anion photoelectron spectroscopic study of indole-water cluster anions, indole(H2O)1,2-. The photoelectron spectra of both cluster anions show the characteristics of dipole-bound anions, and this is confirmed by our theoretical computations. The experimentally determined vertical electron detachment (VDE) energies for indole(H2O)1- and indole(H2O)2- are 144 meV and 251 meV, respectively. The corresponding theoretically determined VDE values for indole(H2O)1- and indole(H2O)2- are 124 meV and 255 meV, respectively. The vibrational features in the photoelectron spectra of these cluster anions are assigned as the vibrations of the water molecule.

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.

Two-dimensional spectra of electron collisions with acrylonitrile and methacrylonitrile reveal nuclear dynamics

NASA Astrophysics Data System (ADS)

Regeta, K.; Allan, M.

2015-05-01

Detailed experimental information on the motion of a nuclear packet on a complex (resonant) anion potential surface is obtained by measuring 2-dimensional (2D) electron energy loss spectra. The cross section is plotted as a function of incident electron energy, which determines which resonant anion state is populated, i.e., along which normal coordinate the wave packet is launched, and of the electron energy loss, which reveals into which final states each specific resonant state decays. The 2D spectra are presented for acrylonitrile and methacrylonitrile, at the incident energy range 0.095-1.0 eV, where the incoming electron is temporarily captured in the lowest π∗ orbital. The 2D spectra reveal selectivity patterns with respect to which vibrations are excited in the attachment and de-excited in the detachment. Further insight is gained by recording 1D spectra measured along horizontal, vertical, and diagonal cuts of the 2D spectrum. The methyl group in methacrylonitrile increases the resonance width 7 times. This converts the sharp resonances of acrylonitrile into boomerang structures but preserves the essence of the selectivity patterns. Selectivity of vibrational excitation by higher-lying shape resonances up to 8 eV is also reported.

Laser induced photo-detachment of O2 in DC discharge

NASA Astrophysics Data System (ADS)

J, R. LEGORRETA; J, L. PATIÑO; F, B. YOUSIF

2018-07-01

Determination of the negative ion number density of {{{O}}}{{2}}- and {{{O}}}- in a DC discharge of oxygen plasma was made employing Langmuir probe in conjunction with eclipse laser photo-detachment technique. The temporal evolution of the extra electrons resulting from the photo-detachment of {{{O}}}{{2}}- and {{{O}}}- were used to evaluate the negative ion number density. The ratio of {{{O}}}{{2}}- number density to {{{O}}}- varied from 0.03 to 0.22. Number density of both {{{O}}}{{2}}- and {{{O}}}- increased with increasing power and decreased as the pressure was increased. Electron number density was evaluated from the electron energy distribution function (EEDF) using the I–V recorded characteristic curves. Electron temperature between 2 and 2.7 eV were obtained. Influence of the {{{O}}}{{2}}({a}{{1}}{{{Δ }}}{{g}}) metastable state is discussed.

Probing the Properties of Polynuclear Superhalogens without Halogen Ligand via ab Initio Calculations: A Case Study on Double-Bridged [Mg2 (CN)5 ](-1) Anions.

PubMed

Li, Jin-Feng; Li, Miao-Miao; Bai, Hongcun; Sun, Yin-Yin; Li, Jian-Li; Yin, Bing

2015-12-01

An ab initio study of the superhalogen properties of eighteen binuclear double-bridged [Mg2 (CN)5 ](-1) clusters is reported herein by using various theoretical methods. High-level CCSD(T) results indicate that all the clusters possess strong superhalogen properties owing to their high vertical electron detachment energies (VDEs), which exceed 6.8 eV (highest: 8.15 eV). The outer valence Green's function method provides inaccurate relative VDE values; hence, this method is not suitable for this kind of polynuclear superhalogens. Both the HF and MP2 results are generally consistent with the CCSD(T) level regarding the relative VDE values and-especially interesting-the average values of the HF and MP2 VDEs are extremely close to the CCSD(T) results. The distributions of the extra electrons of the anions are mainly aggregated into the terminal CN units. These distributions are apparently different from those of previously reported triple-bridged isomers and may be the reason for the decreased VDE values of the clusters. In addition, comparisons of the VDEs of binuclear and mononuclear superhalogens as well as studies of the thermodynamic stabilities with respect to the detachment of various CN(-1) ligands are also performed. These results confirm that polynuclear structures with pseudohalogen ligands can be considered as probable new superhalogens with enhanced properties. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

On the applicability of one- and many-electron quantum chemistry models for hydrated electron clusters

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

Turi, László, E-mail: turi@chem.elte.hu

2016-04-21

We evaluate the applicability of a hierarchy of quantum models in characterizing the binding energy of excess electrons to water clusters. In particular, we calculate the vertical detachment energy of an excess electron from water cluster anions with methods that include one-electron pseudopotential calculations, density functional theory (DFT) based calculations, and ab initio quantum chemistry using MP2 and eom-EA-CCSD levels of theory. The examined clusters range from the smallest cluster size (n = 2) up to nearly nanosize clusters with n = 1000 molecules. The examined cluster configurations are extracted from mixed quantum-classical molecular dynamics trajectories of cluster anions withmore » n = 1000 water molecules using two different one-electron pseudopotenial models. We find that while MP2 calculations with large diffuse basis set provide a reasonable description for the hydrated electron system, DFT methods should be used with precaution and only after careful benchmarking. Strictly tested one-electron psudopotentials can still be considered as reasonable alternatives to DFT methods, especially in large systems. The results of quantum chemistry calculations performed on configurations, that represent possible excess electron binding motifs in the clusters, appear to be consistent with the results using a cavity structure preferring one-electron pseudopotential for the hydrated electron, while they are in sharp disagreement with the structural predictions of a non-cavity model.« less

On the applicability of one- and many-electron quantum chemistry models for hydrated electron clusters

NASA Astrophysics Data System (ADS)

Turi, László

2016-04-01

We evaluate the applicability of a hierarchy of quantum models in characterizing the binding energy of excess electrons to water clusters. In particular, we calculate the vertical detachment energy of an excess electron from water cluster anions with methods that include one-electron pseudopotential calculations, density functional theory (DFT) based calculations, and ab initio quantum chemistry using MP2 and eom-EA-CCSD levels of theory. The examined clusters range from the smallest cluster size (n = 2) up to nearly nanosize clusters with n = 1000 molecules. The examined cluster configurations are extracted from mixed quantum-classical molecular dynamics trajectories of cluster anions with n = 1000 water molecules using two different one-electron pseudopotenial models. We find that while MP2 calculations with large diffuse basis set provide a reasonable description for the hydrated electron system, DFT methods should be used with precaution and only after careful benchmarking. Strictly tested one-electron psudopotentials can still be considered as reasonable alternatives to DFT methods, especially in large systems. The results of quantum chemistry calculations performed on configurations, that represent possible excess electron binding motifs in the clusters, appear to be consistent with the results using a cavity structure preferring one-electron pseudopotential for the hydrated electron, while they are in sharp disagreement with the structural predictions of a non-cavity model.

Multiple ion species fluid modeling of sprite halos and the role of electron detachment from O- in their dynamics

NASA Astrophysics Data System (ADS)

Liu, N.

2011-12-01

Sprite halos are brief descending glows appearing at the lower ionosphere boundary, which follow impulsive cloud-to-ground lightning discharges [e.g., Barrington-Leigh et al., JGR, 106, 1741, 2001, Wescott et al., JGR, 106, 10467, 2001; Pasko, JGR, 115, A00E35, 2010]. They last for a few milliseconds, with horizontal extension of tens of kilometers and vertical thickness of several kilometers. According to global survey of the occurrence of transient luminous events by the ISUAL instruments on the FORMOSAT-2 satellite, on average sprite halos occur once every minute on Earth [Chen et al., JGR, 113, A08306, 2008]. It has been established that sprite halos are caused by electron heating, and molecule excitation and ionization in the lower ionosphere due to lightning quasi-electrostatic field [e.g., Pasko et al., JGR, 102, 4529, 1997; Barrington-Leigh et al., 2001; Pasko, 2010]. Past modeling work on sprite halos was conducted using either a two dimensional (2D) model of at most three charged species or a zero dimensional model of multiple ion species. In this talk, we report a modeling study of sprite halos using a recently developed 2D fluid model of multiple charged species. The model charged species include the ion species set used in [Lehtinen and Inan, GRL, 34, L08804, 2007] to study the dynamics of ionization perturbations produced by gigantic jets in the middle and upper atmosphere. In addition, another charged species, O-, is added to this set, because electron detachment of O- can proceed very fast under moderate electric field [Rayment and Moruzzi, Int. J. Mass Spectrom., 26, 321, 1978], requiring a separate treatment from the other light negative ions. The modeling results of a sprite halo driven by positive cloud-to-ground lightning indicate that the halo can descend to lower altitude with much higher electron density behind its front when the O- detachment process is included. Electron density ahead of the halo front is not significantly reduced from the ambient value, so that there is no attachment "hole" forming in that region that is commonly observed in previous modeling work. According to recent work by Qin et al. [JGR, 116, A06305, 2011], electron density must be around 10^3 1/m^3 or less at sprite initiation altitude in order for individual streamers to form. This requires the ambient electron density at the sprite initiation altitude to be close to 10^3 1/m^3 from our results, because electron density is not greatly decreased below the halo front. In addition, the large downward extent of the halo shown by our results may offer an explanation for the initiation of sprite streamers at 65-70 km altitude observed previously.

Electron Detachment as a Probe of Intrinsic Nucleobase Dynamics in Dianion-Nucleobase Clusters: Photoelectron Spectroscopy of the Platinum II Cyanide Dianion Bound to Uracil, Thymine, Cytosine and Adenine

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

Sen, Ananya; Hou, Gao-Lei; Wang, Xue B.

2015-08-05

We report the first low-temperature photodetachment photoelectron spectra of isolated gas-phase complexes of the platinum II cyanide dianion bound to nucleobases. These systems are model systems for understanding platinum-complex photodynamic therapies, and knowledge of the intrinsic photodetachment properties is crucial for understanding their broader photophysical properties. Well-resolved, distinct peaks are observed in the spectra consistent with the complexes where the Pt(CN)42- moiety is largely intact. The adiabatic electron detachment energies for the dianion-nucleobase complexes are measured to be between 2.39-2.46 eV. The magnitudes of the repulsive Coulomb barriers of the complexes are estimated to be between 1.9 and 2.1 eV,more » values that are lower than for the bare Pt(CN)42- dianion as a result of charge solvation by the nucleobases. In addition to the resolved spectral features, broad featureless bands indicative of delayed electron detachment are observed in the 193 nm photodetachment spectra of the four nucleobase-dianion complexes, and also in the 266 nm spectra of the Pt(CN)42-∙thymine and Pt(CN)42-∙adenine complexes. The selective excitation of these features in the 266 nm spectra is attributed to one-photon excitation of [Pt(CN)42-∙T]* and [Pt(CN)42-∙A]* long-lived excited states that can effectively couple to the electron detachment continuum, producing strong electron detachment signals. We attribute the resonant electron detachment bands observed here for Pt(CN)42-∙T and Pt(CN)42-∙A but not for Pt(CN)42-∙U and Pt(CN)42-∙C to fundamental differences in the individual nucleobase photophysics following 266 nm excitation. This indicates that the Pt(CN)42- dianion in the Pt(CN)42-∙M clusters can be viewed as a “dynamic tag” which has the propensity to emit electrons when the attached nucleobase disaplys a long-lived excited state.« less

Electron accommodation dynamics in the DNA base thymine

NASA Astrophysics Data System (ADS)

King, Sarah B.; Stephansen, Anne B.; Yokoi, Yuki; Yandell, Margaret A.; Kunin, Alice; Takayanagi, Toshiyuki; Neumark, Daniel M.

2015-07-01

The dynamics of electron attachment to the DNA base thymine are investigated using femtosecond time-resolved photoelectron imaging of the gas phase iodide-thymine (I-T) complex. An ultraviolet pump pulse ejects an electron from the iodide and prepares an iodine-thymine temporary negative ion that is photodetached with a near-IR probe pulse. The resulting photoelectrons are analyzed with velocity-map imaging. At excitation energies ranging from -120 meV to +90 meV with respect to the vertical detachment energy (VDE) of 4.05 eV for I-T, both the dipole-bound and valence-bound negative ions of thymine are observed. A slightly longer rise time for the valence-bound state than the dipole-bound state suggests that some of the dipole-bound anions convert to valence-bound species. No evidence is seen for a dipole-bound anion of thymine at higher excitation energies, in the range of 0.6 eV above the I-T VDE, which suggests that if the dipole-bound anion acts as a "doorway" to the valence-bound anion, it only does so at excitation energies near the VDE of the complex.

Electron accommodation dynamics in the DNA base thymine.

PubMed

King, Sarah B; Stephansen, Anne B; Yokoi, Yuki; Yandell, Margaret A; Kunin, Alice; Takayanagi, Toshiyuki; Neumark, Daniel M

2015-07-14

The dynamics of electron attachment to the DNA base thymine are investigated using femtosecond time-resolved photoelectron imaging of the gas phase iodide-thymine (I(-)T) complex. An ultraviolet pump pulse ejects an electron from the iodide and prepares an iodine-thymine temporary negative ion that is photodetached with a near-IR probe pulse. The resulting photoelectrons are analyzed with velocity-map imaging. At excitation energies ranging from -120 meV to +90 meV with respect to the vertical detachment energy (VDE) of 4.05 eV for I(-)T, both the dipole-bound and valence-bound negative ions of thymine are observed. A slightly longer rise time for the valence-bound state than the dipole-bound state suggests that some of the dipole-bound anions convert to valence-bound species. No evidence is seen for a dipole-bound anion of thymine at higher excitation energies, in the range of 0.6 eV above the I(-)T VDE, which suggests that if the dipole-bound anion acts as a "doorway" to the valence-bound anion, it only does so at excitation energies near the VDE of the complex.

Photodetachment and UV-Vis spectral properties of Cl2rad -·nHO clusters: Extrapolation to bulk

NASA Astrophysics Data System (ADS)

Pathak, A. K.; Mukherjee, T.; Maity, D. K.

2008-03-01

Vertical detachment energy (VDE) and UV-Vis spectra of Cl2rad -·nHO clusters ( n = 1-11) are reported based on first principle electronic structure calculations. VDE of the hydrated clusters are calculated following second order Moller-Plesset perturbation (MP2) as well as coupled cluster theory with 6-311++G(d,p) set of basis function. The excess electron in these hydrated clusters is mainly localized over the solute Cl atoms. A linear relationship is obtained for VDE vs. ( n + 2.6) -1/3 and bulk VDE of Cl2rad - aqueous solution is calculated as 10.61 eV at CCSD(T) level of theory. UV-Vis spectra of these hydrated clusters are calculated applying CI with single electron (CIS) excitation procedure. Simulated UV-Vis spectra of Cl2rad -·10HO cluster is noted to be in excellent agreement with the reported spectra of Cl2rad - (aq) system, λmax for Cl2rad -·11HO system is calculated to be red shifted though.

Cisplatin intrastrand adducts sensitize DNA to base damage by hydrated electrons.

PubMed

Behmand, B; Wagner, J R; Sanche, L; Hunting, D J

2014-05-08

The oligonucleotide TTTTTGTGTTT with or without a cisplatin adduct was reacted with hydrated electrons generated by ionizing radiation. Hydroxyl radicals were quenched with ethylenediaminetetraacetic acid (EDTA), and the solutions were bubbled with wet nitrogen to eliminate oxygen, a scavenger of hydrated electrons. Prior to irradiation, the structure of the initial cisplatin adduct was identified by mass spectrometry as G-cisplatin-G. Radiation damage to DNA bases was quantified by high-performance liquid chromatography (HPLC), after enzymatic digestion of the TTTTTGTGTTT-cisplatin complex to deoxyribonucleosides. The masses of the platinum adducts following digestion and separation by HPLC were measured by mass spectrometry. Our results demonstrate that hydrated electrons induce damage to thymines as well as detachment of the cisplatin moiety from both guanines in the oligonucleotide. This detachment regenerates both unmodified guanine and damaged guanine, in equimolar amounts. At 1000 Gy, a net average of 2.5 thymines and 1 guanine are damaged for each platinum lost from the oligonucleotide. Given the extensive base damage that occurs for each cisplatin adduct lost, it is clear that, prior to undergoing detachment, these adducts must catalyze several cycles of reactions of hydrated electrons with DNA bases. It is likely that a single reaction leads to the loss of the cisplatin adduct and the damage observed on the guanine base; however, the damage to the thymine bases must require the continued presence of the cisplatin adduct, acting as a catalyst. To our knowledge, this is the first time that platinum-DNA adducts have been shown to have catalytic activity. We propose two pathways for the interaction of hydrated electrons with TTTTTGTGTTT-cisplatin: (1) the hydrated electron is initially captured by a thymine base and transferred by base to base electron hopping to the guanine site, where the cisplatin moiety detaches from the oligonucleotide via dissociative electron attachment, and (2) the hydrated electron interacts directly with the platinum-guanine adduct and induces detachment of the cisplatin moiety via dissociative electron attachment. Although the precise mechanism remains to be elucidated, our results provide important insights into the radiosensitization of DNA by cisplatin.

Cisplatin Intrastrand Adducts Sensitize DNA to Base Damage by Hydrated Electrons

PubMed Central

Behmand, B.; Wagner, J. R.; Sanche, L.; Hunting, D. J.

2015-01-01

The oligonucleotide TTTTTGTGTTT with or without a cisplatin adduct was reacted with hydrated electrons generated by ionizing radiation. Hydroxyl radicals were quenched with ethylenediaminetetraacetic acid (EDTA), and the solutions were bubbled with wet nitrogen to eliminate oxygen, a scavenger of hydrated electrons. Prior to irradiation, the structure of the initial cisplatin adduct was identified by mass spectrometry as G-cisplatin-G. Radiation damage to DNA bases was quantified by high-performance liquid chromatography (HPLC), after enzymatic digestion of the TTTTTGTGTTT-cisplatin complex to deoxyribonucleosides. The masses of the platinum adducts following digestion and separation by HPLC were measured by mass spectrometry. Our results demonstrate that hydrated electrons induce damage to thymines as well as detachment of the cisplatin moiety from both guanines in the oligonucleotide. This detachment regenerates both unmodified guanine and damaged guanine, in equimolar amounts. At 1000 Gy, a net average of 2.5 thymines and 1 guanine are damaged for each platinum lost from the oligonucleotide. Given the extensive base damage that occurs for each cisplatin adduct lost, it is clear that, prior to undergoing detachment, these adducts must catalyze several cycles of reactions of hydrated electrons with DNA bases. It is likely that a single reaction leads to the loss of the cisplatin adduct and the damage observed on the guanine base; however, the damage to the thymine bases must require the continued presence of the cisplatin adduct, acting as a catalyst. To our knowledge, this is the first time that platinum-DNA adducts have been shown to have catalytic activity. We propose two pathways for the interaction of hydrated electrons with TTTTTGTGTTT-cisplatin: (1) the hydrated electron is initially captured by a thymine base and transferred by base to base electron hopping to the guanine site, where the cisplatin moiety detaches from the oligonucleotide via dissociative electron attachment, and (2) the hydrated electron interacts directly with the platinum-guanine adduct and induces detachment of the cisplatin moiety via dissociative electron attachment. Although the precise mechanism remains to be elucidated, our results provide important insights into the radiosensitization of DNA by cisplatin. PMID:24779712

Experimental Characterization of Plasma Detachment from Magnetic Nozzles

NASA Astrophysics Data System (ADS)

Olsen, Christopher Scott

Magnetic nozzles, like Laval nozzles, are observed in several natural systems and have application in areas such as electric propulsion and plasma processing. Plasma flowing through these nozzles is inherently tied to the field lines and must separate for momentum redirection or particle transport to occur. Plasma detachment and associated mechanisms from a magnetic nozzle are investigated. Experimental results are presented from the plume of the VASIMRRTM VX-200 device flowing along an axisymmetric magnetic nozzle and operated at two ion energies to explore momentum dependent detachment. The argon plume expanded into a 150m3 vacuum chamber where the background pressure was low enough that charge-exchange mean-free-paths were longer than experiment scale lengths. This magnetic nozzle system is demonstrated to hydrodynamically scale up to astrophysical plasmas, particularly the solar chromosphere, implying general relevance to many systems. Plasma parameters were mapped over a large spatial range using measurements from multiple plasma diagnostics. The data show that the plume does not follow the magnetic field lines. A mapped integration of the ion flux shows the plume may be divided into three regions where 1) the plume briefly follows the magnetic flux, 2) diverges quadratically before 3) expanding with linear trajectories. Transitioning from region 1→2, the ion flux departs from the magnetic flux suggesting ion detachment. An instability forms in region 2 driving an oscillating electric field that causes ions to expand before enhancing electron cross-field transport through anomalous resistivity. Transitioning from region 2→3 the electric field dissipates, the trajectories linearize, and the plume effectively detaches. A delineation of sub-to-super Alfvenic flow aligns well with the inflection points of the linearization without a change in magnetic topology. The detachment process is best described as a two part process: First, ions detach by a breakdown of the magnetic moment when the quantity |v/fcLB| becomes of order unity. Second, the turbulent electric field enhances electron transport up to a factor of 4+/-1 above collisional diffusion; electron cross-field velocities approximate that of the ions and depart on more centralized field lines. Electrons are believed to detach by breakdown of magnetic moment further downstream in the weaker magnetic field.

Numerical simulations used for a validity check on the laser induced photo-detachment diagnostic method in electronegative plasmas

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

Oudini, N.; Taccogna, F.; Bendib, A.

2014-06-15

Laser photo-detachment is used as a method to measure or determine the negative ion density and temperature in electronegative plasmas. In essence, the method consists of producing an electropositive channel (negative ion free region) via pulsed laser photo-detachment within an electronegative plasma bulk. Electrostatic probes placed in this channel measure the change in the electron density. A second pulse might be used to track the negative ion recovery. From this, the negative ion density and temperature can be determined. We study the formation and relaxation of the electropositive channel via a two-dimensional Particle-In-Cell/Mote Carlo collision model. The simulation is mainlymore » carried out in a Hydrogen plasma with an electronegativity of α = 1, with a parametric study for α up to 20. The temporal and spatial evolution of the plasma potential and the electron densities shows the formation of a double layer (DL) confining the photo-detached electrons within the electropositive channel. This DL evolves into two fronts that move in the opposite directions inside and outside of the laser spot region. As a consequence, within the laser spot region, the background and photo-detached electron energy distribution function relaxes/thermalizes via collisionless effects such as Fermi acceleration and Landau damping. Moreover, the simulations show that collisional effects and the DL electric field strength might play a non-negligible role in the negative ion recovery within the laser spot region, leading to a two-temperature negative ion distribution. The latter result might have important effects in the determination of the negative ion density and temperature from laser photo detachment diagnostic.« less

Numerical simulations used for a validity check on the laser induced photo-detachment diagnostic method in electronegative plasmas

NASA Astrophysics Data System (ADS)

Oudini, N.; Taccogna, F.; Bendib, A.; Aanesland, A.

2014-06-01

Laser photo-detachment is used as a method to measure or determine the negative ion density and temperature in electronegative plasmas. In essence, the method consists of producing an electropositive channel (negative ion free region) via pulsed laser photo-detachment within an electronegative plasma bulk. Electrostatic probes placed in this channel measure the change in the electron density. A second pulse might be used to track the negative ion recovery. From this, the negative ion density and temperature can be determined. We study the formation and relaxation of the electropositive channel via a two-dimensional Particle-In-Cell/Mote Carlo collision model. The simulation is mainly carried out in a Hydrogen plasma with an electronegativity of α = 1, with a parametric study for α up to 20. The temporal and spatial evolution of the plasma potential and the electron densities shows the formation of a double layer (DL) confining the photo-detached electrons within the electropositive channel. This DL evolves into two fronts that move in the opposite directions inside and outside of the laser spot region. As a consequence, within the laser spot region, the background and photo-detached electron energy distribution function relaxes/thermalizes via collisionless effects such as Fermi acceleration and Landau damping. Moreover, the simulations show that collisional effects and the DL electric field strength might play a non-negligible role in the negative ion recovery within the laser spot region, leading to a two-temperature negative ion distribution. The latter result might have important effects in the determination of the negative ion density and temperature from laser photo detachment diagnostic.

Stackable multi-port gas nozzles

DOEpatents

Poppe, Steve; Rozenzon, Yan; Ding, Peijun

2015-03-03

One embodiment provides a reactor for material deposition. The reactor includes a chamber and at least one gas nozzle. The chamber includes a pair of susceptors, each having a front side and a back side. The front side mounts a number of substrates. The susceptors are positioned vertically so that the front sides of the susceptors face each other, and the vertical edges of the susceptors are in contact with each other, thereby forming a substantially enclosed narrow channel between the substrates mounted on different susceptors. The gas nozzle includes a gas-inlet component situated in the center and a detachable gas-outlet component stacked around the gas-inlet component. The gas-inlet component includes at least one opening coupled to the chamber, and is configured to inject precursor gases into the chamber. The detachable gas-outlet component includes at least one opening coupled to the chamber, and is configured to output exhaust gases from the chamber.

Ab initio correlated study of the Al13H- anion: Isomers, their kinetic stability and vertical detachment energies

NASA Astrophysics Data System (ADS)

Moc, Jerzy

2012-01-01

We report correlated ab initio calculations for the Al13H- cluster anion isomers, their kinetic stability and vertical detachment energies (VDEs). Of the two most energetically favored anion structures involving H atom in terminal and threefold bridged sites of the icosahedral Al13-, the higher energy ‘threefold bridged' isomer is shown to be of low kinetic stability. Our results are consistent with the recent photoelectron spectroscopy (PE) study of Grubisic et al. who observed two distinct Al13H- isomers, one of them identified as ‘metastable'. The VDE energies computed at the CCSD(T)/aug-cc-pVTZ//MP2/aug-cc-pVDZ level for the ‘terminal' and ‘threefold bridged' Al13H- isomers of 3.21 and 2.32 eV are in good agreement with those determined in the PE study.

Bacteria use type IV pili to walk upright and detach from surfaces.

PubMed

Gibiansky, Maxsim L; Conrad, Jacinta C; Jin, Fan; Gordon, Vernita D; Motto, Dominick A; Mathewson, Margie A; Stopka, Wiktor G; Zelasko, Daria C; Shrout, Joshua D; Wong, Gerard C L

2010-10-08

Bacterial biofilms are structured multicellular communities involved in a broad range of infections. Knowing how free-swimming bacteria adapt their motility mechanisms near surfaces is crucial for understanding the transition between planktonic and biofilm phenotypes. By translating microscopy movies into searchable databases of bacterial behavior, we identified fundamental type IV pili-driven mechanisms for Pseudomonas aeruginosa surface motility involved in distinct foraging strategies. Bacteria stood upright and "walked" with trajectories optimized for two-dimensional surface exploration. Vertical orientation facilitated surface detachment and could influence biofilm morphology.

Studies of protonated and anionic artemisinin in the gas-phase by infrared multi-photon dissociation and by negative ion photoelectron spectroscopies

NASA Astrophysics Data System (ADS)

Seydou, M.; Gillet, J. C.; Li, X.; Wang, H.; Posner, G. H.; Grégoire, G.; Schermann, J. P.; Bowen, K. H.; Desfrançois, C.

2007-12-01

Protonated and anionic artemisinin in the gas phase have respectively been studied by infrared multi-photon dissociation (IRMPD) spectroscopy and by anion photoelectron spectroscopy. Comparison of the measured IRMPD spectrum with calculated spectra of various conformations showed that the two lowest-energy protonated structures, both corresponding to protonation at the C dbnd O 14 carbonyl site, were observed experimentally. The calculations also indicated that the peroxide bridge in artemisinin is only slightly modified by protonation. Additionally, stable, intact (parent) artemisinin radical anions have been obtained for the first time in the gas phase and the photoelectron spectrum supports the computational finding that the excess electron is mainly localized on the σ ∗ orbital of the peroxide bond. The vertical detachment energy and adiabatic electron affinity, calculated at the MP2/6-31+G ∗ level, are in good agreement with the experimental data and the O-O distance is calculated to be stretched by more than 50% in the anion.

Broad photoelectron spectrum and lowered electron affinity due to hydrogen in ZnOH: A joint experimental and theoretical study

NASA Astrophysics Data System (ADS)

Iordanov, I.; Gunaratne, K. D. D.; Harmon, C. L.; Sofo, J. O.; Castleman, A. W.

2012-06-01

We report a combined experimental and theoretical photoelectron spectroscopy study of ZnOH-. We find that the electron binding energy spectrum of ZnOH- reveals a broad and featureless peak between 1.4 and 2.4 eV in energy. The vertical detachment energy (VDE) of ZnOH- is determined to be 1.78 eV, which is lower than the 2.08 eV VDE of ZnO-. Our theoretical calculations match the VDE of ZnOH- accurately, but we find that the broadness of the peak cannot be explained by rotational or vibrational state excitation. The broadness of this peak is in strong contrast to the narrow and easily understood first peak of the ZnO spectrum, which features a well-resolved vibrational progression that can be readily explained by calculating the Franck-Condon transition factors. This study provides spectroscopic evidence of the effect of hydrogen on diatomic ZnO.

Broad photoelectron spectrum and lowered electron affinity due to hydrogen in ZnOH: a joint experimental and theoretical study.

PubMed

Iordanov, I; Gunaratne, K D D; Harmon, C L; Sofo, J O; Castleman, A W

2012-06-07

We report a combined experimental and theoretical photoelectron spectroscopy study of ZnOH(-). We find that the electron binding energy spectrum of ZnOH(-) reveals a broad and featureless peak between 1.4 and 2.4 eV in energy. The vertical detachment energy (VDE) of ZnOH(-) is determined to be 1.78 eV, which is lower than the 2.08 eV VDE of ZnO(-). Our theoretical calculations match the VDE of ZnOH(-) accurately, but we find that the broadness of the peak cannot be explained by rotational or vibrational state excitation. The broadness of this peak is in strong contrast to the narrow and easily understood first peak of the ZnO spectrum, which features a well-resolved vibrational progression that can be readily explained by calculating the Franck-Condon transition factors. This study provides spectroscopic evidence of the effect of hydrogen on diatomic ZnO.

Observation of Thermal Electron Detachment from Cyclo-C4F8 in FALP experiments

DTIC Science & Technology

1994-01-01

Maxwell- Boltzmann distri- electron affinity of C6 F6 was thought to be in bution of internal energy among the cyclo- the neighborhood of 1 eV, but...is not known but may be unimolecular rate for thermal electron detach- estimated as 0.63 eV from the results of the ment from C 6 F6 in the...delivery via SAL (Surface Air Lift) mail is ensured: Argentina, Australia, Brazil, Canada, Horg Kong, India, Israel, Japan, Malaysia , Mexico, New

Heterogeneous substitution effects in chlorocyanomethyl radical and chlorocyanocarbene.

PubMed

Khuseynov, Dmitry; Dixon, Andrew R; Goebbert, Daniel J; Sanov, Andrei

2013-10-17

We report a photoelectron-imaging investigation of the chlorocyanomethyl radical (CHClCN) and the corresponding carbene (CClCN). The results are discussed in comparison with the corresponding dichloro- and dicyano-substituted species, focusing on the divergent effects of the halogen and pseudohalogen (CN) substitutions. A cooperative (captodative) interaction of the π-donor Cl and π-acceptor cyano groups favors the increased stability of the CHClCN radical, but a competition of the two substituents is observed in the singlet-triplet splitting of the carbene. The vertical detachment energy (VDE) of CHClCN(-) is determined to be 2.39 ± 0.04 eV, with the broad photoelectron band consistent with the significant geometry change predicted by theory for the detachment transition. The adiabatic electron affinity of CHClCN, EA = 1.86 ± 0.08 eV, is estimated on the basis of the experimental VDE and the computed difference between the VDE and EA values. This result allows the calculation of the bond dissociation energy of chloroacetonitrile, DH298(H-CHClCN) = 87.0 ± 2.7 kcal/mol. Photoelectron imaging of CClCN(-) reveals two main transitions, assigned to the singlet ((1)A') and triplet ((3)A″) states of the CClCN carbene. The respective VDEs are 2.76 ± 0.05 and 3.25 ± 0.05 eV. The experimental results are in good agreement with the theoretically predicted singlet-triplet vertical energy gap at the anion geometry, but inconclusive with regard to the adiabatic singlet-triplet splitting in CClCN. Consistent with the experimental findings, ab initio calculations using the spin-flip approach in combination with the coupled-cluster theory, indicate that the (1)A' and (3)A″ states are nearly degenerate, with the singlet state lying adiabatically only ∼0.01 eV below the triplet.

Stressing of the New Madrid seismic zone by a lower crust detachment fault

USGS Publications Warehouse

Stuart, W.D.; Hildenbrand, T.G.; Simpson, R.W.

1997-01-01

A new mechanical model for the cause of the New Madrid seismic zone in the central United States is analyzed. The model contains a subhorizontal detachment fault which is assumed to be near the domed top surface of locally thickened anomalous lower crust ("rift pillow"). Regional horizontal compression induces slip on the fault, and the slip creates a stress concentration in the upper crust above the rift pillow dome. In the coseismic stage of the model earthquake cycle, where the three largest magnitude 7-8 earthquakes in 1811-1812 are represented by a single model mainshock on a vertical northeast trending fault, the model mainshock has a moment equivalent to a magnitude 8 event. During the interseismic stage, corresponding to the present time, slip on the detachment fault exerts a right-lateral shear stress on the locked vertical fault whose failure produces the model mainshock. The sense of shear is generally consistent with the overall sense of slip of 1811-1812 and later earthquakes. Predicted rates of horizontal strain at the ground surface are about 10-7 year-1 and are comparable to some observed rates. The model implies that rift pillow geometry is a significant influence on the maximum possible earthquake magnitude.

An all-electron density functional theory study of the structure and properties of the neutral and singly charged M12 and M13 clusters: M = Sc-Zn.

PubMed

Gutsev, G L; Weatherford, C W; Belay, K G; Ramachandran, B R; Jena, P

2013-04-28

The electronic and geometrical structures of the M12 and M13 clusters where M = Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, and Zn along with their singly negatively and positively charged ions are studied using all-electron density functional theory within the generalized gradient approximation. The geometries corresponding to the lowest total energy states of singly and negatively charged ions of V13, Mn12, Co12, Ni13, Cu13, Zn12, and Zn13 are found to be different from the geometries of the corresponding neutral parents. The computed ionization energies of the neutrals, vertical electron detachment energies from the anions, and energies required to remove a single atom from the M13 and M13(+) clusters are in good agreement with experiment. The change in a total spin magnetic moment of the cation or anion with respect to a total spin magnetic moment of the corresponding neutral is consistent with the one-electron model in most cases, i.e., they differ by ±1.0 μ(B). Exceptions are found only for Sc12(-), Ti12(+), Mn12(-), Mn12(+), Fe12(-), Fe13(+), and Co12(+).

Photoelectron spectroscopy of the 6-azauracil anion.

PubMed

Chen, Jing; Buonaugurio, Angela; Dolgounitcheva, Olga; Zakrzewski, V G; Bowen, Kit H; Ortiz, J V

2013-02-14

We report the photoelectron spectrum of the 6-azauracil anion. The spectrum is dominated by a broad band exhibiting a maximum at an electron binding energy (EBE) of 1.2 eV. This spectral pattern is indicative of a valence anion. Our calculations were carried out using ab initio electron propagator and other many-body methods. Comparison of the anion and corresponding neutral of 6-azauracil with those of uracil shows that substituting a nitrogen atom for C-H at the C6 position of uracil gives rise to significant changes in the electronic structure of 6-azauracil versus that of uracil. The adiabatic electron affinity (AEA) of the canonical 6-azauracil tautomer is substantially larger than that of canonical uracil. Among the five tautomeric, 6-azauracil anions studied computationally, the canonical structure was found to be the most stable. The vertical detachment energies (VDE) of the canonical, valence-bound anion of 6-azauracil and its closest "very-rare" tautomer have been calculated. Electron propagator calculations on the canonical anion yield a VDE value that is in close agreement with the experimentally determined VDE value of 1.2 eV. The AEA value of 6-azauracil, assessed at the CCSD(T) level of theory to be 0.5 eV, corresponds with the EBE value of the onset of the experimental spectrum.

An Assessment of Molten Metal Detachment Hazards During Electron Beam Welding in the Space Shuttle Bay at LEO for the International Space Welding Experiment

NASA Technical Reports Server (NTRS)

Fragomeni, James M.

1996-01-01

In 1997, the United States [NASA] and the Paton Electric Welding Institute are scheduled to cooperate in a flight demonstration on the U.S. Space Shuttle to demonstrate the feasibility of welding in space for a possible repair option for the International Space Station Alpha. This endeavor, known as the International Space Welding Experiment (ISWE), will involve astronauts performing various welding exercises such as brazing, cutting, welding, and coating using an electron beam space welding system that was developed by the E.O. Paton Electric Welding Institute (PWI), Kiev Ukraine. This electron beam welding system known as the "Universal Weld System" consists of hand tools capable of brazing, cutting, autogeneous welding, and coating using an 8 kV (8000 volts) electron beam. The electron beam hand tools have also been developed by the Paton Welding Institute with greater capabilities than the original hand tool, including filler wire feeding, to be used with the Universal Weld System on the U.S. Space Shuttle Bay as part of ISWE. The hand tool(s) known as the Ukrainian Universal Hand [Electron Beam Welding] Tool (UHT) will be utilized for the ISWE Space Shuttle flight welding exercises to perform welding on various metal alloy samples. A total of 61 metal alloy samples, which include 304 stainless steel, Ti-6AI-4V, 2219 aluminum, and 5456 aluminum alloys, have been provided by NASA for the ISWE electron beam welding exercises using the UHT. These samples were chosen to replicate both the U.S. and Russian module materials. The ISWE requires extravehicular activity (EVA) of two astronauts to perform the space shuttle electron beam welding operations of the 61 alloy samples. This study was undertaken to determine if a hazard could exist with ISWE during the electron beam welding exercises in the Space Shuttle Bay using the Ukrainian Universal Weld System with the UHT. The safety issue has been raised with regard to molten metal detachments as a result of several possible causes such as welder procedural error, externally applied impulsive forces(s), filler wire entrainment and snap-out, cutting expulsion, and puddle expulsion. Molten metal detachment from either the weld/cut substrate or weld wire could present harm to a astronaut in the space environment it the detachment was ti burn through the fabric of the astronaut Extravehicular Mobility Unit (EMC). In this paper an experimental test was performed in a 4 ft. x 4 ft. vacuum chamber at MSFC enabling protective garment to be exposed to the molten metal drop detachments to over 12 inches. The chamber was evacuated to vacuum levels of at least 1 x 10(exp -5) torr (50 micro-torr) during operation of the 1.0 kW Universal Hand Tool (UHT). The UHT was manually operated at the power mode appropriate for each material and thickness. The space suit protective welding garment, made of Teflon fabric (10 oz. per yard) with a plain weave, was placed on the floor of the vacuum chamber to catch the molten metal drop detachments. A pendulum release mechanism consisting of four hammers, each weighing approximately 3.65 lbs, was used to apply an impact forces to the weld sample/plate during both the electron beam welding and cutting exercises. Measurements were made of the horizontal fling distances of the detached molten metal drops. The volume of a molten metal drop can also be estimated from the size of the cut. Utilizing equations, calculations were made to determine chande in surafec area (Delat a(surface)) for 304 stainless steel for cutting based on measurements of metal drop sizes at the cut edges. For the cut sample of 304 stainless steel based on measurement of the drop size at the edge, Delta-a(surface) was determined to be 0.0054 2 in . Calculations have indicated only a small amount of energy is required to detach a liquid metal drop. For example, approximately only 0.000005 ft-lb of energy is necessary to detach a liquid metal steel drop based on the above theoretical analysis. However, some of the energy will be absorbed by the plate before it reaches the metal drop. Based on the theoretical calculations, it was determined that during a weld cutting exercise, the titanium alloy would be the most difficult to detach molten metal droplets followed by stainless steel and then by aluminum. The results of the experimental effort have shown that molten metal will detach if large enough of a hammer blow is applied to the weld sample plate during the full penetration welding and cutting exercises. However, no molten metal detachments occurred as a result of the filler wire snap-out tests from the weld puddle since it was too difficult to cause the metal to flick-out from the pool. Molten metal detachments, though not large in size, did result from the direct application of the electron beam on the end of the filler weld wire.

Single-Photon, Double Photodetachment of Nickel Phthalocyanine Tetrasulfonic Acid 4- Anions.

PubMed

Daly, Steven; Girod, Marion; Vojkovic, Marin; Giuliani, Alexandre; Antoine, Rodolphe; Nahon, Laurent; O'Hair, Richard A J; Dugourd, Philippe

2016-07-07

Single-photon, two-electron photodetachment from nickel phthalocyanine tetrasulfonic acid tetra anions, [NiPc](4-), was examined in the gas-phase using a linear ion trap coupled to the DESIRS VUV beamline of the SOLEIL Synchrotron. This system was chosen since it has a low detachment energy, known charge localization, and well-defined geometrical and electronic structures. A threshold for two-electron loss is observed at 10.2 eV, around 1 eV lower than previously observed double detachment thresholds on multiple charged protein anions. The photodetachment energy of [NiPc](4-) has been previously determined to be 3.5 eV and the photodetachment energy of [NiPc](3-•) is determined in this work to be 4.3 eV. The observed single photon double electron detachment threshold is hence 5.9 eV higher than the energy required for sequential single electron loss. Possible mechanisms are for double photodetachment are discussed. These observations pave the way toward new, exciting experiments for probing double photodetachment at relatively low energies, including correlation measurements on emitted photoelectrons.

Human Factors Affecting Pilot Performance in Vertical and Translational Instrument Flight.

DTIC Science & Technology

1983-12-01

measures. DD I 1473 EDITION OF I NOV SS 0WITI UnclassifiedS’N 002-L-014-601 d Mhoi~~ ~~~~~~~ SEUIYCASFCAINO HSP BEHAVORAL ENGINEERING LABORATORY e.-)(Co...Dr. A. L. Slafkosky Mr. R. Lawson Scientific Advisor ONR Detachment Commandant of the Marine Corps 1030 East Green Street Code RD-i SPasadena, CA 91106...Center ONR Detachment Orlando, FL 32b13 1030 East Green Street3. Pasadena, CA 911u6 CDR INouiian ’L. Lane Code N-7A Naval Training Equipment Center

Heavy atom vibrational modes and low-energy vibrational autodetachment in nitromethane anions

NASA Astrophysics Data System (ADS)

Thompson, Michael C.; Baraban, Joshua H.; Matthews, Devin A.; Stanton, John F.; Weber, J. Mathias

2015-06-01

We report infrared spectra of nitromethane anion, CH3NO2-, in the region 700-2150 cm-1, obtained by Ar predissociation spectroscopy and electron detachment spectroscopy. The data are interpreted in the framework of second-order vibrational perturbation theory based on coupled-cluster electronic structure calculations. The modes in the spectroscopic region studied here are mainly based on vibrations involving the heavier atoms; this work complements earlier studies on nitromethane anion that focused on the CH stretching region of the spectrum. Electron detachment begins at photon energies far below the adiabatic electron affinity due to thermal population of excited vibrational states.

Heavy atom vibrational modes and low-energy vibrational autodetachment in nitromethane anions.

PubMed

Thompson, Michael C; Baraban, Joshua H; Matthews, Devin A; Stanton, John F; Weber, J Mathias

2015-06-21

We report infrared spectra of nitromethane anion, CH3NO2 (-), in the region 700-2150 cm(-1), obtained by Ar predissociation spectroscopy and electron detachment spectroscopy. The data are interpreted in the framework of second-order vibrational perturbation theory based on coupled-cluster electronic structure calculations. The modes in the spectroscopic region studied here are mainly based on vibrations involving the heavier atoms; this work complements earlier studies on nitromethane anion that focused on the CH stretching region of the spectrum. Electron detachment begins at photon energies far below the adiabatic electron affinity due to thermal population of excited vibrational states.

Photoelectron Angular Distributions of Transition Metal Dioxide Anions - a joint experimental and theoretical study

NASA Astrophysics Data System (ADS)

Iordanov, Ivan; Gunaratne, Dasitha; Harmon, Christopher; Sofo, Jorge; Castleman, A. W., Jr.

2012-02-01

Angular-resolved photoelectron spectroscopy (PES) studies of the MO2- (M=Ti, Zr, Hf, Co, Rh) clusters are presented for the first time along with theoretical calculations of their properties. We confirm previously reported non-angular PES results for the vertical detachment energies (VDE), vibrational energies and geometric structures of these clusters and further explore the effect of the 'lanthanide contraction' on the MO2- clusters by comparing the electronic spectra of 4d and 5d transition metal dioxides. Angular-resolved PES provides the angular momentum contributions to the HOMO of these clusters and we use theoretical calculations to examine the HOMO and compare to our experimental results. First-principles calculations are done using both density functional theory (DFT) and the coupled-cluster, singles, doubles and triples (CCSD(T)) methods.

Thermochemistry and electronic structure of small boron clusters (B(n), n = 5-13) and their anions.

PubMed

Truong, Ba Tai; Grant, Daniel J; Nguyen, Minh Tho; Dixon, David A

2010-01-21

Thermochemical parameters of a set of small-sized neutral (B(n)) and anionic (B(n)(-)) boron clusters, with n = 5-13, were determined using coupled-cluster theory CCSD(T) calculations with the aug-cc-pVnZ (n = D, T, and Q) basis sets extrapolated to the complete basis set limit (CBS) plus addition corrections and/or G3B3 calculations. Enthalpies of formation, adiabatic electron affinities (EA), vertical (VDE), and adiabatic (ADE) detachment energies were evaluated. Our calculated EAs are in good agreement with recent experiments (values in eV): B(5) (CBS, 2.29; G3B3, 2.48; exptl., 2.33 +/- 0.02), B(6) (CBS, 2.59; G3B3, 3.23; exptl., 3.01 +/- 0.04), B(7) (CBS, 2.62; G3B3, 2.67; exptl., 2.55 +/- 0.05), B(8) (CBS, 3.02; G3B3, 3.11; exptl., 3.02 +/- 0.02), B(9) (G3B3, 3.03; exptl., 3.39 +/- 0.06), B(10) (G3B3, 2.85; exptl., 2.88 +/- 0.09), B(11) (G3B4, 3.48;, exptl., 3.43 +/- 0.01), B(12) (G3B3, 2.33; exptl., 2.21 +/- 0.04), and B(13) (G3B3, 3.62; exptl., 3.78 +/- 0.02). The difference between the calculated adiabatic electron affinity and the adiabatic detachment energy for B(6) is due to the fact that the geometry of the anion is not that of the ground-state neutral. The calculated adiabatic detachment energies to the (3)A(u), C(2h) and (1)A(g), D(2h) excited states of B(6), which have geometries similar to the (1)A(g), D(2h) state of B(6)(-), are 2.93 and 3.06 eV, in excellent agreement with experiment. The VDEs were also well reproduced by the calculations. Partitioning of the electron localization functions into pi and sigma components allows probing of the partial and local delocalization in global nonaromatic systems. The larger clusters appear to exhibit multiple aromaticity. The binding energies per atom vary in a parallel manner for both neutral and anionic series and approach the experimental value for the heat of atomization of B. The resonance energies and the normalized resonance energies are convenient indices to quantify the stabilization of a cluster of elements.

Face-capping μ3-BO in B6(BO)7-: boron oxide analogue of B6H7- with rhombic 4c-2e bonds.

PubMed

Guo, Jin-Chang; Lu, Hai-Gang; Zhai, Hua-Jin; Li, Si-Dian

2013-11-14

Using the first-principle approaches, we predict a B6(BO)7(-) cluster with a face-capping μ(3)-BO, which is the boron oxide analogue of closo-B6H7(-) with a face-capping μ(3)-H. Detailed topological analysis of electron density clearly reveals the existence of three rhombic 4c-2e bonds around the B/H apex in both C3v B6(BO)7(-) and C3v B6H7(-), which possesses similar electron densities at their bond and ring critical points. The adaptive natural density partitioning (AdNDP) analysis provides a direct and visual picture of the B-B-B-B/H 4c-2e bonds for the first time. Adiabatic and vertical electron detachment energies of the concerned monoanions are calculated to facilitate their future photoelectron spectroscopy measurements and characterizations. The presence of the B6(BO)7(-) and B6H7(-) clusters extends the BO/H isolobal analogy to the whole μ(n)-BO/H series (n = 1, 2, and 3) and enriches the chemistry of boronyl.

Photoelectron imaging spectroscopy of niobium mononitride anion NbN{sup −}

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

Berkdemir, Cuneyt; Department of Physics, Faculty of Science, Erciyes University, Kayseri 38039; Gunaratne, K. Don Dasitha

2016-07-21

In this gas-phase photoelectron spectroscopy study, we present the electron binding energy spectrum and photoelectron angular distributions of NbN{sup −} by the velocity-map imaging technique. The electron binding energy of NbN{sup −} is measured to be 1.42 ± 0.02 eV from the X band maximum which defines the 0-0 transition between ground states of anion and neutral. Theoretical binding energies which are the vertical and adiabatic detachment energies are computed by density functional theory to compare them with experiment. The ground state of NbN{sup −} is assigned to the {sup 2}Δ{sub 3/2} state and then the electronic transitions originating frommore » this state into X{sup 3}Δ{sub Ω} (Ω = 1-3), a{sup 1}Δ{sub 2}, A{sup 3}Σ{sub 1}{sup −}, and b{sup 1}Σ{sub 0}{sup +} states of NbN are reported to interpret the spectral features. As a prospective study for catalytic materials, spectral features of NbN{sup −} are compared with those of isovalent ZrO{sup −} and Pd{sup −}.« less

Nuclear Quantum Effects on Aqueous Electron Attachment and Redox Properties.

PubMed

Rybkin, Vladimir V; VandeVondele, Joost

2017-04-06

Nuclear quantum effects (NQEs) on the reduction and oxidation properties of small aqueous species (CO 2 , HO 2 , and O 2 ) are quantified and rationalized by first-principles molecular dynamics and thermodynamic integration. Vertical electron attachment, or electron affinity, and detachment energies (VEA and VDE) are strongly affected by NQEs, decreasing in absolute value by 0.3 eV going from a classical to a quantum description of the nuclei. The effect is attributed to NQEs that lessen the solvent response upon oxidation/reduction. The reduction of solvent reorganization energy is expected to be general for small solutes in water. In the thermodynamic integral that yields the free energy of oxidation/reduction, these large changes enter with opposite sign, and only a small net effect (0.1 eV) remains. This is not obvious for CO 2 , where the integrand is strongly influenced by NQEs due to the onset of interaction of the reduced orbital with the conduction band of the liquid during thermodynamic integration. We conclude that NQEs might not have to be included in the computation of redox potentials, unless high accuracy is needed, but are important for VEA and VDE calculations.

Two-Phase Exhumation of the Santa Rosa Mountains: Low- and High-Angle Normal Faulting During Initiation and Evolution of the Southern San Andreas Fault System

NASA Astrophysics Data System (ADS)

Mason, Cody C.; Spotila, James A.; Axen, Gary; Dorsey, Rebecca J.; Luther, Amy; Stockli, Daniel F.

2017-12-01

Low-angle detachment fault systems are important elements of oblique-divergent plate boundaries, yet the role detachment faulting plays in the development of such boundaries is poorly understood. The West Salton Detachment Fault (WSDF) is a major low-angle normal fault that formed coeval with localization of the Pacific-North America plate boundary in the northern Salton Trough, CA. Apatite U-Th/He thermochronometry (AHe; n = 29 samples) and thermal history modeling of samples from the Santa Rosa Mountains (SRM) reveal that initial exhumation along the WSDF began at circa 8 Ma, exhuming footwall material from depths of >2 to 3 km. An uplifted fossil (Miocene) helium partial retention zone is present in the eastern SRM, while a deeper crustal section has been exhumed along the Pleistocene high-angle Santa Rosa Fault (SFR) to much higher elevations in the southwest SRM. Detachment-related vertical exhumation rates in the SRM were 0.15-0.36 km/Myr, with maximum fault slip rates of 1.2-3.0 km/Myr. Miocene AHe isochrons across the SRM are consistent with northeast crustal tilting of the SRM block and suggest that the post-WSDF vertical exhumation rate along the SRF was 1.3 km/Myr. The timing of extension initiation in the Salton Trough suggests that clockwise rotation of relative plate motions that began at 8 Ma is associated with initiation of the southern San Andreas system. Pleistocene regional tectonic reorganization was contemporaneous with an abrupt transition from low- to high-angle faulting and indicates that local fault geometry may at times exert a fundamental control on rock uplift rates along strike-slip fault systems.

A Simple ab initio Model for the Hydrated Electron that Matches Experiment

PubMed Central

Kumar, Anil; Walker, Jonathan A.; Bartels, David M.; Sevilla, Michael D.

2015-01-01

Since its discovery over 50 years ago, the “structure” and properties of the hydrated electron has been a subject for wonderment and also fierce debate. In the present work we seriously explore a minimal model for the aqueous electron, consisting of a small water anion cluster embedded in a polarized continuum, using several levels of ab initio calculation and basis set. The minimum energy zero “Kelvin” structure found for any 4-water (or larger) anion cluster, at any post-Hartree-Fock theory level, is very similar to a recently reported embedded-DFT-in-classical-water-MD simulation (UMJ: Uhlig, Marsalek, and Jungwirth, Journal of Physical Chemistry Letters 2012, 3, 3071-5), with four OH bonds oriented toward the maximum charge density in a small central “void”. The minimum calculation with just four water molecules does a remarkably good job of reproducing the resonance Raman properties, the radius of gyration derived from the optical spectrum, the vertical detachment energy, and the hydration free energy. For the first time we also successfully calculate the EPR g-factor and (low temperature ice) hyperfine couplings. The simple tetrahedral anion cluster model conforms very well to experiment, suggesting it does in fact represent the dominant structural motif of the hydrated electron. PMID:26275103

Electron pressure balance in the SOL through the transition to detachment

DOE PAGES

McLean, A. G.; Leonard, A. W.; Makowski, M. A.; ...

2015-02-07

Upgrades to core and divertor Thomson scattering (DTS) diagnostics at DIII-D have provided measurements of electron pressure profiles in the lower divertor from attached- to fully-detached divertor plasma conditions. Detailed, multistep sequences of discharges with increasing line-averaged density were run at several levels of P inj. Strike point sweeping allowed 2D divertor characterization using DTS optimized to measure T e down to 0.5 eV. The ionization front at the onset of detachment is found to move upwards in a controlled manner consistent with the indication that scrape-off layer parallel power flux is converted from conducted to convective heat transport. Measurementsmore » of n e, T e and p e in the divertor versus Lparallel demonstrate a rapid transition from Te ≥ 15 eV to ≤3 eV occurring both at the outer strike point and upstream of the X-point. Furthermore, these observations provide a strong benchmark for ongoing modeling of divertor detachment for existing and future tokamak devices.« less

Electron pressure balance in the SOL through the transition to detachment

NASA Astrophysics Data System (ADS)

McLean, A. G.; Leonard, A. W.; Makowski, M. A.; Groth, M.; Allen, S. L.; Boedo, J. A.; Bray, B. D.; Briesemeister, A. R.; Carlstrom, T. N.; Eldon, D.; Fenstermacher, M. E.; Hill, D. N.; Lasnier, C. J.; Liu, C.; Osborne, T. H.; Petrie, T. W.; Soukhanovskii, V. A.; Stangeby, P. C.; Tsui, C.; Unterberg, E. A.; Watkins, J. G.

2015-08-01

Upgrades to core and divertor Thomson scattering (DTS) diagnostics at DIII-D have provided measurements of electron pressure profiles in the lower divertor from attached- to fully-detached divertor plasma conditions. Detailed, multistep sequences of discharges with increasing line-averaged density were run at several levels of Pinj. Strike point sweeping allowed 2D divertor characterization using DTS optimized to measure Te down to 0.5 eV. The ionization front at the onset of detachment is found to move upwards in a controlled manner consistent with the indication that scrape-off layer parallel power flux is converted from conducted to convective heat transport. Measurements of ne, Te and pe in the divertor versus Lparallel demonstrate a rapid transition from Te ⩾ 15 eV to ⩽3 eV occurring both at the outer strike point and upstream of the X-point. These observations provide a strong benchmark for ongoing modeling of divertor detachment for existing and future tokamak devices.

Associative electron detachment - O(-) + H yields OH + e(-)

NASA Astrophysics Data System (ADS)

Acharya, P. K.; Kendall, R. A.; Simons, J.

1985-10-01

Diatomic associative electron detachment (AED) involves the ejection of an electron when a atomic anion and another atom collisionally associate to produce a neutral diatomic molecule in a vibration-rotation state labeled V-prime, J-prime. Electron ejection rate calculations are discussed, taking into account aspects of rate expressions, calculations of ingredients in rate expression, initial-condition weighting factors, and the vibration and rotation dependence of ejection rates. The results of ab initio theoretical simulations indicate that AED in O(-) + H is so slow (approximately 10,000 per s) that it is likely to be inaccessible to present experimental observation. Propensity for producing OH in high vibrational levels does occur but the propensity is not sharp.

Heavy atom vibrational modes and low-energy vibrational autodetachment in nitromethane anions

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

Thompson, Michael C.; Weber, J. Mathias, E-mail: weberjm@jila.colorado.edu; Department of Chemistry and Biochemistry, University of Colorado at Boulder, 215UCB, Boulder, Colorado 80309-0215

2015-06-21

We report infrared spectra of nitromethane anion, CH{sub 3}NO{sub 2}{sup −}, in the region 700–2150 cm{sup −1}, obtained by Ar predissociation spectroscopy and electron detachment spectroscopy. The data are interpreted in the framework of second-order vibrational perturbation theory based on coupled-cluster electronic structure calculations. The modes in the spectroscopic region studied here are mainly based on vibrations involving the heavier atoms; this work complements earlier studies on nitromethane anion that focused on the CH stretching region of the spectrum. Electron detachment begins at photon energies far below the adiabatic electron affinity due to thermal population of excited vibrational states.

Low oxidation state aluminum-containing cluster anions: Cp{sup ∗}Al{sub n}H{sup −}, n = 1–3

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

Zhang, Xinxing; Ganteför, Gerd; Bowen, Kit, E-mail: AKandalam@wcupa.edu, E-mail: kbowen@jhu.edu

Three new, low oxidation state, aluminum-containing cluster anions, Cp*Al{sub n}H{sup −}, n = 1–3, were prepared via reactions between aluminum hydride cluster anions, Al{sub n}H{sub m}{sup −}, and Cp*H ligands. These were characterized by mass spectrometry, anion photoelectron spectroscopy, and density functional theory based calculations. Agreement between the experimentally and theoretically determined vertical detachment energies and adiabatic detachment energies validated the computed geometrical structures. Reactions between aluminum hydride cluster anions and ligands provide a new avenue for discovering low oxidation state, ligated aluminum clusters.

Photoelectron spectroscopic studies of 5-halouracil anions

PubMed Central

Radisic, Dunja; Ko, Yeon Jae; Nilles, John M.; Stokes, Sarah T.; Sevilla, Michael D.; Rak, Janusz; Bowen, Kit H.

2011-01-01

The parent negative ions of 5-chlorouracil, UCl− and 5-fluorouracil, UF− have been studied using anion photoelectron spectroscopy in order to investigate the electrophilic properties of their corresponding neutral halouracils. The vertical detachment energies (VDE) of these anions and the adiabatic electron affinities (EA) of their neutral molecular counterparts are reported. These results are in good agreement with the results of previously published theoretical calculations. The VDE values for both UCl− and UF− and the EA values for their neutral molecular counterparts are much greater than the corresponding values for both anionic and neutral forms of canonical uracil and thymine. These results are consistent with the observation that DNA is more sensitive to radiation damage when thymine is replaced by halouracil. While we also attempted to prepare the parent anion of 5-bromouracil, UBr−, we did not observe it, the mass spectrum exhibiting only Br− fragments, i.e., 5-bromouracil apparently underwent dissociative electron attachment. This observation is consistent with a previous assessment, suggesting that 5-bromouracil is the best radio-sensitizer among these three halo-nucleobases. PMID:21219027

Intrinsic electrophilic properties of nucleosides: Photoelectron spectroscopy of their parent anions

NASA Astrophysics Data System (ADS)

Stokes, Sarah T.; Li, Xiang; Grubisic, Andrej; Ko, Yeon Jae; Bowen, Kit H.

2007-08-01

The nucleoside parent anions 2'-deoxythymidine-, 2'-deoxycytidine-, 2'-deoxyadenosine-, uridine-, cytidine-, adenosine-, and guanosine- were generated in a novel source, employing a combination of infrared desorption, electron photoemission, and a gas jet expansion. Once mass selected, the anion photoelectron spectrum of each of these was recorded. In the three cases in which comparisons were possible, the vertical detachment energies and likely adiabatic electron affinities extracted from these spectra agreed well with the values calculated both by Richardson et al. [J. Am. Chem. Soc. 126, 4404 (2004)] and by Li et al. [Radiat. Res. 165, 721 (2006)]. Through the combination of our experimental results and their theoretical calculations, several implications emerge. (1) With the possible exception of dG-, the parent anions of nucleosides exist, and they are stable. (2) These nucleoside anions are valence anions, and in most cases the negative charge is closely associated with the nucleobase moiety. (3) The nucleoside parent anions we have generated and studied are the negative ions of canonical, neutral nucleosides, similar to those found in DNA.

Intrinsic electrophilic properties of nucleosides: photoelectron spectroscopy of their parent anions.

PubMed

Stokes, Sarah T; Li, Xiang; Grubisic, Andrej; Ko, Yeon Jae; Bowen, Kit H

2007-08-28

The nucleoside parent anions 2(')-deoxythymidine(-), 2(')-deoxycytidine(-), 2(')-deoxyadenosine(-), uridine(-), cytidine(-), adenosine(-), and guanosine(-) were generated in a novel source, employing a combination of infrared desorption, electron photoemission, and a gas jet expansion. Once mass selected, the anion photoelectron spectrum of each of these was recorded. In the three cases in which comparisons were possible, the vertical detachment energies and likely adiabatic electron affinities extracted from these spectra agreed well with the values calculated both by Richardson et al. [J. Am. Chem. Soc. 126, 4404 (2004)] and by Li et al. [Radiat. Res. 165, 721 (2006)]. Through the combination of our experimental results and their theoretical calculations, several implications emerge. (1) With the possible exception of dG(-), the parent anions of nucleosides exist, and they are stable. (2) These nucleoside anions are valence anions, and in most cases the negative charge is closely associated with the nucleobase moiety. (3) The nucleoside parent anions we have generated and studied are the negative ions of canonical, neutral nucleosides, similar to those found in DNA.

Electronegative plasma diagnostic by laser photo-detachment combined with negatively biased Langmuir probe

NASA Astrophysics Data System (ADS)

Oudini, N.; Sirse, N.; Taccogna, F.; Ellingboe, A. R.; Bendib, A.

2018-05-01

We propose a new technique for diagnosing negative ion properties using Langmuir probe assisted pulsed laser photo-detachment. While the classical technique uses a laser pulse to convert negative ions into electron-atom pairs and a positively biased Langmuir probe tracking the change of electron saturation current, the proposed method uses a negatively biased Langmuir probe to track the temporal evolution of positive ion current. The negative bias aims to avoid the parasitic electron current inherent to probe tip surface ablation. In this work, we show through analytical and numerical approaches that, by knowing electron temperature and performing photo-detachment at two different laser wavelengths, it is possible to deduce plasma electronegativity (ratio of negative ion to electron densities) α, and anisothermicity (ratio of electron to negative ion temperatures) γ-. We present an analytical model that links the change in the collected positive ion current to plasma electronegativity and anisothermicity. Particle-In-Cell simulation is used as a numerical experiment covering a wide range of α and γ- to test the new analysis technique. The new technique is sensitive to α in the range 0.5 < α < 10 and yields γ- for large α, where negative ion flux affects the probe sheath behavior, typically α > 1.

Germylenes: structures, electron affinities, and singlet-triplet gaps of the conventional XGeCY(3) (X = H, F, Cl, Br, and I; Y = F and Cl) species and the unexpected cyclic XGeCY(3) (Y = Br and I) systems.

PubMed

Bundhun, Ashwini; Abdallah, Hassan H; Ramasami, Ponnadurai; Schaefer, Henry F

2010-12-23

A systematic investigation of the X-Ge-CY(3) (X = H, F, Cl, Br, and I; Y = F, Cl, Br, and I) species is carried out using density functional theory. The basis sets used for all atoms (except iodine) in this work are of double-ζ plus polarization quality with additional s- and p-type diffuse functions, and denoted DZP++. Vibrational frequency analyses are performed to evaluate zero-point energy corrections and to determine the nature of the stationary points located. Predicted are four different forms of neutral-anion separations: adiabatic electron affinity (EA(ad)), zero-point vibrational energy corrected EA(ad(ZPVE)), vertical electron affinity (EA(vert)), and vertical detachment energy (VDE). The electronegativity (χ) reactivity descriptor for the halogens (X = F, Cl, Br, and I) is used as a tool to assess the interrelated properties of these germylenes. The topological position of the halogen atom bound to the divalent germanium center is well correlated with the trend in the electron affinities and singlet-triplet gaps. For the expected XGeCY(3) structures (X = H, F, Cl, Br, and I; Y = F and Cl), the predicted trend in the electron affinities is well correlated with simpler germylene derivatives (J. Phys. Chem. A 2009, 113, 8080). The predicted EA(ad(ZPVE)) values with the BHLYP functional range from 1.66 eV (FGeCCl(3)) to 2.20 eV (IGeCF(3)), while the singlet-triplet splittings range from 1.28 eV (HGeCF(3)) to 2.22 eV (FGeCCl(3)). The XGeCY(3) (Y = Br and I) species are most often characterized by three-membered cyclic systems involving the divalent germanium atom, the carbon atom, and a halogen atom.

A dipole-bound dianion

NASA Astrophysics Data System (ADS)

Skurski, Piotr; Simons, Jack

2000-04-01

The possibility of binding two electrons by the dipole potential of a molecule was examined earlier by us using model potentials. That study suggested that large dipole moments μ=qR and large charge separation distances R (or equivalently large charges q) would be required to achieve binding two electrons. For example, even with a charge q=1.5 a.u. which might be achieved using di- or tri-valent cations, a dipole moment exceeding 15.922 D is needed. The presence of inner-shell electrons even further increases the value of μ that is required because the dipole-bound electrons' orbital must be orthogonal to and excluded from such inner shells. In the present work, we discuss our efforts to find a real molecule that can actually bind two electrons to a single dipole site. Numerical results are presented for the mono- and dianions of a double 5-member carbon ring system substituted with a Ca atom and three superhalogen -PF5 groups. The dianion of this molecule is found to be geometrically stable and to have a vertical electron detachment energy of ca. 0.8 eV. Its two excess electrons occupy the same fully symmetric a1 molecular orbital localized at the electropositive Ca end of the neutral system as is routinely observed in dipole-bound monoanions. Although our final candidate is chemically unusual, it is hoped that our predictions about it will encourage others to search for more synthetically tractable alternatives.

Investigation on Active Thermal Control Method with Pool Boiling Heat Transfer at Low Pressure

NASA Astrophysics Data System (ADS)

Sun, Chuang; Guo, Dong; Wang, Zhengyu; Sun, Fengxian

2018-06-01

In order to maintain a desirable temperature level of electronic equipment at low pressure, the thermal control performance with pool boiling heat transfer of water was examined based on experimental measurement. The total setup was designed and performed to accomplish the experiment with the pressure range from 4.5 kPa to 20 kPa and the heat flux between 6 kW/m2 and 20 kW/m2. The chosen material of the heat surface was aluminium alloy and the test cavity had the capability of varying the direction for the heat surface from vertical to horizontal directions. Through this study, the steady and transient temperature of the heat surface at different pressures and directions were obtained. Although the temperature non-uniformity of the heat surface from the centre to the edge could reach 10°C for the aluminium alloy due to the varying pressures, the whole temperature results successfully satisfied with the thermal control requirements for electronic equipment, and the temperature control effect of the vertically oriented direction was better than that of the horizontally oriented direction. Moreover, the behaviour of bubbles generating and detaching from the heat surface was recorded by a high-resolution camera, so as to understand the pool boiling heat transfer mechanism at low-load heat flux. These pictures showed that the bubbles departure diameter becomes larger, and departure frequency was slower at low pressure, in contrast to 1.0 atm.

Deformation of Fold-and-Thrust Belts above a Viscous Detachment: New Insights from Analogue Modelling Experiments

NASA Astrophysics Data System (ADS)

Nogueira, Carlos R.; Marques, Fernando O.

2015-04-01

Theoretical and experimental studies on fold-and-thrusts belts (FTB) have shown that, under Coulomb conditions, deformation of brittle thrust wedges above a dry frictional basal contact is characterized by dominant frontward vergent thrusts (forethrusts) with thrust spacing and taper angle being directly influenced by the basal strength (increase in basal strength leading to narrower thrust spacing and higher taper angles); whereas thrust wedges deformed above a weak viscous detachment, such as salt, show a more symmetric thrust style (no prevailing vergence of thrusting) with wider thrust spacing and shallower wedges. However, different deformation patterns can be found on this last group of thrust wedges both in nature and experimentally. Therefore we focused on the strength (friction) of the wedge basal contact, the basal detachment. We used a parallelepiped box with four fixed walls and one mobile that worked as a vertical piston drove by a computer controlled stepping motor. Fine dry sand was used as the analogue of brittle rocks and silicone putty (PDMS) with Newtonian behaviour as analogue of the weak viscous detachment. To investigate the strength of basal contact on thrust wedge deformation, two configurations were used: 1) a horizontal sand pack with a dry frictional basal contact; and 2) a horizontal sand pack above a horizontal PDMS layer, acting as a basal weak viscous contact. Results of the experiments show that: the model with a dry frictional basal detachment support the predictions for the Coulomb wedges, showing a narrow wedge with dominant frontward vergence of thrusting, close spacing between FTs and high taper angle. The model with a weak viscous frictional basal detachment show that: 1) forethrusts (FT) are dominant showing clearly an imbricate asymmetric geometry, with wider spaced thrusts than the dry frictional basal model; 2) after FT initiation, the movement on the thrust can last up to 15% model shortening, leading to great amount of displacement along the FT; 3) intermittent reactivation of FTs also occurs despite the steepening of the FT plane and existence of new FT ahead, creating a high critical taper angle; 4) injection of PDMS from the basal weak layer into the FTs planes also favours to the long living of FTs and to the high critical taper angle; 5) vertical sand thickening in the hanging block also added to the taper angle.

Bench vise adapter grips tubing securely and safely

NASA Technical Reports Server (NTRS)

Howland, B. T.; Jones, A. S., Jr.

1966-01-01

Plastic self-compressing adapter with grooves, attached to the jaws of a bench vise, secures thin-wall tubing vertically or horizontally during cutting and flaring operations without marring or damaging it. Magnets incorporated in both sections of the adapter prevent detachment from the jaws when the vise is opened.

Characterization of partial resistance to black spot disease of Rosa spp.

USDA-ARS?s Scientific Manuscript database

Black spot disease (BSD) is one of the most serious diseases of garden roses. Both complete (vertical) resistance and partial (horizontal) resistance have been identified in 16 rose genotypes using two laboratory assays, the detached leaf assay (DLA) and the whole plant inoculation (WPI) approaches...

Raman mapping and in situ SERS spectroelectrochemical studies of 6-mercaptopurine SAMs on the gold electrode.

PubMed

Yang, Haifeng; Liu, Yanli; Liu, Zhimin; Yang, Yu; Jiang, Jianhui; Zhang, Zongrang; Shen, Guoli; Yu, Ruqin

2005-02-24

The self-assembled monolayers (SAMs) of 6-mercaptopurine (6MP) were formed at the roughened polycrystalline gold surfaces in acid and alkaline media. The time-dependent Raman mapping spectral analysis in conjunction with the quantum calculations for the vibrational modes using ab initio BLYP/6-31G method suggested that both of the resulted 6MP SAMs adopted the same adsorption mode through the S atom of pyrimidine moiety and the N7 atom of the imidazole moiety anchoring the gold surface in a vertical way. The in situ surface-enhanced Raman scattering spectroelectrochemical experiment was conducted to examine the stability of the SAMs at various bias potentials. It was found that the detaching process of the 6MP SAMs from the surface involved one electron reduction as the voltage was applied at ca. 0.7 V vs a standard calomel electrode.

Are trinuclear superhalogens promising candidates for building blocks of novel magnetic materials? A theoretical prospect from combined broken-symmetry density functional theory and ab initio study.

PubMed

Yu, Yang; Li, Chen; Yin, Bing; Li, Jian-Li; Huang, Yuan-He; Wen, Zhen-Yi; Jiang, Zhen-Yi

2013-08-07

The structures, relative stabilities, vertical electron detachment energies, and magnetic properties of a series of trinuclear clusters are explored via combined broken-symmetry density functional theory and ab initio study. Several exchange-correlation functionals are utilized to investigate the effects of different halogen elements and central atoms on the properties of the clusters. These clusters are shown to possess stronger superhalogen properties than previously reported dinuclear superhalogens. The calculated exchange coupling constants indicate the antiferromagnetic coupling between the transition metal ions. Spin density analysis demonstrates the importance of spin delocalization in determining the strengths of various couplings. Spin frustration is shown to occur in some of the trinuclear superhalogens. The coexistence of strong superhalogen properties and spin frustration implies the possibility of trinuclear superhalogens working as the building block of new materials of novel magnetic properties.

Development of a Method for Local Electron Temperature and Density Measurements in the Divertor of the JET Tokamak

NASA Technical Reports Server (NTRS)

Jupen, C.; Meigs, A.; Bhatia, A. K.; Brezinsek, S.; OMullane, M.

2004-01-01

Plasma volume recombination in the divertor, a process in which charged particles recombine to neutral atoms, contributes to plasma detachment and hence cooling at the divertor target region. Detachment has been observed at JET and other tokamaks and is known to occur at low electron temperatures (T(sub e)<1 eV) and at high electron density (n(sub e)>10(exp 20)/m(exp 3)). The ability to measure such low temperatures is therefore of interest for modelling the divertor. In present work we report development of a new spectroscopic technique for investigation of local electron density (n(sub e)) and temperature (T,) in the outer divertor at JET.

Two-Electron Photoejection of He and H{sup {minus}}

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

Meyer, K.W.; Greene, C.H.; Esry, B.D.

1997-06-01

In order to overcome difficulties in the description of the two-electron continuum problem, we develop a finite element method to treat two-electron escape processes. Two-electron photoejection cross sections are obtained for helium and H{sup {minus}} at photon energies in the range of 79{endash}460 and 14.4{endash}110eV. The H{sup {minus}} double detachment calculations are apparently the first nonperturbative quantum results in this energy range since the pioneering work of Broad and Reinhardt in 1976. Our branching ratio between single and double detachment of H{sup {minus}} peaks at a value 25{percent}{endash}40{percent} higher than the results from that early study. {copyright} {ital 1997} {italmore » The American Physical Society}« less

Is the regulation of the electronic properties of organic molecules by polynuclear superhalogens more effective than that by mononuclear superhalogens? A high-level ab initio case study.

PubMed

Li, Miao-Miao; Li, Jin-Feng; Bai, Hongcun; Sun, Yin-Yin; Li, Jian-Li; Yin, Bing

2015-08-21

The regulation of the electronic properties of organic molecules induced by polynuclear superhalogens is theoretically explored here for sixteen composite structures. It is clearly indicated by the higher vertical electron detachment energy (VDE) that polynuclear superhalogens are more effective in regulating the electronic properties than mononuclear structures. However, this enhanced regulation is not only determined by superhalogens themselves but also related to the distribution of the extra electron of the final composites. The composites, in which the extra electron is mainly aggregated into the superhalogen moiety, will possess higher VDE values, as reported in the case of C1', 7.12 eV at the CCSD(T) level. This is probably due to the fact that, compared with organic molecules, superhalogens possess stronger attraction towards the extra electron and thus should lead to lower energies of the extra electrons and to higher VDE values eventually. Compared with CCSD(T), the Outer Valence Green's Function (OVGF) method fails completely for composite structures containing Cl atoms, while MP2 results are generally consistent in terms of the relative order of VDEs. Actually if the extra electron distribution of the systems could be approximated by the HOMO, the results at the OVGF level will be consistent with the CCSD(T) results. Conversely, the difference in VDEs between OVGF and CCSD(T) is significantly large. Besides superhalogen properties, the structures, relative stabilities and thermodynamic stabilities with respect to various fragmentation channels were also investigated for all the composite structures.

Syn-extensional lithogenetic sequences of the Soledad basin, central Transverse Ranges: Implications for detachment-fault models

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

Hendrix, E.D.

1993-04-01

The Soledad Basin (central Transverse Ranges, CA) contains the first recognized example of mid-Tertiary detachment-faulting west of the San Andreas fault. Displacements along the Pelona detachment fault and syn-extensional upper-plate sedimentation occurred between [approximately] 26--18 Ma, resulting in deposition of at least 4 separate lithogenetic sequences (LS) which record distinct phases of crustal response to extension. The 1st LS (lower Vasquez Fm.) predates syn-extensional volcanism and records initial basin subsidence along small, discontinuous faults. The 2nd LS (middle Vasquez Fm.) consists of both volcanic and sedimentary strata and signals simultaneous onset of magmatism and initial development of a well-defined networkmore » of high-angle, upper-plate normal faults, creating 2 separate sub-basins. Resulting alluvial fans were non-entrenched, implying that subsidence rates, and thus vertical displacement rates on high-angle faults, equaled or exceeded an estimated average sedimentation rate of 1.4 mm/yr. The 3rd LS (upper Vasquez Fm.) reflects transition to a single, well-integrated depositional basin characterized by streamflood sedimentation. This suggests an enlarged drainage basin and a decrease in subsidence rate relative to sedimentation rate, triggered possibly by uplift of the detachment lower-plate. The 4th LS (Tick Canyon Fm.) lies with angular unconformity above the 3rd LS and contains the 1st clasts eroded from the detachment lower plate. Detachment faulting in the Soledad basin appears to involve, in part, reactivation of structural zones of weakness along the Vincent thrust. Preliminary reconstructions of Soledad extension imply 25--30 km of displacement along the Pelona detachment fault system at an averaged slip rate of 3.6--4.3 mm/yr.« less

Models for extracting vertical crustal movements from leveling data

NASA Technical Reports Server (NTRS)

Holdahl, S. H.

1978-01-01

Various adjustment strategies are being used in North America to obtain vertical crustal movements from repeated leveling. The more successful models utilize polynomials or multiquadric analysis to describe elevation change with a velocity surface. Other features permit determination of nonlinear motions, motions associated with earthquakes or episodes, and vertical motions of blocks where boundaries are prespecified. The preferred models for estimating crustal motions permit the use of detached segments of releveling to govern the shape of a velocity surface and allow for input from nonleveling sources such as tide gages and paired lake gages. Some models for extracting vertical crustal movements from releveling data are also excellent for adjusting leveling networks, and permit mixing old and new data in areas exhibiting vertical motion. The new adjustment techniques are more general than older static models and will undoubtedly be used routinely in the future as the constitution of level networks becomes mainly relevelings.

Nonlinear Response of Iceberg Melting to Ocean Currents

NASA Astrophysics Data System (ADS)

Cenedese, C.; FitzMaurice, A.; Straneo, F.

2017-12-01

Icebergs calving into Greenlandic Fjords frequently experience strongly sheared flows over their draft, but the impact of this flow past the iceberg on the melt plumes generated along the iceberg sides is not fully captured by existing parameterizations. We present a series of novel laboratory experiments to determine the dependence of side submarine melt rates on a background flow. We show, for the first time, that two distinct regimes of melting exist depending on the melt plume behavior (side-attached or side-detached). These two regimes produce a nonlinear dependence of melt rate on velocity, and different distributions of meltwater in the water column. Iceberg meltwater may either be confined to a thin surface layer, when the melt plumes are side-attached, or mixed down to the iceberg draft, when the melt plumes are side-detached. In a two-layer vertically sheared flow the average flow speed in existing melt parameterizations gives an underestimate of the submarine melt rate, in part due to the nonlinearity of the dependence of melt rate on flow speed, but also because vertical shear in the velocity profile fundamentally changes the flow splitting around the ice block and consequently the velocity felt by the ice surface. Including this nonlinear velocity dependence in melting parameterizations applied to observed icebergs increases iceberg side melt in the attached regime, improving agreement with observations of iceberg submarine melt rates. We show that both attached and detached plume regimes are relevant to icebergs observed in a Greenland fjord.

Toward the Development of Aluminum Cluster-Containing Materials for Propulsion Applications

DTIC Science & Technology

2011-02-22

our main example. Photoelectron spectroscopy revealed that Al13H - has two isomers and for both provided vertical detachment energies ( VDE ) for their...The relative energies for both isomers in their anionic and their neutral charge states as well as EAa and VDE values for both isomers were also

Excess electrons in methanol clusters: Beyond the one-electron picture

NASA Astrophysics Data System (ADS)

Pohl, Gábor; Mones, Letif; Turi, László

2016-10-01

We performed a series of comparative quantum chemical calculations on various size negatively charged methanol clusters, ("separators=" CH 3 OH ) n - . The clusters are examined in their optimized geometries (n = 2-4), and in geometries taken from mixed quantum-classical molecular dynamics simulations at finite temperature (n = 2-128). These latter structures model potential electron binding sites in methanol clusters and in bulk methanol. In particular, we compute the vertical detachment energy (VDE) of an excess electron from increasing size methanol cluster anions using quantum chemical computations at various levels of theory including a one-electron pseudopotential model, several density functional theory (DFT) based methods, MP2 and coupled-cluster CCSD(T) calculations. The results suggest that at least four methanol molecules are needed to bind an excess electron on a hydrogen bonded methanol chain in a dipole bound state. Larger methanol clusters are able to form stronger interactions with an excess electron. The two simulated excess electron binding motifs in methanol clusters, interior and surface states, correlate well with distinct, experimentally found VDE tendencies with size. Interior states in a solvent cavity are stabilized significantly stronger than electron states on cluster surfaces. Although we find that all the examined quantum chemistry methods more or less overestimate the strength of the experimental excess electron stabilization, MP2, LC-BLYP, and BHandHLYP methods with diffuse basis sets provide a significantly better estimate of the VDE than traditional DFT methods (BLYP, B3LYP, X3LYP, PBE0). A comparison to the better performing many electron methods indicates that the examined one-electron pseudopotential can be reasonably used in simulations for systems of larger size.

Excess electrons in methanol clusters: Beyond the one-electron picture.

PubMed

Pohl, Gábor; Mones, Letif; Turi, László

2016-10-28

We performed a series of comparative quantum chemical calculations on various size negatively charged methanol clusters, CH 3 OH n - . The clusters are examined in their optimized geometries (n = 2-4), and in geometries taken from mixed quantum-classical molecular dynamics simulations at finite temperature (n = 2-128). These latter structures model potential electron binding sites in methanol clusters and in bulk methanol. In particular, we compute the vertical detachment energy (VDE) of an excess electron from increasing size methanol cluster anions using quantum chemical computations at various levels of theory including a one-electron pseudopotential model, several density functional theory (DFT) based methods, MP2 and coupled-cluster CCSD(T) calculations. The results suggest that at least four methanol molecules are needed to bind an excess electron on a hydrogen bonded methanol chain in a dipole bound state. Larger methanol clusters are able to form stronger interactions with an excess electron. The two simulated excess electron binding motifs in methanol clusters, interior and surface states, correlate well with distinct, experimentally found VDE tendencies with size. Interior states in a solvent cavity are stabilized significantly stronger than electron states on cluster surfaces. Although we find that all the examined quantum chemistry methods more or less overestimate the strength of the experimental excess electron stabilization, MP2, LC-BLYP, and BHandHLYP methods with diffuse basis sets provide a significantly better estimate of the VDE than traditional DFT methods (BLYP, B3LYP, X3LYP, PBE0). A comparison to the better performing many electron methods indicates that the examined one-electron pseudopotential can be reasonably used in simulations for systems of larger size.

Vertical detachment energies of anionic thymidine: Microhydration effects.

PubMed

Kim, Sunghwan; Schaefer, Henry F

2010-10-14

Density functional theory has been employed to investigate microhydration effects on the vertical detachment energy (VDE) of the thymidine anion by considering the various structures of its monohydrates. Structures were located using a random searching procedure. Among 14 distinct structures of the anionic thymidine monohydrate, the low-energy structures, in general, have the water molecule bound to the thymine base unit. The negative charge developed on the thymine moiety increases the strength of the intermolecular hydrogen bonding between the water and base units. The computed VDE values of the thymidine monohydrate anions are predicted to range from 0.67 to 1.60 eV and the lowest-energy structure has a VDE of 1.32 eV. The VDEs of the monohydrates of the thymidine anion, where the N(1)[Single Bond]H hydrogen of thymine has been replaced by a 2(')-deoxyribose ring, are greater by ∼0.30 eV, compared to those of the monohydrates of the thymine anion. The results of the present study are in excellent agreement with the accompanying experimental results of Bowen and co-workers [J. Chem. Phys. 133, 144304 (2010)].

Hydrated electrons react with high specificity with cisplatin bound to single-stranded DNA.

PubMed

Behmand, B; Cloutier, P; Girouard, S; Wagner, J R; Sanche, L; Hunting, D J

2013-12-19

Short oligonucleotides TTTTTGTGTTT and TTTTTTTGTTT in solution with and without cisplatin (cisPt) bound to the guanine bases were irradiated with γ-rays at doses varying from 0 to 2500 Gy. To determine the effect of hydrated electrons from water radiolysis on the oligonucleotides, we quenched (•)OH radicals with ethylenediaminetetraacetic acid (EDTA) and displaced oxygen, which reacts with hydrated electrons, by bubbling the solution with wet nitrogen. DNA strand breaks and platinum detachment were quantified by gel electrophoresis. Our results demonstrate that hydrated electrons react almost exclusively at the position of the cisPt adduct, where they induce cisPt detachment from one or both guanines in the oligonucleotide. Given the high yield of hydrated electrons in irradiated tissues, this reaction may be an important step in the mechanism of radiosensitization of DNA by cisPt.

Ballistic magnetotransport in a suspended two-dimensional electron gas with periodic antidot lattices

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

Zhdanov, E. Yu., E-mail: zhdanov@isp.nsc.ru; Pogosov, A. G.; Budantsev, M. V.

2017-01-15

The magnetoresistance of suspended semiconductor nanostructures with a two-dimensional electron gas structured by periodic square antidot lattices is studied. It is shown that the ballistic regime of electron transport is retained after detaching the sample from the substrate. Direct comparative analysis of commensurability oscillations of magnetoresistance and their temperature dependences in samples before and after suspension is performed. It is found that the temperature dependences are almost identical for non-suspended and suspended samples, whereas significant differences are observed in the nonlinear regime, caused by direct current passage. Commensurability oscillations in the suspended samples are more stable with respect to exposuremore » to direct current, which can be presumably explained by electron–electron interaction enhancement after detaching nanostructures from the high-permittivity substrate.« less

Stabilizing detached Bridgman melt crystal growth: Proportional-integral feedback control

NASA Astrophysics Data System (ADS)

Yeckel, Andrew; Daoutidis, Prodromos; Derby, Jeffrey J.

2012-10-01

The dynamics, operability limits, and tuning of a proportional-integral feedback controller to stabilize detached vertical Bridgman crystal growth are analyzed using a capillary model of shape stability. The manipulated variable is the pressure difference between upper and lower vapor spaces, and the controlled variable is the gap width at the triple-phase line. Open and closed loop dynamics of step changes in these state variables are analyzed under both shape stable and shape unstable growth conditions. Effects of step changes in static contact angle and growth angle are also studied. Proportional and proportional-integral control can stabilize unstable growth, but only within tight operability limits imposed by the narrow range of allowed meniscus shapes. These limits are used to establish safe operating ranges of controller gain. Strong nonlinearity of the capillary model restricts the range of perturbations that can be stabilized, and under some circumstances, stabilizes a spurious operating state far from the set point. Stabilizing detachment at low growth angle proves difficult and becomes impossible at zero growth angle.

Detached Bridgman Growth of Germanium and Germanium-Silicon Alloy Crystals

NASA Technical Reports Server (NTRS)

Szofran, F. R.; Volz, M. P.; Schweizer, M.; Cobb, S. D.; Motakef, S.; Croell, A.; Dold, P.; Curreri, Peter A. (Technical Monitor)

2002-01-01

Earth based experiments on the science of detached crystal growth are being conducted on germanium and germanium-silicon alloys (2 at% Si average composition) in preparation for a series of experiments aboard the International Space Station (ISS). The purpose of the microgravity experiments includes differentiating among proposed mechanisms contributing to detachment, and confirming or refining our understanding of the detachment mechanism. Because large contact angle are critical to detachment, sessile drop measurements were used to determine the contact angles as a function of temperature and composition for a large number of substrates made of potential ampoule materials. Growth experiments have used pyrolytic boron nitride (pBN) and fused silica ampoules with the majority of the detached results occurring predictably in the pBN. The contact angles were 173 deg (Ge) and 165 deg (GeSi) for pBN. For fused silica, the contact angle decreases from 150 deg to an equilibrium value of 117 deg (Ge) or from 129 deg to an equilibrium value of 100 deg (GeSi) over the duration of the experiment. The nature and extent of detachment is determined by using profilometry in conjunction with optical and electron microscopy. The stability of detachment has been analyzed, and an empirical model for the conditions necessary to achieve sufficient stability to maintain detached growth for extended periods has been developed. Results in this presentation will show that we have established the effects on detachment of ampoule material, pressure difference above and below the melt, and silicon concentration; samples that are nearly completely detached can be grown repeatedly in pBN.

Studies of Copper, Silver, and Gold Cluster Anions: Evidence of Electronic Shell Structure.

NASA Astrophysics Data System (ADS)

Pettiette, Claire Lynn

A new Ultraviolet Magnetic Time-of-Flight Photoelectron Spectrometer (MTOFPES) has been developed for the study of the electronic structure of clusters produced in a pulsed supersonic molecular beam. This is the first technique which has been successful in probing the valence electronic states of metal clusters. The ultraviolet photoelectron spectra of negative cluster ions of the noble metals have been taken at several different photon energies. These are presented along with the electron affinity and HOMO-LUMO gap measurements for Cu_6^- to Cu_ {41}^-, using 4.66 eV and 6.42 eV detachment energies; Ag_3^- to Ag_{21}^-, using 6.42 eV detachment energy; and Au_3^ - to Au_{21}^-, using 6.42 eV and 7.89 eV detachment energies. The spectra provide the first detailed probes of the s valence electrons of the noble metal clusters. In addition, the 6.42 eV and 7.89 eV spectra probe the first one to two electron volts of the molecular orbitals of the d valence electrons of copper and gold clusters. The electron affinity and HOMO-LUMO gap measurements of the noble metal clusters agree with the predictions of the ellipsoidal shell model for mono-valent metal clusters. In particular, cluster numbers 8, 20, and 40--which correspond to the spherical shell closings of this model--have low electron affinities and large HOMO-LUMO gaps. The spectra of the gold cluster ions indicate that the molecular orbital energies of the cluster valence electrons are more widely spaced for gold than for copper or silver. This is to be expected for the heavy atom clusters when relativistic effects are taken into account.

A Survey of Electron Impact Cross-Sections for Halogens and Halogen Compounds of Interest to Plasma Processing

NASA Technical Reports Server (NTRS)

Sharma, S. P.; Rao, M. V. V. S.; Arnold, James O. (Technical Monitor)

1998-01-01

Published electron impact cross section data on halogens Cl2, F2, and halogen containing compounds such as Cx Fy, HCl, Cx Cly Fz are reviewed and critically evaluated based on the information provided by various researchers. The present work reports data on electron impact excitation, ionization, dissociation, electron attachment, electron detachment, and photo detachment. Elastic scattering cross sections and data on bulk properties such as diffusion coefficients in various background gases are also evaluated. Since some of the cross sectional data is derived from indirect measurements such as drift velocity, care has been taken to reconcile the differences among the reported data with due attention to the measurement technique. In conclusion, the processes with no or very limited amount of data and questionable set of data are identified and recommendation for further research direction is made.

Hydrated Electrons React with High Specificity with Cisplatin Bound to Single-Stranded DNA

PubMed Central

Behmand, B.; Cloutier, P.; Girouard, S.; Wagner, J. R.; Sanche, L.; Hunting, D. J.

2015-01-01

Short oligonucleotides TTTTTGTGTTT and TTTTTTTGTTT in solution with and without cisplatin (cisPt) bound to the guanine bases were irradiated with γ-rays at doses varying from 0 to 2500 Gy. To determine the effect of hydrated electrons from water radiolysis on the oligonucleotides, we quenched •OH radicals with ethylenediaminetetraacetic acid (EDTA) and displaced oxygen, which reacts with hydrated electrons, by bubbling the solution with wet nitrogen. DNA strand breaks and platinum detachment were quantified by gel electrophoresis. Our results demonstrate that hydrated electrons react almost exclusively at the position of the cisPt adduct, where they induce cisPt detachment from one or both guanines in the oligonucleotide. Given the high yield of hydrated electrons in irradiated tissues, this reaction may be an important step in the mechanism of radiosensitization of DNA by cisPt. PMID:24205952

Barrier-free proton transfer in the valence anion of 2'-deoxyadenosine-5'-monophosphate. II. A computational study.

PubMed

Kobyłecka, Monika; Gu, Jiande; Rak, Janusz; Leszczynski, Jerzy

2008-01-28

The propensity of four representative conformations of 2(')-deoxyadenosine-5(')-monophosphate (5(')-dAMPH) to bind an excess electron has been studied at the B3LYP6-31++G(d,p) level. While isolated canonical adenine does not support stable valence anions in the gas phase, all considered neutral conformations of 5(')-dAMPH form adiabatically stable anions. The type of an anionic 5(')-dAMPH state, i.e., the valence, dipole bound, or mixed (valence/dipole bound), depends on the internal hydrogen bond(s) pattern exhibited by a particular tautomer. The most stable anion results from an electron attachment to the neutral syn-south conformer. The formation of this anion is associated with a barrier-free proton transfer triggered by electron attachment and the internal rotation around the C4(')-C5(') bond. The adiabatic electron affinity of the a_south-syn anion is 1.19 eV, while its vertical detachment energy is 1.89 eV. Our results are compared with the photoelectron spectrum (PES) of 5(')-dAMPH(-) measured recently by Stokes et al., [J. Chem. Phys. 128, 044314 (2008)]. The computational VDE obtained for the most stable anionic structure matches well with the experimental electron binding energy region of maximum intensity. A further understanding of DNA damage might require experimental and computational studies on the systems in which purine nucleotides are engaged in hydrogen bonding.

Barrier-free proton transfer in the valence anion of 2'-deoxyadenosine-5'-monophosphate. II. A computational study

NASA Astrophysics Data System (ADS)

Kobyłecka, Monika; Gu, Jiande; Rak, Janusz; Leszczynski, Jerzy

2008-01-01

The propensity of four representative conformations of 2'-deoxyadenosine-5'-monophosphate (5'-dAMPH) to bind an excess electron has been studied at the B3LYP /6-31++G(d,p) level. While isolated canonical adenine does not support stable valence anions in the gas phase, all considered neutral conformations of 5'-dAMPH form adiabatically stable anions. The type of an anionic 5'-dAMPH state, i.e., the valence, dipole bound, or mixed (valence/dipole bound), depends on the internal hydrogen bond(s) pattern exhibited by a particular tautomer. The most stable anion results from an electron attachment to the neutral syn-south conformer. The formation of this anion is associated with a barrier-free proton transfer triggered by electron attachment and the internal rotation around the C4'-C5' bond. The adiabatic electron affinity of the a&barbelow;south-syn anion is 1.19eV, while its vertical detachment energy is 1.89eV. Our results are compared with the photoelectron spectrum (PES) of 5'-dAMPH- measured recently by Stokes et al., [J. Chem. Phys. 128, 044314 (2008)]. The computational VDE obtained for the most stable anionic structure matches well with the experimental electron binding energy region of maximum intensity. A further understanding of DNA damage might require experimental and computational studies on the systems in which purine nucleotides are engaged in hydrogen bonding.

Lithospheric "corner flow" via extensional faulting and tectonic rotation at non-volcanic, slow-spreading ridges

NASA Astrophysics Data System (ADS)

Schroeder, T.; Cheadle, M. J.; Dick, H. J.; Faul, U.

2005-12-01

Large degrees (up to 90°) of tectonic rotation may be the norm at slow-spreading, non-volcanic ridges. Vertically upwelling mantle beneath all mid-ocean ridges must undergo corner flow to move horizontally with the spreading plate. Because little or no volcanic crust is produced at some slow-spreading ridges, the uppermost lithospheric mantle must undergo this rotation in the regime of localized, rather than distributed deformation. Anomalous paleomagnetic inclinations in peridotite and gabbro cores drilled near the 15-20 Fracture Zone (Mid-Atlantic Ridge, ODP Leg 209) support such large rotations, with sub-Curie-temperature rotations up to 90° (Garces et al., 2004). Here, we present two end-member tectonic mechanisms, with supporting data from Leg 209 cores and bathymetry, to show how rotation is accomplished via extensional faults and shear zones: 1) long-lived detachment faults, and 2) multiple generations of high-angle normal faults. Detachment faults accommodate rotation by having a moderate to steep dip at depth, and rotating to horizontal through a rolling hinge as the footwall is tectonically denuded. Multiple generations of high-angle normal faults accommodate large rotations in a domino fashion; early faults become inactive when rotated to inopportune slip angles, and are cut by younger high-angle faults. Thus, each generation of high-angle faults accommodates part of the total rotation. There is likely a gradation between the domino and detachment mechanisms; transition from domino to detachment faulting occurs when a single domino fault remains active at inopportune slip angles and evolves into a detachment that accommodates all corner flow for that region. In both cases, the original attitude of layering within mantle-emplaced gabbro bodies must be significantly different than present day observed attitudes; sub-horizontal bodies may have been formed sub-vertically and vice-versa. Leg 209 cores record an average major brittle fault spacing of approximately 100 m, suggesting that the width of individual rotating fault blocks may be on the order of 100-200 m. Numerous fault bounded domino slices could therefore be formed within a 10km wide axial valley, with large rotations (and commensurate extension) leading to the exposure of 1km wide shallow-dipping fault surfaces, as are seen in the 15-20 FZ region bathymetry. The region's bathymetry is dominated by irregular, low-relief ridges that were likely formed by domino faulting of lithosphere with a small elastic thickness. The region contains relatively few corrugated detachment fault domes, suggesting that domino faulting may be the normal mode of lithospheric corner flow at non-volcanic ridges.

Reduction of Defects in Germanium-Silicon

NASA Technical Reports Server (NTRS)

2003-01-01

Crystals grown without contact with a container have far superior quality to otherwise similar crystals grown in direct contact with a container. In addition to float-zone processing, detached- Bridgman growth is a promising tool to improve crystal quality, without the limitations of float zoning or the defects introduced by normal Bridgman growth. Goals of this project include the development of the detached Bridgman process to be reproducible and well understood and to quantitatively compare the defect and impurity levels in crystals grown by these three methods. Germanium (Ge) and germanium-silicon (Ge-Si) alloys are being used. At MSFC, we are responsible for the detached Bridgman experiments intended to differentiate among proposed mechanisms of detachment, and to confirm or refine our understanding of detachment. Because the contact angle is critical to determining the conditions for detachment, the sessile drop method was used to measure the contact angles as a function of temperature and composition for a large number of substrates made of potential ampoule materials. Growth experiments have used pyrolytic boron nitride (pBN) and fused silica ampoules with the majority of the detached results occurring predictably in the pBN. Etch pit density (EPD) measurements of normal and detached Bridgman-grown Ge samples show a two order of magnitude improvement in the detached-grown samples. The nature and extent of detachment is determined by using profilometry in conjunction with optical and electron microscopy. The stability of detachment has been analyzed, and an empirical model for the conditions necessary to achieve sufficient stability to maintain detached growth for extended periods has been developed. We have investigated the effects on detachment of ampoule material, pressure difference above and below the melt, and Si concentration; samples that are nearly completely detached can be grown repeatedly in pBN. Current work is concentrated on developing a method to make in situ pressure measurements in the growth ampoules.

Structures and electron affinities of the di-arsenic fluorides As2Fn/As2Fn- (n=1-8).

PubMed

Kasalová, Veronika; Schaefer, Henry F

2005-04-15

Developments in the preparation of new materials for microelectronics are focusing new attention on molecular systems incorporating several arsenic atoms. A systematic investigation of the As2Fn/As2Fn- systems was carried out using Density Functional Theory methods and a DZP++ quality basis set. Global and low-lying local geometric minima and relative energies are discussed and compared. The three types of neutral-anion separations reported in this work are: the adiabatic electron affinity (EAad), the vertical electron affinity (EAvert), and the vertical detachment energy (VDE). Harmonic vibrational frequencies pertaining to the global minimum for each compound are reported. From the first four studied species (As2Fn, n=1-4), all neutral molecules and their anions are shown to be stable with respect to As-As bond breaking. The neutral As2F molecule and its anion are predicted to have Cs symmetry. We find the trans F-As-As-F isomer of C2h symmetry and a pyramidalized vinylidene-like As-As-F2- isomer of Cs symmetry to be the global minima for the As2F2 and As2F2- species, respectively. The lowest lying minima of As2F3 and As2F3- are vinyl radical-like structures F-As-As-F2 of Cs symmetry. The neutral As2F4 global minimum is a trans-bent (like Si2H4) F2-As-As-F2 isomer of C2 symmetry, while its anion is predicted to have an unusual fluorine-bridged (C(1)) structure. The global minima of the neutral As2Fn species, n=5-8, are weakly bound complexes, held together by dipole-dipole interactions. All such structures have the AsFm-AsFn form, where (m,n) is (2,3) for As2F5, (3,3) for As2F6, (4,3) for As2F7), and (5,3) for As2F8. For As2F8 the beautiful pentavalent F4As-AsF4 structure (analogous to the stable AsF5 molecule) lies about 30 kcal/mol above the AsF3 . . . AsF5 complex. The stability of AsF(5) depends crucially on the strong As-F bonds, and replacing one of these with an As-As bond (in F4As-AsF4) has a very negative impact on the molecule's stability. The anions As2Fn-, n=5-8, are shown to be stable with respect to the As-As bond breaking, and we predict that all of them have fluorine-bridged or fluorine-linked structures. The zero-point vibrational energy corrected adiabatic electron affinities are predicted to be 2.28 eV (As2F), 1.95 eV (As2F2), 2.39 eV (As2F3), 1.71 eV (As2F4), 2.72 eV (As2F5), 1.79 eV (As2F6), 5.26 eV (As2F7), and 3.40 eV (As2F8) from the BHLYP method. Vertical detachment energies are rather large, especially for species with fluorine-bridged global minima, having values up to 6.45 eV (As2F7, BHLYP).

Orientation, composition, and entrapment conditions of fluid inclusions in the footwall of the northern Snake Range detachment, Nevada

NASA Astrophysics Data System (ADS)

Carter, Matthew J.; Siebenaller, Luc; Teyssier, Christian

2015-12-01

Footwall rocks of the northern Snake Range detachment fault (Hampton and Hendry's Creeks) offer exposures of quartzite mylonites (sub-horizontal foliation) that were permeated by surface fluids. An S-C-C‧ mylonitic fabric is defined by dynamically recrystallized quartz and mica. Electron backscatter diffraction analyses indicate a strong preferred orientation of quartz that is overprinted by two sets of sub-vertical, ESE and NNE striking fractures. Analyses of sets of three perpendicular thin sections indicate that fluid inclusions (FIs) are arranged according to macroscopic fracture patterns. FIs associated with NNE and ESE-striking fractures coevally trapped unmixed CO2 and H2O-rich fluids at conditions near the critical CO2-H2O solvus, giving minimum trapping conditions of T = 175-200 °C and ∼100 MPa H2O-rich FIs trapped along ESE-trending microcracks in single crystals of quartz may have been trapped at conditions as low as 150 °C and 50 MPa indicating the latest microfracturing and annealing of quartz in an overall extensional system. Results suggest that the upper crust was thin (4-8 km) during FI trapping and had an elevated geotherm (>50 °C/km). Footwall rocks that have been exhumed through the brittle-ductile transition in such extensional systems experience both brittle and crystal-plastic deformation that may allow for circulation of meteoric fluids and grain-scale fluid-rock interactions.

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

Mazurkiewicz, Kamil; Haranczyk, Maciej; Gutowski, Maciej S.

The electron affinity and the propensity to electron-induced proton transfer (PT) of hydrogen-bonded complexes between the Watson–Crick adenine–thymine pair (AT) and simple organic acid (HX), attached to adenine in the Hoogsteen-type configuration, were studied at the B3LYP/6-31+G** level. Although the carboxyl group is deprotonated at physiological pH, its neutral form, COOH, resembles the peptide bond or the amide fragment in the side chain of asparagine (Asn) or glutamine (Gln). Thus, these complexes mimic the interaction between the DNA environment (e.g., proteins) and nucleobase pairs incorporated in the biopolymer. Electron attachment is thermodynamically feasible and adiabatic electron affinities range from 0.41more » to 1.28 eV, while the vertical detachment energies of the resulting anions span the range of 0.39 –2.88 eV. Low-energy activation barriers separate the anionic minima: aHX(AT) from the more stable single-PT anionic geometry, aHX(AT)-SPT, and aHX(AT)-SPT from the double-PT anionic geometry, aHX(AT)-DPT. Interaction between the adenine of the Watson–Crick AT base pair with an acidic proton donor probably counterbalances the larger EA of isolated thymine, as SOMO is almost evenly delocalized over both types of nucleic bases in the aHX(AT) anions. Moreover, as a result of PT the excess electron localizes entirely on adenine. Thus, in DNA interacting with its physiological environment, damage induced by low-energy electrons could begin, contrary to the current view, with the formation of purine anions, which are not formed in isolated DNA because of the greater stability of anionic pyrimidines.« less

Icebergs Melting in Uniform and Vertically Sheared Flows

NASA Astrophysics Data System (ADS)

Cenedese, Claudia; Fitzmaurice, Anna; Straneo, Fiammetta

2017-11-01

Icebergs calving into Greenlandic Fjords frequently experience strongly sheared flows over their draft, but the impact of this flow past the iceberg on the melt plumes generated along the iceberg sides is not fully captured by existing melt parameterizations. A series of novel laboratory experiments showed that side melting of icebergs subject to relative velocities is controlled by two distinct regimes, which depend on the melt plume behavior (side-attached or side-detached). These two regimes produce a nonlinear dependence of melt rate on velocity, and different distributions of meltwater in the water column. Iceberg meltwater may either be confined to a thin surface layer, when the melt plumes are side-attached, or mixed down to the iceberg draft, when the melt plumes are side-detached. In a two-layer vertically sheared flow, the average flow speed in existing melt parameterizations gives an underestimate of the submarine melt rate, in part due to the nonlinearity of the dependence of melt rate on flow speed, but also because vertical shear in the velocity profile fundamentally changes the flow splitting around the ice block and consequently the velocity felt by the ice surface. Including this nonlinear velocity dependence in melting parameterizations applied to observed icebergs increases iceberg side melt in the side-attached regime, improving agreement with observations of iceberg submarine melt rates. AF was supported by NA14OAR4320106, CC by NSF OCE-1434041 and OCE-1658079, and FS by NSF PLR-1332911 and OCE-1434041.

Investigation on the neutral and anionic BxAlyH2 (x + y = 7, 8, 9) clusters using density functional theory combined with photoelectron spectroscopy.

PubMed

Ding, Li-Ping; Shao, Peng; Lu, Cheng; Zhang, Fang-Hui; Ding, Lei; Yuan, Tao Li

2016-08-17

The structure and bonding nature of neutral and negatively charged BxAlyH2 (x + y = 7, 8, 9) clusters are investigated with the aid of previously published experimental photoelectron spectra combined with the present density functional theory calculations. The comparison between the experimental photoelectron spectra and theoretical simulated spectra helps to identify the ground state structures. The accuracy of the obtained ground state structures is further verified by calculating their adiabatic electron affinities and vertical detachment energies and comparing them against available experimental data. The results show that the structures of BxAlyH2 transform from three-dimensional to planar structures as the number of boron atoms increases. Moreover, boron atoms tend to bind together forming Bn units. The hydrogen atoms prefer to bind with boron atoms rather than aluminum atoms. The analyses of the molecular orbital on the ground state structures further support the abovementioned results.

GoPro HERO 4 Black recording of scleral buckle placement during retinal detachment repair.

PubMed

Ho, Vincent Y; Shah, Vaishali G; Yates, David M; Shah, Gaurav K

2017-08-01

GoPro and Google Glass technology have previously been used to record procedures in ophthalmology and other medical fields. In this manuscript, GoPro's latest HERO 4 Black edition camera (GoPro Inc, San Mateo, Calif.) will be used to record the placement of a scleral buckle during retinal detachment surgery. GoPro HERO 4 Black edition camera, which records 4K-quality video with a resolution of 3840 (pixels) x 2160 (lines), was mounted on a head strap to record placement of a scleral buckle for a retinal detachment. Excellent video quality was achieved with the 4K SuperView setting. Bluetooth connection with an Apple iPad (Apple Inc, Cupertino, Calif.) provided live streaming and use of the GoPro App. Zoom, horizontal/vertical alignment, exposure, and contrast adjustments were made with postproduction editing on GoPro Studio software. Video recording with the GoPro HERO 4 Black edition camera is an excellent way to document extraocular procedures to improve medical education, self-training, or medicolegal documentation. Copyright © 2017 Canadian Ophthalmological Society. Published by Elsevier Inc. All rights reserved.

Influence of cell detachment on the respiration rate of tumor and endothelial cells.

PubMed

Danhier, Pierre; Copetti, Tamara; De Preter, Géraldine; Leveque, Philippe; Feron, Olivier; Jordan, Bénédicte F; Sonveaux, Pierre; Gallez, Bernard

2013-01-01

Cell detachment is a procedure routinely performed in cell culture and a necessary step in many biochemical assays including the determination of oxygen consumption rates (OCR) in vitro. In vivo, cell detachment has been shown to exert profound metabolic influences notably in cancer but also in other pathologies, such as retinal detachment for example. In the present study, we developed and validated a new technique combining electron paramagnetic resonance (EPR) oximetry and the use of cytodex 1 and collagen-coated cytodex 3 dextran microbeads, which allowed the unprecedented comparison of the OCR of adherent and detached cells with high sensitivity. Hence, we demonstrated that both B16F10 melanoma cells and human umbilical vein endothelial cells (HUVEC) experience strong OCR decrease upon trypsin or collagenase treatments. The reduction of cell oxygen consumption was more pronounced with a trypsin compared to a collagenase treatment. Cells remaining in suspension also encounter a marked intracellular ATP depletion and an increase in the lactate production/glucose uptake ratio. These findings highlight the important influence exerted by cell adhesion/detachment on cell respiration, which can be probed with the unprecedented experimental assay that was developed and validated in this study.

Influence of Cell Detachment on the Respiration Rate of Tumor and Endothelial Cells

PubMed Central

Danhier, Pierre; Copetti, Tamara; De Preter, Géraldine; Leveque, Philippe; Feron, Olivier; Jordan, Bénédicte F.; Sonveaux, Pierre; Gallez, Bernard

2013-01-01

Cell detachment is a procedure routinely performed in cell culture and a necessary step in many biochemical assays including the determination of oxygen consumption rates (OCR) in vitro. In vivo, cell detachment has been shown to exert profound metabolic influences notably in cancer but also in other pathologies, such as retinal detachment for example. In the present study, we developed and validated a new technique combining electron paramagnetic resonance (EPR) oximetry and the use of cytodex 1 and collagen-coated cytodex 3 dextran microbeads, which allowed the unprecedented comparison of the OCR of adherent and detached cells with high sensitivity. Hence, we demonstrated that both B16F10 melanoma cells and human umbilical vein endothelial cells (HUVEC) experience strong OCR decrease upon trypsin or collagenase treatments. The reduction of cell oxygen consumption was more pronounced with a trypsin compared to a collagenase treatment. Cells remaining in suspension also encounter a marked intracellular ATP depletion and an increase in the lactate production/glucose uptake ratio. These findings highlight the important influence exerted by cell adhesion/detachment on cell respiration, which can be probed with the unprecedented experimental assay that was developed and validated in this study. PMID:23382841

Electron affinities, molecular structures, and thermochemistry of the fluorine, chlorine and bromine substituted methyl radicals

NASA Astrophysics Data System (ADS)

Li, Qian-Shu; Zhao, Jun-Fang; Xie, Yaoming; Schaefer, Henry F., III

Four independent density functional theory (DFT) methods have been employed to study the structures and electron affinities of the methyl and F-, Cl- and Br-substituted methyl radicals and their anions. The methods used have been carefully calibrated against a comprehensive tabulation of experimental electron affinities (Chemical Reviews, 2002, 102, 231). The first dissociation energies together with the vibrational frequencies of these species are also reported. The basis sets used in this work are of double- ζ plus polarization quality with additional s- and p-type diffuse functions, labelled as DZP++. Previously observed trends in the prediction of bond lengths by the DFT methods are also demonstrated for the F-, Cl- and Br-substituted methyl radicals and their anions. Generally, the Hartree-Fock/DFT hybrid methods predict shorter and more reliable bond lengths than the pure DFT methods. Neutral-anion energy differences reported in this work are the adiabatic electron affinity (EAad), the vertical electron affinity (EAvert), and the vertical detachment energy (VDE). Compared with the available experimental electron affinities, the BHLYP method predicts much lower values, while the other methods predict values (EAad, EAvert, VDE) close to each other and almost within the experimental range. For those systems without reliable experimental measurements, our best adiabatic EAs predicted by BLYP are 0.78 (CHF2), 1.23 (CHFCl), 1.44 (CHFBr), 1.61 (CHClBr), 2.24 (CF2Cl), 2.42 (CF2Br), 2.56 (CFBr2), 2.36 (CCl2Br), 2.46 (CClBr2), and 2.44 eV (CFClBr). The most striking feature of these predictions is that they display an inverse relationship between halogen electronegativity and EA. The DZP++ B3LYP method determines the vibrational frequencies in best agreement with available experimental results for this series, with an average relative error of ~2%. The value of using a variety of DFT methods is observed in that BHLYP does best for geometries, BLYP for electron affinities, and B3LYP for vibrational frequencies. These theoretical results serve to resolve several disagreements between competing experiments. Several other experiments appear to have drawn incorrect conclusions. For example, CHCl2 is significantly pyramidal, unlike the experimental inferences, and clearly the experimental CCl2 - Cl dissociation energy is too large.

Electron affinity and excited states of methylglyoxal

NASA Astrophysics Data System (ADS)

Dauletyarov, Yerbolat; Dixon, Andrew R.; Wallace, Adam A.; Sanov, Andrei

2017-07-01

Using photoelectron imaging spectroscopy, we characterized the anion of methylglyoxal (X2A″ electronic state) and three lowest electronic states of the neutral methylglyoxal molecule: the closed-shell singlet ground state (X1A'), the lowest triplet state (a3A″), and the open-shell singlet state (A1A″). The adiabatic electron affinity (EA) of the ground state, EA(X1A') = 0.87(1) eV, spectroscopically determined for the first time, compares to 1.10(2) eV for unsubstituted glyoxal. The EAs (adiabatic attachment energies) of two excited states of methylglyoxal were also determined: EA(a3A″) = 3.27(2) eV and EA(A1A″) = 3.614(9) eV. The photodetachment of the anion to each of these two states produces the neutral species near the respective structural equilibria; hence, the a3A″ ← X2A″ and A1A″ ← X2A″ photodetachment transitions are dominated by intense peaks at their respective origins. The lowest-energy photodetachment transition, on the other hand, involves significant geometry relaxation in the X1A' state, which corresponds to a 60° internal rotation of the methyl group, compared to the anion structure. Accordingly, the X1A' ← X2A″ transition is characterized as a broad, congested band, whose vertical detachment energy, VDE = 1.20(4) eV, significantly exceeds the adiabatic EA. The experimental results are in excellent agreement with the ab initio predictions using several equation-of-motion methodologies, combined with coupled-cluster theory.

Dynamics of electron solvation in I(-)(CH3OH)n clusters (4 ≤ n ≤ 11).

PubMed

Young, Ryan M; Yandell, Margaret A; Neumark, Daniel M

2011-03-28

The dynamics of electron solvation following excitation of the charge-transfer-to-solvent precursor state in iodide-doped methanol clusters, I(-)(CH(3)OH)(n = 4-11), are studied with time-resolved photoelectron imaging. This excitation produces a I···(CH(3)OH)(n)(-) cluster that is unstable with respect to electron autodetachment and whose autodetachment lifetime increases monotonically from ~800 fs to 85 ps as n increases from 4 to 11. The vertical detachment energy (VDE) and width of the excited state feature in the photoelectron spectrum show complex time dependence during the lifetime of this state. The VDE decreases over the first 100-400 fs, then rises exponentially to a maximum with a ~1 ps time constant, and finally decreases by as much as 180 meV with timescales of 3-20 ps. The early dynamics are associated with electron transfer from the iodide to the methanol cluster, while the longer-time changes in VDE are attributed to solvent reordering, possibly in conjunction with ejection of neutral iodine from the cluster. Changes in the observed width of the spectrum largely follow those of the VDEs; the dynamics of both are attributed to the major rearrangement of the solvent cluster during relaxation. The relaxation dynamics are interpreted as a reorientation of at least one methanol molecule and the disruption and formation of the solvent network in order to accommodate the excess charge.

On the role of metastable states in low pressure oxygen discharges

NASA Astrophysics Data System (ADS)

Gudmundsson, J. T.; Hannesdóttir, H.

2017-03-01

We use the one-dimensional object-oriented particle-in-cell Monte Carlo collision code oopd1 to explore the spatio-temporal evolution of the electron heating mechanism in a capacitively coupled oxygen discharge in the pressure range 10 - 200 mTorr. The electron heating is most significant in the sheath vicinity during the sheath expansion phase. We explore how including and excluding detachment by the singlet metastable states O2(a1 Δg) and O2(b1Σ+g) influences the heating mechanism, the effective electron temperature and electronegativity, in the oxygen discharge. We demonstrate that the detachment processes have a significant influence on the discharge properties, in particular for the higher pressures. At 10 mTorr the time averaged electron heating shows mainly ohmic heating in the plasma bulk (the electronegative core) and at higher pressures there is no ohmic heating in the plasma bulk, that is electron heating in the sheath regions dominates.

Interpretation of the photoelectron spectra of FeS(2)(-) by a multiconfiguration computational approach.

PubMed

Clima, Sergiu; Hendrickx, Marc F A

2007-11-01

The ground states of FeS(2) and FeS(2)(-), and several low-lying excited electronic states of FeS(2) that are responsible for the FeS(2)(-) photoelectron spectrum, are calculated. At the B3LYP level an open, quasi-linear [SFeS](-) conformation is found as the most stable structure, which is confirmed at the ab initio CASPT2 computational level. Both the neutral and the anionic unsaturated complexes possess high-spin electronic ground states. For the first time a complete assignment of the photoelectron spectrum of FeS(2)(-) is proposed. The lowest energy band in this spectrum is ascribed to an electron detachment from the two highest-lying 3dpi antibonding orbitals (with respect to the iron-sulfur bonding) of iron. The next-lowest experimental band corresponds to an electron removal from nonbonding, nearly pure sulfur orbitals. The two highest bands in the spectra are assigned as electron detachments from pi and sigma bonding mainly sulfur orbitals.

Onset of frictional sliding of rubber–glass contact under dry and lubricated conditions

PubMed Central

Tuononen, Ari J.

2016-01-01

Rubber friction is critical in many applications ranging from automotive tyres to cylinder seals. The process where a static rubber sample transitions to frictional sliding is particularly poorly understood. The experimental and simulation results in this paper show a completely different detachment process from the static situation to sliding motion under dry and lubricated conditions. The results underline the contribution of the rubber bulk properties to the static friction force. In fact, simple Amontons’ law is sufficient as a local friction law to produce the correct detachment pattern when the rubber material and loading conditions are modelled properly. Simulations show that micro-sliding due to vertical loading can release initial shear stresses and lead to a high static/dynamic friction coefficient ratio, as observed in the measurements. PMID:27291939

Stabilizing detached Bridgman melt crystal growth: Model-based nonlinear feedback control

NASA Astrophysics Data System (ADS)

Yeckel, Andrew; Daoutidis, Prodromos; Derby, Jeffrey J.

2012-12-01

The dynamics and operability limits of a nonlinear-proportional-integral controller designed to stabilize detached vertical Bridgman crystal growth are studied. The manipulated variable is the pressure difference between upper and lower vapor spaces, and the controlled variable is the gap width at the triple-phase line. The controller consists of a model-based nonlinear component coupled with a standard proportional-integral controller. The nonlinear component is based on a capillary model of shape stability. Perturbations to gap width, pressure difference, wetting angle, and growth angle are studied under both shape stable and shape unstable conditions. The nonlinear-PI controller allows a wider operating range of gain than a standard PI controller used alone, is easier to tune, and eliminates solution multiplicity from closed-loop operation.

Prediction of the Iron-Based Polynuclear Magnetic Superhalogens with Pseudohalogen CN as Ligands.

PubMed

Ding, Li-Ping; Shao, Peng; Lu, Cheng; Zhang, Fang-Hui; Liu, Yun; Mu, Qiang

2017-07-17

To explore stable polynuclear magnetic superhalogens, we perform an unbiased structure search for polynuclear iron-based systems based on pseudohalogen ligand CN using the CALYPSO method in conjunction with density functional theory. The superhalogen properties, magnetic properties, and thermodynamic stabilities of neutral and anionic Fe 2 (CN) 5 and Fe 3 (CN) 7 clusters are investigated. The results show that both of the clusters have superhalogen properties due to their electron affinities (EAs) and that vertical detachment energies (VDEs) are significantly larger than those of the chlorine element and their ligand CN. The distribution of the extra electron analysis indicates that the extra electron is aggregated mainly into pseudohalogen ligand CN units in Fe 2 (CN) 5 ¯ and Fe 3 (CN) 7 ¯ cluster. These features contribute significantly to their high EA and VDE. Besides superhalogen properties, these two anionic clusters carry a large magnetic moment just like the Fe 2 F 5 ¯ cluster. Additionally, the thermodynamic stabilities are also discussed by calculating the energy required to fragment the cluster into various smaller stable clusters. It is found that Fe(CN) 2 is the most favorable fragmentation product for anionic Fe 2 (CN) 5 ¯ and Fe 3 (CN) 7 ¯ clusters, and both of the anions are less stable against ejection of Fe atoms than Fe(CN) n-x .

Structures and electron affinity of XO30,-, XOF40,- and XO2F20,- (X = P, As, Sb, Bi): a theoretical study of novel superhalogen formulae and exceptions of superhalogen formulae

NASA Astrophysics Data System (ADS)

Yang, Yi-Fan; Cui, Zhong-Hua; Ding, Yi-Hong

2015-03-01

Most superhalogen species are in the form of oxides or halides. To enrich the family of superhalogen species, herein, we investigated the structures and electron affinity (EA) values of higher group 15 elements (X = P, As, Sb, Bi) oxyfluoride species XO30,-, XOF40,- and XO2F20,-, at the CCSD(T)/aug-cc-pVTZ-pp & aug-cc-pVTZ //B3LYP/aug-cc-pVTZ-pp & aug-cc-pVTZ levels (aug-cc-pVTZ-pp for X = Sb and Bi). Some oxyfluoride species, i.e., PO2F20,-, AsO2F20,-, SbO2F20,-, POF40,-, AsOF40,-, SbOF40,- and BiOF40,-, were found to possess higher EA (VDE: 5.0-6.2 eV; ADE: 4.5-5.5 eV) than halogens (F: 3.4 eV; Cl: 3.6 eV). Thus, we recommended that the oxyfluorides in the form of XO2F20,- and XOF40,- should be considered as potential superhalogens, which have not been considered previously. Surprisingly, we showed that BiO3 and BiO2F2, in superhalogen formulae, possess a high vertical detachment energy (VDE) yet a low adiabatic detachment energy (ADE). This is in marked contrast to the previously reported superhalogens, which generally contain both the high VDE and high ADE values. It is the first report about exceptions of superhalogen formulae. These findings revealed that for the analogous main-group compounds with the same structural formula, the difference in the metallic property of the core element could lead to the significant difference in the ground structures of either the anionic or neutral structures, which would result in the much differed superhalogen features.

Late Miocene uplift in the Romagnan Apennines and the detachment of subducted lithosphere

NASA Astrophysics Data System (ADS)

van der Meulen, M. J.; Kouwenhoven, T. J.; van der Zwaan, G. J.; Meulenkamp, J. E.; Wortel, M. J. R.

1999-12-01

We report part of a test of the hypothesis that detachment of subducted lithosphere may be a process of lateral propagation of a horizontal tear [Wortel and Spakman, Proc. Kon. Ned. Akad. Wetensch., 95 (1992) 325-347]. We have used the Apennines as a test area. The test procedure consists of the comparison of hypothetical vertical motions, predicted from the expected redistribution of slab pull forces, with observed vertical motions. We demonstrate that a Late Miocene depocentre migration from the Northern towards the Central Apennines is associated with uplift of (the fore-arc of) the Northern Apennines. Such a combination of a depocentre shift and uplift is thought to be diagnostic for lateral migration of slab detachment. The depocentre migration was identified in earlier work [van der Meulen et al., Earth Planet. Sci. Lett., 154 (1998) 203-219]. This contribution focuses on uplift, which has primarily been identified through the geohistory analysis of the Monte del Casino Section (Romagnan Apennines, Northern Italy). Owing to methodological problems, the start and duration of the uplift phase could not be constrained, and only a minimum estimate of the total amount of uplift (483±180 m) is obtained. The data do allow for an estimate of the uplift rate: 163±61 cm/ky. A review of regional data results in better constraints on the timing of the above lateral reorganisation of the fore-arc, and on the spatial extent of the uplifted area. Depocentre development in the Central Apennines began between 8.6 and 8.3 Ma B.P. Uplift started between 9 and 8 Ma B.P., and affected the entire northernmost Apennines.

Tunable wavefront coded imaging system based on detachable phase mask: Mathematical analysis, optimization and underlying applications

NASA Astrophysics Data System (ADS)

Zhao, Hui; Wei, Jingxuan

2014-09-01

The key to the concept of tunable wavefront coding lies in detachable phase masks. Ojeda-Castaneda et al. (Progress in Electronics Research Symposium Proceedings, Cambridge, USA, July 5-8, 2010) described a typical design in which two components with cosinusoidal phase variation operate together to make defocus sensitivity tunable. The present study proposes an improved design and makes three contributions: (1) A mathematical derivation based on the stationary phase method explains why the detachable phase mask of Ojeda-Castaneda et al. tunes the defocus sensitivity. (2) The mathematical derivations show that the effective bandwidth wavefront coded imaging system is also tunable by making each component of the detachable phase mask move asymmetrically. An improved Fisher information-based optimization procedure was also designed to ascertain the optimal mask parameters corresponding to specific bandwidth. (3) Possible applications of the tunable bandwidth are demonstrated by simulated imaging.

Comparison of three different orthodontic wires for bonded lingual retainer fabrication

PubMed Central

Uysal, Tancan; Gul, Nisa; Alan, Melike Busra; Ramoglu, Sabri Ilhan

2012-01-01

Objective We evaluated the detachment force, amount of deformation, fracture mode, and pull-out force of 3 different wires used for bonded lingual retainer fabrication. Methods We tested 0.0215-inch five-stranded wire (PentaOne, Masel; group I), 0.016 × 0.022-inch dead-soft eight-braided wire (Bond-A-Braid, Reliance; group II), and 0.0195-inch dead-soft coaxial wire (Respond, Ormco; group III). To test detachment force, deformation, and fracture mode, we embedded 94 lower incisor teeth in acrylic blocks in pairs. Retainer wires were bonded to the teeth and vertically directed force was applied to the wire. To test pull-out force, wires were embedded in composite that was placed in a hole at the center of an acrylic block. Tensile force was applied along the long axis of the wire. Results Detachment force and mode of fracture were not different between groups. Deformation was significantly higher in groups II and III than in group I (p < 0.001). Mean pull-out force was significantly higher for group I compared to groups II and III (p < 0.001). Conclusions Detachment force and fracture mode were similar for all wires, but greater deformations were seen in dead-soft wires. Wire pull-out force was significantly higher for five-stranded coaxial wire than for the other wires tested. Five-stranded coaxial wires are suggested for use in bonded lingual retainers. PMID:23112930

Partial detachment of high power discharges in ASDEX Upgrade

NASA Astrophysics Data System (ADS)

Kallenbach, A.; Bernert, M.; Beurskens, M.; Casali, L.; Dunne, M.; Eich, T.; Giannone, L.; Herrmann, A.; Maraschek, M.; Potzel, S.; Reimold, F.; Rohde, V.; Schweinzer, J.; Viezzer, E.; Wischmeier, M.; the ASDEX Upgrade Team

2015-05-01

Detachment of high power discharges is obtained in ASDEX Upgrade by simultaneous feedback control of core radiation and divertor radiation or thermoelectric currents by the injection of radiating impurities. So far 2/3 of the ITER normalized heat flux Psep/R = 15 MW m-1 has been obtained in ASDEX Upgrade under partially detached conditions with a peak target heat flux well below 10 MW m-2. When the detachment is further pronounced towards lower peak heat flux at the target, substantial changes in edge localized mode (ELM) behaviour, density and radiation distribution occur. The time-averaged peak heat flux at both divertor targets can be reduced below 2 MW m-2, which offers an attractive DEMO divertor scenario with potential for simpler and cheaper technical solutions. Generally, pronounced detachment leads to a pedestal and core density rise by about 20-40%, moderate (<20%) confinement degradation and a reduction of ELM size. For AUG conditions, some operational challenges occur, like the density cut-off limit for X-2 electron cyclotron resonance heating, which is used for central tungsten control.

The Detached Auroras Induced by the Solar Wind Pressure Enhancement in Both Hemispheres From Imaging and In Situ Particle Observations

NASA Astrophysics Data System (ADS)

Zhou, Su; Luan, Xiaoli; Søraas, Finn; Østgaard, Nikolai; Raita, Tero

2018-04-01

This paper presents simultaneous detached proton auroras that appeared in both hemispheres at 11:06 UT, 08 March 2012, just 2 min after a sudden solar wind pressure enhancement ( 11:04 UT) hit the Earth. They were observed under northward interplanetary magnetic field Bz condition and during the recovery phase of a moderate geomagnetic storm. In the Northern Hemisphere, Defense Meteorological Satellite Program/Special Sensor Ultraviolet Spectrographic Imager observed that the detached arc occurred within 60°-65° magnetic latitude and covered a few magnetic local time (MLT) hours ranging from 0530 to 0830 MLT with a possible extension toward noon. At the same time (11:06 UT), Polar Orbiting Environment Satellites 19 detected a detached proton aurora around 1300 MLT in the Southern Hemisphere, centering 62° magnetic latitude, which was at the same latitudes as the northern detached arc. This southern aurora was most probably a part of a dayside detached arc that was conjugate to the northern one. In situ particle observations indicated that the detached auroras were dominated by protons/ions with energies ranging from around 20 keV to several hundreds of keV, without obvious electron precipitations. These detached arcs persisted for less than 6 min, consistent with the impact from pressure enhancement and the observed electromagnetic ion cyclotron (EMIC) waves. It is suggested that the increasing solar wind pressure pushed the hot ions in the ring current closer to Earth where the steep gradient of cold plasma favored EMIC wave growth. By losing energy to EMIC waves the energetic protons (>20 keV) were scattered into the loss cone and produced the observed detached proton auroras.

Molecules for materials: germanium hydride neutrals and anions. Molecular structures, electron affinities, and thermochemistry of GeHn/GeHn- (n = 0-4) and Ge2Hn/Ge2Hn(-) (n = 0-6).

PubMed

Li, Qian-Shu; Lü, Rui-Hua; Xie, Yaoming; Schaefer, Henry F

2002-12-01

The GeH(n) (n = 0-4) and Ge(2)H(n) (n = 0-6) systems have been studied systematically by five different density functional methods. The basis sets employed are of double-zeta plus polarization quality with additional s- and p-type diffuse functions, labeled DZP++. For each compound plausible energetically low-lying structures were optimized. The methods used have been calibrated against a comprehensive tabulation of experimental electron affinities (Chemical Reviews 102, 231, 2002). The geometries predicted in this work include yet unknown anionic species, such as Ge(2)H(-), Ge(2)H(2)(-), Ge(2)H(3)(-), Ge(2)H(4)(-), and Ge(2)H(5)(-). In general, the BHLYP method predicts the geometries closest to the few available experimental structures. A number of structures rather different from the analogous well-characterized hydrocarbon radicals and anions are predicted. For example, a vinylidene-like GeGeH(2) (-) structure is the global minimum of Ge(2)H(2) (-). For neutral Ge(2)H(4), a methylcarbene-like HGë-GeH(3) is neally degenerate with the trans-bent H(2)Ge=GeH(2) structure. For the Ge(2)H(4) (-) anion, the methylcarbene-like system is the global minimum. The three different neutral-anion energy differences reported in this research are: the adiabatic electron affinity (EA(ad)), the vertical electron affinity (EA(vert)), and the vertical detachment energy (VDE). For this family of molecules the B3LYP method appears to predict the most reliable electron affinities. The adiabatic electron affinities after the ZPVE correction are predicted to be 2.02 (Ge(2)), 2.05 (Ge(2)H), 1.25 (Ge(2)H(2)), 2.09 (Ge(2)H(3)), 1.71 (Ge(2)H(4)), 2.17 (Ge(2)H(5)), and -0.02 (Ge(2)H(6)) eV. We also reported the dissociation energies for the GeH(n) (n = 1-4) and Ge(2)H(n) (n = 1-6) systems, as well as those for their anionic counterparts. Our theoretical predictions provide strong motivation for the further experimental study of these important germanium hydrides. Copyright 2002 Wiley Periodicals, Inc.

Vertical and Lateral Electron Content in the Martian Ionosphere

NASA Astrophysics Data System (ADS)

Paetzold, M. P.; Peter, K.; Bird, M. K.; Häusler, B.; Tellmann, S.

2016-12-01

The radio-science experiment MaRS (Mars Express Radio Science) on the Mars Express spacecraft sounds the neutral atmosphere and ionosphere of Mars since 2004. Approximately 800 vertical profiles of the ionospheric electron density have been acquired until today. The vertical electron content (TEC) is easily computed from the vertical electron density profile by integrating along the altitude. The TEC is typically a fraction of a TEC unit (1E16 m^-2) and depends on the solar zenith angle. The magnitude of the TEC is however fully dominated by the electron density contained in the main layer M2. The contributions by the M1 layer below M2 or the topside is marginal. MaRS is using two radio frequencies for the sounding of the ionosphere. The directly observed differential Doppler from the two received frequencies is a measure of the lateral electron content that means along the ray path and perpendicular to the vertical electron density profile. Combining both the vertical electron density profile, the vertical TEC and the directly observed lateral TEC describes the lateral electron density distribution in the ionosphere.

Photoelectron spectroscopy and density functional calculations of CunBO2(OH)- (n = 1,2) clusters

NASA Astrophysics Data System (ADS)

Feng, Yuan; Hou, Gao-Lei; Xu, Hong-Guang; Zhang, Zeng-Guang; Zheng, Wei-Jun

2012-08-01

CunBO2(OH)- (n = 1, 2) clusters were studied by anion photoelectron spectroscopy and density functional calculations. From the experimental photoelectron spectra, the adiabatic detachment energy (ADE) and vertical detachment energy (VDE) of CuBO2(OH)- are determined to be 4.00 ± 0.08 and 4.26 ± 0.08 eV, and those of Cu2BO2(OH)- to be 2.30 ± 0.08 and 2.58 ± 0.08 eV. The structures of CunBO2(OH)- and their corresponding neutrals are assigned by comparison between theoretical calculations and experimental measurements. Both experiment and theory show that CuBO2(OH) can be viewed as a superhalogen, thus, confirmed that OH can behave like a halogen atom to participate in superhalogen formation.

Planar CoB18- Cluster: a New Motif for - and Metallo-Borophenes

NASA Astrophysics Data System (ADS)

Chen, Teng-Teng; Jian, Tian; Lopez, Gary; Li, Wan-Lu; Chen, Xin; Li, Jun; Wang, Lai-Sheng

2016-06-01

Combined Photoelectron Spectroscopy (PES) and theoretical calculations have found that anion boron clusters (Bn-) are planar and quasi-planar up to B25-. Recent works show that anion pure boron clusters continued to be planar at B27-,B30-,B35- and B36-. B35- and B36- provide the first experimental evidence for the viability of the two-dimensional (2D) boron sheets (Borophene). The 2D to three-dimensional (3D) transitions are shown to happen at B40-,B39- and B28-, which possess cage-like structures. These fullerene-like boron cage clusters are named as Borospherene. Recently, borophenes or similar structures are claimed to be synthesized by several groups. Following an electronic design principle, a series of transition-metal-doped boron clusters (M©Bn-, n=8-10) are found to possess the monocyclic wheel structures. Meanwhile, CoB12- and RhB12- are revealed to adopt half-sandwich-type structures with the quasi-planar B12 moiety similar to the B12- cluster. Very lately, we show that the CoB16- cluster possesses a highly symmetric Cobalt-centered drum-like structure, with a new record of coordination number at 16. Here we report the CoB18- cluster to possess a unique planar structure, in which the Co atom is doped into the network of a planar boron cluster. PES reveals that the CoB18- cluster is a highly stable electronic system with the first adiabatic detachment energy (ADE) at 4.0 eV. Global minimum searches along with high-level quantum calculations show the global minimum for CoB18- is perfectly planar and closed shell (1A1) with C2v symmetry. The Co atom is bonded with 7 boron atoms in the closest coordination shell and the other 11 boron atoms in the outer coordination shell. The calculated vertical detachment energy (VDE) values match quite well with our experimental results. Chemical bonding analysis by the Adaptive Natural Density Partitioning (AdNDP) method shows the CoB18- cluster is π-aromatic with four 4-centered-2-electron (4c-2e) π bonds and one 19-centered-2-electron (19c-2e) π bond, 10 π electrons in total. This perfectly planar structure reveals the viability of creating a new class of hetero-borophenes and metallo-borophenes by doping metal atoms into the plane of monolayer boron atoms. This gives a new approach to design perspective hetero-borophenes and metallo-borophenes materials with tunable chemical, magnetic and optical properties.

Study of MoNbO(y) (y = 2-5) anion and neutral clusters using photoelectron spectroscopy and density functional theory calculations: impact of spin contamination on single point calculations.

PubMed

Waller, Sarah E; Mann, Jennifer E; Rothgeb, David W; Jarrold, Caroline C

2012-10-04

Results of a study combining anion photoelectron spectroscopy and density functional theory calculations on the heteronuclear MoNbO(y)(-) (y = 2-5) transition metal suboxide cluster series are reported and analyzed. The photoelectron spectra, which exhibit broad electronic bands with partially resolved vibrational structure, were compared to spectral simulations generated from calculated spectroscopic parameters for all computationally determined energetically competitive structures. Although computational results on the less oxidized clusters could not be satisfactorily reconciled with experimental spectra, possibly because of heavy spin contamination found in a large portion of the computational results, the results suggest that (1) neutral cluster electron affinity is a strong indicator of whether O-atoms are bound in M-O-M bridge positions or M═O terminal positions, (2) MoNbO(y) anions and neutrals have structures that can be described as intermediate with respect to the unary (homonuclear) Mo(2)O(y) and Nb(2)O(y) clusters, and (3) structures in which O-atoms preferentially bind to the Nb center are slightly more stable than alternative structures. Several challenges associated with the calculations are considered, including spin contamination, which appears to cause spurious single point calculations used to determine vertical detachment energies.

F-22 Operational Squadron and T-38 Detachment Beddown at Tyndall Air Force Base, Florida

DTIC Science & Technology

2011-08-01

tactics, radar employment, identification, weapons employment, defensive response, electronic countermeasures, and electronic counter...use, and electronic countermeasures. Warning Area, MOA, and ATCAA 2,000 AGL to 60,000 MSL 0.75 to 1.5 hour (Dissimilar) Air Combat...night), air refueling, and strike-force rendezvous, conducting air-to-ground strikes, strike force defense and escort, air intercepts, electronic

Low-energy measurements of electron-photon angular correlation in electron-impact excitation of the 2/sup 1/P state of helium

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

Steph, N.C.; Golden, D.E.

1983-03-01

Electron-photon angular correlations between electrons which have excited the 2/sup 1/P state of He and photons from the 2/sup 1/P..-->..1/sup 1/S transition have been studied for 27-, 30-, 35-, and 40-eV incident electrons. Values of lambda and Vertical BarchiVertical Bar obtained from these measurements are compared to values obtained in distorted-wave and R-matrix calculations. The values of lambda and Vertical BarchiVertical Bar have been combined to examine the behavior of Vertical BarO/sub 1//sub -//sup colvertical-bar/ (lambda(1-lambda)sinVertical BarchiVertical Bar), the nonvanishing component of orientation. At 27 eV, a substantial decrease was observed in the values of lambda and Vertical BarO/sub 1//submore » -//sup colvertical-bar/, compared with their values for E> or =30 eV.« less

Detachment of Tertiary Dendrite Arms during Controlled Directional Solidification in Aluminum - 7 wt Percent Silicon Alloys: Observations from Ground-based and Microgravity Processed Samples

NASA Technical Reports Server (NTRS)

Grugel, Richard N.; Erdman, Robert; Van Hoose, James R.; Tewari, Surendra; Poirier, David

2012-01-01

Electron Back Scattered Diffraction results from cross-sections of directionally solidified aluminum 7wt% silicon alloys unexpectedly revealed tertiary dendrite arms that were detached and mis-oriented from their parent arm. More surprisingly, the same phenomenon was observed in a sample similarly processed in the quiescent microgravity environment aboard the International Space Station (ISS) in support of the joint US-European MICAST investigation. The work presented here includes a brief introduction to MICAST and the directional solidification facilities, and their capabilities, available aboard the ISS. Results from the ground-based and microgravity processed samples are compared and possible mechanisms for the observed tertiary arm detachment are suggested.

Plasma separation from magnetic field lines in a magnetic nozzle

NASA Technical Reports Server (NTRS)

Kaufman, D. A.; Goodwin, D. G.; Sercel, J. C.

1993-01-01

This paper discusses conditions for separation of a plasma from the magnetic field of a magnetic nozzle. The analysis assumes a collisionless, quasineutral plasma, and therefore the results represent a lower bound on the amount of detachment possible for a given set of plasma conditions. We show that collisionless separation can occur because finite electron mass inhibits the flow of azimuthal currents in the nozzle. Separation conditions are governed by a parameter G which depends on plasma and nozzle conditions. Several methods of improving plasma detachment are presented, including moving the plasma generation zone downstream from the region of strongest magnetic field and using dual magnets to focus the plasma beam. Plasma detachment can be enhanced by manipulation of the nozzle configuration.

Aggregation of Culture Expanded Human Mesenchymal Stem Cells in Microcarrier-based Bioreactor.

PubMed

Yuan, Xuegang; Tsai, Ang-Chen; Farrance, Iain; Rowley, Jon; Ma, Teng

2018-03-15

Three-dimensional aggregation of human mesenchymal stem cells (hMSCs) has been used to enhance their therapeutic properties but current fabrication protocols depend on laboratory methods and are not scalable. In this study, we developed thermal responsive poly(N-isopropylacrylamide) grafted microcarriers (PNIPAM-MCs), which supported expansion and thermal detachment of hMSCs at reduced temperature (23.0 °C). hMSCs were cultured on the PNIPAM-MCs in both spinner flask (SF) and PBS Vertical-Wheel (PBS-VW) bioreactors for expansion. At room temperature, hMSCs were detached as small cell sheets, which subsequently self-assembled into 3D hMSC aggregates in PBS-VW bioreactor and remain as single cells in SF bioreactor owing to different hydrodynamic conditions. hMSC aggregates generated from the bioreactor maintained comparable immunomodulation and cytokine secretion properties compared to the ones made from the AggreWell ® . The results of the current study demonstrate the feasibility of scale-up production of hMSC aggregates in the suspension bioreactor using thermal responsive microcarriers for integrated cell expansion and 3D aggregation in a close bioreactor system and highlight the critical role of hydrodynamics in self-assembly of detached hMSC in suspension.

Quantifying the atomic-level mechanics of single long physisorbed molecular chains.

PubMed

Kawai, Shigeki; Koch, Matthias; Gnecco, Enrico; Sadeghi, Ali; Pawlak, Rémy; Glatzel, Thilo; Schwarz, Jutta; Goedecker, Stefan; Hecht, Stefan; Baratoff, Alexis; Grill, Leonhard; Meyer, Ernst

2014-03-18

Individual in situ polymerized fluorene chains 10-100 nm long linked by C-C bonds are pulled vertically from an Au(111) substrate by the tip of a low-temperature atomic force microscope. The conformation of the selected chains is imaged before and after manipulation using scanning tunneling microscopy. The measured force gradient shows strong and periodic variations that correspond to the step-by-step detachment of individual fluorene repeat units. These variations persist at constant intensity until the entire polymer is completely removed from the surface. Calculations based on an extended Frenkel-Kontorova model reproduce the periodicity and magnitude of these features and allow us to relate them to the detachment force and desorption energy of the repeat units. The adsorbed part of the polymer slides easily along the surface during the pulling process, leading to only small oscillations as a result of the high stiffness of the fluorenes and of their length mismatch with respect to the substrate surface structure. A significant lateral force also is caused by the sequential detachment of individual units. The gained insight into the molecule-surface interactions during sliding and pulling should aid the design of mechanoresponsive nanosystems and devices.

Excess electron is trapped in a large single molecular cage C60F60.

PubMed

Wang, Yin-Feng; Li, Zhi-Ru; Wu, Di; Sun, Chia-Chung; Gu, Feng-Long

2010-01-15

A new kind of solvated electron systems, sphere-shaped e(-)@C60F60 (I(h)) and capsule-shaped e(-)@C60F60 (D6h), in contrast to the endohedral complex M@C60, is represented at the B3LYP/6-31G(d) + dBF (diffusive basis functions) density functional theory. It is proven, by examining the singly occupied molecular orbital (SOMO) and the spin density map of e(-)@C60F60, that the excess electron is indeed encapsulated inside the C60F60 cage. The shape of the electron cloud in SOMO matches with the shape of C60F60 cage. These cage-like single molecular solvated electrons have considerably large vertical electron detachment energies VDE of 4.95 (I(h)) and 4.67 eV (D6h) at B3LYP/6-31+G(3df) + dBF level compared to the VDE of 3.2 eV for an electron in bulk water (Coe et al., Int Rev Phys Chem 2001, 20, 33) and that of 3.66 eV for e(-)@C20F20 (Irikura, J Phys Chem A 2008, 112, 983), which shows their higher stability. The VDE of the sphere-shaped e(-)@C60F60 (I(h)) is greater than that of the capsule-shaped e(-)@C60F60 (D6h), indicating that the excess electron prefers to reside in the cage with the higher symmetry to form the more stable solvated electron. It is also noticed that the cage size [7.994 (I(h)), 5.714 and 9.978 A (D6h) in diameter] is much larger than that (2.826 A) of (H2O)20- dodecahedral cluster (Khan, Chem Phys Lett 2005, 401, 85). Copyright 2009 Wiley Periodicals, Inc.

Benzonitrile: Electron affinity, excited states, and anion solvation

NASA Astrophysics Data System (ADS)

Dixon, Andrew R.; Khuseynov, Dmitry; Sanov, Andrei

2015-10-01

We report a negative-ion photoelectron imaging study of benzonitrile and several of its hydrated, oxygenated, and homo-molecularly solvated cluster anions. The photodetachment from the unsolvated benzonitrile anion to the X ˜ 1 A 1 state of the neutral peaks at 58 ± 5 meV. This value is assigned as the vertical detachment energy (VDE) of the valence anion and the upper bound of adiabatic electron affinity (EA) of benzonitrile. The EA of the lowest excited electronic state of benzonitrile, a ˜ 3 A 1 , is determined as 3.41 ± 0.01 eV, corresponding to a 3.35 eV lower bound for the singlet-triplet splitting. The next excited state, the open-shell singlet A ˜ 1 A 1 , is found about an electron-volt above the triplet, with a VDE of 4.45 ± 0.01 eV. These results are in good agreement with ab initio calculations for neutral benzonitrile and its valence anion but do not preclude the existence of a dipole-bound state of similar energy and geometry. The step-wise and cumulative solvation energies of benzonitrile anions by several types of species were determined, including homo-molecular solvation by benzonitrile, hydration by 1-3 waters, oxygenation by 1-3 oxygen molecules, and mixed solvation by various combinations of O2, H2O, and benzonitrile. The plausible structures of the dimer anion of benzonitrile were examined using density functional theory and compared to the experimental observations. It is predicted that the dimer anion favors a stacked geometry capitalizing on the π-π interactions between the two partially charged benzonitrile moieties.

Quantification and modeling of mechanical degradation in lithium-ion batteries based on nanoscale imaging.

PubMed

Müller, Simon; Pietsch, Patrick; Brandt, Ben-Elias; Baade, Paul; De Andrade, Vincent; De Carlo, Francesco; Wood, Vanessa

2018-06-14

Capacity fade in lithium-ion battery electrodes can result from a degradation mechanism in which the carbon black-binder network detaches from the active material. Here we present two approaches to visualize and quantify this detachment and use the experimental results to develop and validate a model that considers how the active particle size, the viscoelastic parameters of the composite electrode, the adhesion between the active particle and the carbon black-binder domain, and the solid electrolyte interphase growth rate impact detachment and capacity fade. Using carbon-silicon composite electrodes as a model system, we demonstrate X-ray nano-tomography and backscatter scanning electron microscopy with sufficient resolution and contrast to segment the pore space, active particles, and carbon black-binder domain and quantify delamination as a function of cycle number. The validated model is further used to discuss how detachment and capacity fade in high-capacity materials can be minimized through materials engineering.

Chin plate with a detachable C-tube head serves for both osteotomy fixation and orthodontic anchorage.

PubMed

Seo, Kyung-Won; Nahm, Kyung-Yen; Kim, Seong-Hun; Chung, Kyu-Rhim; Nelson, Gerald

2013-07-01

This article reports the dual function of a double-Y miniplate with a detachable C-tube head (C-chin plate; Jin Biomed Co., Bucheon, Korea) used to fixate an anterior segmental osteotomy and provide skeletal anchorage during orthodontic tooth movement. Cases were selected for this study from patients who underwent anterior segmental osteotomy under local anesthesia. A detachable C-tube head portion was combined with a double-Y chin plate. The double-Y chin plates were fixated between the osteotomy segments and the mandibular base with screws in a conventional way. The C-tube head portion exited the tissue near the mucogingival junction. Biocreative Chin Plates were placed on the anterior segmental osteotomy sites. The device allowed 3 points of fixation: 1, minor postosteotomy vertical adjustment of the segment during healing; 2, minor shift of the midline during healing; and 3, to serve as temporary skeletal anchorage device during the post-anterior segmental osteotomy orthodontic treatment. When tooth movement goals are accomplished, the C-tube head of the chin plate can be easily detached from the fixation miniplate by twisting the head using a Weingart plier under local anesthesia. This dual-purpose device spares the patient from the need for 2 separate installations for stabilization of osteotomy segments. The dual-purpose double-Y miniplate combined with a C-tube head (Biocreative Chin Plate) provided versatile application of 3 points of post-osteotomy fixation and of temporary skeletal anchorage for orthodontic tooth movement.

Cohesive detachment of an elastic pillar from a dissimilar substrate

NASA Astrophysics Data System (ADS)

Fleck, N. A.; Khaderi, S. N.; McMeeking, R. M.; Arzt, E.

The adhesion of micron-scale surfaces due to intermolecular interactions is a subject of intense interest spanning electronics, biomechanics and the application of soft materials to engineering devices. The degree of adhesion is sensitive to the diameter of micro-pillars in addition to the degree of elastic mismatch between pillar and substrate. Adhesion-strength-controlled detachment of an elastic circular cylinder from a dissimilar substrate is predicted using a Dugdale-type of analysis, with a cohesive zone of uniform tensile strength emanating from the interface corner. Detachment initiates when the opening of the cohesive zone attains a critical value, giving way to crack formation. When the cohesive zone size at crack initiation is small compared to the pillar diameter, the initiation of detachment can be expressed in terms of a critical value Hc of the corner stress intensity. The estimated pull-off force is somewhat sensitive to the choice of stick/slip boundary condition used on the cohesive zone, especially when the substrate material is much stiffer than the pillar material. The analysis can be used to predict the sensitivity of detachment force to the size of pillar and to the degree of elastic mismatch between pillar and substrate.

Bilateral midperipheral large drusen and retinal pigment epithelial detachments associated with multifocal areas of choroidal neovascularization: a histopathologic study.

PubMed

Tabandeh, Homayoun; Dubovy, Sander; Green, W Richard

2006-01-01

The ocular histopathologic features of a patient with bilateral multiple midperipheral areas of choroidal vascularization, large drusen, and detachments of the retinal pigment epithelium (RPE) are presented. The eyes were obtained at autopsy and fixed in 4% buffered formaldehyde. Serial sections through the macula area and inferior segments were prepared. Light as well as electron microscopy was performed. Microscopic examination disclosed numerous large drusen measuring up to 200 micro m in height and 280 micro m in diameter and areas of serous RPE detachments in the midperiphery of both eyes. Some of the large drusen had choroidal vascularization. Areas of sub-RPE neovascularization that measured up to 6.5 mm in diameter were present in the midperiphery of both eyes. The choroidal origin for neovascularization was evident in 10 areas. A 1-mm area of hemorrhagic detachment of the RPE contiguous with choroidal neovascularization (CNV) was present in the immediate postequatorial area temporally in the left eye. No drusen, basal deposit, or CNV was present in the macular area. Multifocal midperipheral RPE detachments and CNV can occur in the absence of significant age-related macular disease.

Developing physics basis for the snowflake divertor in the DIII-D tokamak

DOE PAGES

Soukhanovskii, V. A.; Allen, S. L.; Fenstermacher, M. E.; ...

2018-02-01

Recent DIII-D results demonstrate that the snowflake (SF) divertor geometry (cf. standard divertor) enables significant manipulation of divertor heat transport for heat spreading and reduction in attached and radiative divertor regimes, between and during edge localized modes (ELMs), while maintaining good H-mode confinement. Snowflake divertor configurations have been realized in the DIII-D tokamak for several seconds in H-mode discharges with heating power PNBImore » $$\\leqslant$$ 4-5 MW and a range of plasma currents Ip = 0.8-1.2 MA. In this work, inter-ELM transport and radiative SF divertor properties are studied. Significant impact of geometric properties on SOL and divertor plasma parameters, including increased poloidal magnetic flux expansion, divertor magnetic field line length and divertor volume, is confirmed. In the SF-minus configuration, heat deposition is affected by the geometry, and peak divertor heat fluxes are significantly reduced. In the SF-plus and near-exact SF configurations, divertor peak heat flux reduction and outer strike point heat flux profile broadening are observed. Inter-ELM sharing of power and particle fluxes between the main and additional snowflake divertor strike points has been demonstrated. The additional strike points typically receive up to 10-15% of total outer divertor power. Measurements of electron pressure and poloidal beta !p support the theoretically proposed churning mode that is driven by toroidal curvature and vertical pressure gradient in the weak poloidal field region. A comparison of the 4-4.5 MW NBI-heated H-mode plasmas with radiative SF divertor and the standard radiative divertor (both induced with additional gas puffing) shows a nearly complete power detachment and broader divertor radiated power distribution in the SF, as compared to a partial detachment and peaked localized radiation in the standard divertor. However, insignificant difference in the detachment onset w.r.t. density between the SF and the standard divertor was found. The results complement the initial SF divertor studies in the NSTX and DIII-D tokamaks and contribute to the physics basis of the SF divertor as a power exhaust concept for future tokamaks.« less

Developing physics basis for the snowflake divertor in the DIII-D tokamak

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

Soukhanovskii, V. A.; Allen, S. L.; Fenstermacher, M. E.

Recent DIII-D results demonstrate that the snowflake (SF) divertor geometry (cf. standard divertor) enables significant manipulation of divertor heat transport for heat spreading and reduction in attached and radiative divertor regimes, between and during edge localized modes (ELMs), while maintaining good H-mode confinement. Snowflake divertor configurations have been realized in the DIII-D tokamak for several seconds in H-mode discharges with heating power PNBImore » $$\\leqslant$$ 4-5 MW and a range of plasma currents Ip = 0.8-1.2 MA. In this work, inter-ELM transport and radiative SF divertor properties are studied. Significant impact of geometric properties on SOL and divertor plasma parameters, including increased poloidal magnetic flux expansion, divertor magnetic field line length and divertor volume, is confirmed. In the SF-minus configuration, heat deposition is affected by the geometry, and peak divertor heat fluxes are significantly reduced. In the SF-plus and near-exact SF configurations, divertor peak heat flux reduction and outer strike point heat flux profile broadening are observed. Inter-ELM sharing of power and particle fluxes between the main and additional snowflake divertor strike points has been demonstrated. The additional strike points typically receive up to 10-15% of total outer divertor power. Measurements of electron pressure and poloidal beta !p support the theoretically proposed churning mode that is driven by toroidal curvature and vertical pressure gradient in the weak poloidal field region. A comparison of the 4-4.5 MW NBI-heated H-mode plasmas with radiative SF divertor and the standard radiative divertor (both induced with additional gas puffing) shows a nearly complete power detachment and broader divertor radiated power distribution in the SF, as compared to a partial detachment and peaked localized radiation in the standard divertor. However, insignificant difference in the detachment onset w.r.t. density between the SF and the standard divertor was found. The results complement the initial SF divertor studies in the NSTX and DIII-D tokamaks and contribute to the physics basis of the SF divertor as a power exhaust concept for future tokamaks.« less

The Detached Haze Layer in Titan's Mesosphere

NASA Astrophysics Data System (ADS)

Lavvas, P.; Yelle, R. V.; Vuitton, V.

2008-12-01

The Cassini observations reveal the presence of a detached haze layer in Titan's mesosphere at an altitude of 520 km, well above the stratosphere. Observations of scattered light made by the Imaging Science Subsystem (ISS) reveal a clearly defined layer encircling low and mid-latitude regions. The aerosol layer is also detected in stellar occultation measurements of UV extinction by the UltraViolet Imaging Spectrometer (UVIS). The haze is a global and permanent feature of Titan's atmosphere. Furthermore the location of the detached haze layer is coincident with and the likely cause of a local maximum in the temperature profile measured by the Huygens Atmospheric Structure Instrument (HASI). This temperature inversion is also permanent and global, having been detected in ground-based stellar occultations. The correlation between the extinction profile and the temperature maximum imply that the detached haze cannot be due to condensation, as previously suggested. Previously, Voyager high phase angle images at 500 nm revealed a detached haze layer near 350 km, more than 150 km lower than the Cassini layer. Close examination of the Voyager images suggests that the Cassini detached layer at 520 km is a separate phenomenon rather than a change in the Voyager detached layer. Analysis of the observed optical properties suggests that the average size of particles in the Cassini detached layer is < 45 nm, with an imaginary index k < 0.3 at 187.5 nm, while Non-LTE calculations of the temperature perturbation induced by the detached haze show that the average particle size must be greater than 35 nm for reproducing the heating rate implied by the HASI temperature profile. Calculation of the sedimentation velocity of the particles, coupled with the derived number density, imply a mass flux of 1.9-3.2 × 10-14 g cm-2 s-1. This is approximately equal to the mass flux required to explain the main haze layer and suggests that the stratospheric haze is formed primarily by sedimentation and coagulation of particles in the detached layer. This is further supported from the particle size range retrieved for the detached layer (35-45 nm), being approximately equal to the radii of ~50 nm for the monomers of the aggregate aerosols in the main haze layer. It follows that aerosols on Titan are formed primarily in the thermosphere, rather than the stratosphere as assumed in many pre-Cassini studies. This is consistent with the detection of negatively charged aerosols in the thermosphere by Cassini/CAPS. These conclusions are supported by microphysical aerosol models that couple the detached haze layer and the main haze layer and extend into the thermosphere. Our calculations suggest that the detached haze layer is due to the transition in the growth of particles from spherical shape to aggregates of fractal structure. The rapid increase in the size of the particles with the onset of fractal growth, in combination with the decrease of their settling velocity, casts them invisible in the transition region. This optical illusion process explains the well-defined and symmetric structure of the detached layer, something difficult to explain under a pure advection scenario. Further investigation of the processes defining the growth of the particles is required in order to understand why the transition takes place at this region and how the particles produced at higher altitudes by high energy radical and ion chemistry, are defining the vertical haze opacity in Titan's atmosphere.

Spatiotemporal dynamics of charged species in the afterglow of plasmas containing negative ions.

PubMed

Kaganovich, I D; Ramamurthi, B N; Economou, D J

2001-09-01

The spatiotemporal evolution of charged species densities and wall fluxes during the afterglow of an electronegative discharge has been investigated. The decay of a plasma with negative ions consists of two stages. During the first stage of the afterglow, electrons dominate plasma diffusion and negative ions are trapped inside the vessel by the static electric field; the flux of negative ions to the walls is nearly zero. During this stage, the electron escape frequency increases considerably in the presence of negative ions, and can eventually approach free electron diffusion. During the second stage of the afterglow, electrons have disappeared, and positive and negative ions diffuse to the walls with the ion-ion ambipolar diffusion coefficient. Theories for plasma decay have been developed for equal and strongly different ion (T(i)) and electron (T(e)) temperatures. In the case T(i)=T(e), the species spatial profiles are similar and an analytic solution exists. When detachment is important in the afterglow (weakly electronegative gases, e.g., oxygen) the plasma decay crucially depends on the product of negative ion detachment frequency (gamma(d)) and diffusion time (tau(d)). If gamma(d)tau(d)>2, negative ions convert to electrons during their diffusion towards the walls. The presence of detached electrons results in "self-trapping" of the negative ions, due to emerging electric fields, and the negative ion flux to the walls is extremely small. In the case T(i)

AT base pair anions versus (9-methyl-A)(1-methyl-T) base pair anions.

PubMed

Radisic, Dunja; Bowen, Kit H; Dabkowska, Iwona; Storoniak, Piotr; Rak, Janusz; Gutowski, Maciej

2005-05-04

The anionic base pairs of adenine and thymine, (AT)(-), and 9-methyladenine and 1-methylthymine, (MAMT)(-), have been investigated both theoretically and experimentally in a complementary, synergistic study. Calculations on (AT)(-) found that it had undergone a barrier-free proton transfer (BFPT) similar to that seen in other dimer anion systems and that its structural configuration was neither Watson-Crick (WC) nor Hoogsteen (HS). The vertical detachment energy (VDE) of (AT)(-) was determined by anion photoelectron spectroscopy and found to be in agreement with the VDE value predicted by theory for the BFPT mechanism. An AT pair in DNA is structurally immobilized into the WC configuration, in part, by being bonded to the sugars of the double helix. This circumstance was mimicked by methylating the sites on both A and T where these sugars would have been tied, viz., 9-methyladenine and 1-methylthymine. Calculations found no BFPT in (MAMT)(-) and a resulting (MAMT)(-) configuration that was either HS or WC, with the configurations differing in stability by ca. 2 kcal/mol. The photoelectron spectrum of (MAMT)(-) occurred at a completely different electron binding energy than had (AT)(-). Moreover, the VDE value of (MAMT)(-) was in agreement with that predicted by theory. The configuration of (MAMT)(-) and its lack of electron-induced proton transfer are inter-related. While there may be other pathways for electron-induced DNA alterations, BFPT in the WC/HS configurations of (AT)(-) is not feasible.

Onyx embolization with the Apollo detachable tip microcatheter: A single-center experience.

PubMed

Miller, Timothy R; Giacon, Luciano; Kole, Matthew J; Chen, Rong; Jindal, Gaurav; Gandhi, Dheeraj

2018-06-01

Purpose The Apollo Onyx Delivery Microcatheter (Ev3, Irvine, CA) is a detachable-tip microcatheter that was developed to reduce the risk of microcatheter entrapment during ethylene-vinyl alcohol copolymer (Onyx) embolizations. We report our experience with the microcatheter in a variety of neurointerventional procedures. Methods We retrospectively reviewed all Onyx embolizations performed in the head, neck, and spine using the Apollo Onyx Delivery Microcatheter from its introduction at our institution in July 2014 to August 2016. Information regarding patient diagnoses, procedural details, as well as clinical outcomes were obtained from the electronic medical record, procedure reports, and relevant angiographic imaging. Results A total of 58 arterial pedicle Onyx embolizations were performed in 37 patients. There were no cases of microcatheter entrapment, early/inadvertent tip detachment, or vessel injury upon removal of the device. There were two instances (3.5%) of leakage of Onyx from the microcatheter detachment site during embolization, which did not result in adverse sequelae. Clinical outcomes were excellent, with nearly all embolizations achieving the intended goal. In multivariate analysis, length of Onyx reflux along the microcatheter tip and utilization of a higher viscosity agent, Onyx 34, were significantly associated with tip detachment. Conclusion The use of the Apollo Microcatheter is both safe and effective during neurointerventional embolizations using Onyx. Leakage of liquid embolic agent from the detachment site is an infrequent technical complication that may be encountered with the device.

Shortening accommodated by extension-parallel folding of detachment faults during oblique rifting in the Gulf of California

NASA Astrophysics Data System (ADS)

Seiler, Christian; Fletcher, John

2013-04-01

Large-scale fault corrugations or megamullions are a common feature of detachment faults and form either as original fault grooves, displacement-gradient folds or constrictional folds parallel to the extension direction. In highly oblique extensional settings such as the Gulf of California, horizontal shortening perpendicular to the extension direction is an inherent part of the regional stress field and likely forms a key factor during the development of extension-parallel fault corrugations. However, the amount of horizontal shortening absorbed by megamullions is difficult to quantify, and constrictional folding is not normally thought to accommodate significant strike-slip deformation. The Las Cuevitas and Santa Rosa detachments are two low-angle normal fault systems exposed on the Gulf of California rifted margin in northeastern Baja California, Mexico. The two detachments accommodate between ~7-9km of SE-directed extension and represent the next significant set of faults in direction of transport from the rift breakaway fault. Fault kinematics are highly complex, but suggest integrated normal, oblique- and strike-slip faulting, with kinematics controlled by the orientation of faults with respect to the regional transtensional stress field. Both fault systems are strongly corrugated, with megamullion amplitudes of ~4-7km and half wavelenghts of between ~15 to 20km. Differential folding of the syntectonic basin-fill of the supradetachment basins strongly suggest that the observed megamullions formed largely, though not exclusively, due to constrictional folding associated with the transtensional stress regime of the plate boundary. This is consistent with basin-scale facies variations that record differential uplift and subsidence in antiformal and synformal megamullion domains, respectively. Compared to the two detachments, the San Pedro Martir fault - the master fault of the rift system at this latitude - shows more subtle fault corrugations with amplitudes of <3km. Unlike the Las Cuevitas and Santa Rosa detachments, though, there is no evidence for constrictional folding on the San Pedro Martir fault. Instead, the observed corrugations likely represent original grooves of the fault plane, formed as adjacent fault nuclei joined along-strike during fault growth. Comparison between the sinuosity of the San Pedro Martir fault (1.08), attributed entirely to original fault asperities, with the sinuosity of the two detachment systems (Las Cuevitas detachment: 1.17, Santa Rosa detachment: 1.22), suggests that about 10% of shortening occurred on each of the two detachments due to synextensional constrictional folding. This corresponds to a combined total of ~8km of N-S shortening, or ~10km of dextral shear resolved in direction of the relative plate motion, and occurs in addition to ~21km of right-lateral strain accommodated by clockwise vertical-axis block rotations. Thus, strain in this part of the rift system was partitioned between discrete extensional faulting on the two detachment systems, and significant right-lateral shear accommodated by distributed volume deformation.

A technological advance for 21st century obstetricians: the electronically-controlled vacuum extractor.

PubMed

Perone, Nicola

2018-04-25

To describe an innovative electronically-controlled vacuum extractor (VE) in detail and to illustrate its performance characteristics, as observed in a laboratory study. Thirty simulated, vacuum-assisted deliveries. (1) The ability to measure in real-time of the pull applied and to sound an alert, when the traction approaches the negative pressure under the cup, to prevent its detachment. (2) The recording and printing of a graphic representation of the pull applied (vacuum delivery graph). (3) The emission of a warning signal when the 15-min time limit of continuous cup application on the fetal scalp, is reached. No cup detachment occurred in any of the 15 vacuum-assisted deliveries, in which traction was kept below the adhesive force of the cup [44 lb (20 kg)], except in three cases, due to loss of negative pressure. In the remaining 15 tests, in which traction was greater than the adhesive force of the cup, "pull-offs" inevitably occurred. Furthermore, upon reaching the 15-min time limit of continuous cup application on the fetal cephalic model, a warning signal was emitted, as programmed. Conclusions We demonstrated that the electronically-controlled VE, with its distinctive pull-sensing handle, performs suitably for its intended purposes. The ability of the modernized device to decrease the incidence of cup detachment, secondary to the inadvertent application of excessive traction, may result in considerable safety, medico-legal and didactic advantages.

Benchmark calculations of excess electrons in water cluster cavities: balancing the addition of atom-centered diffuse functions versus floating diffuse functions.

PubMed

Zhang, Changzhe; Bu, Yuxiang

2016-09-14

Diffuse functions have been proved to be especially crucial for the accurate characterization of excess electrons which are usually bound weakly in intermolecular zones far away from the nuclei. To examine the effects of diffuse functions on the nature of the cavity-shaped excess electrons in water cluster surroundings, both the HOMO and LUMO distributions, vertical detachment energies (VDEs) and visible absorption spectra of two selected (H2O)24(-) isomers are investigated in the present work. Two main types of diffuse functions are considered in calculations including the Pople-style atom-centered diffuse functions and the ghost-atom-based floating diffuse functions. It is found that augmentation of atom-centered diffuse functions contributes to a better description of the HOMO (corresponding to the VDE convergence), in agreement with previous studies, but also leads to unreasonable diffuse characters of the LUMO with significant red-shifts in the visible spectra, which is against the conventional point of view that the more the diffuse functions, the better the results. The issue of designing extra floating functions for excess electrons has also been systematically discussed, which indicates that the floating diffuse functions are necessary not only for reducing the computational cost but also for improving both the HOMO and LUMO accuracy. Thus, the basis sets with a combination of partial atom-centered diffuse functions and floating diffuse functions are recommended for a reliable description of the weakly bound electrons. This work presents an efficient way for characterizing the electronic properties of weakly bound electrons accurately by balancing the addition of atom-centered diffuse functions and floating diffuse functions and also by balancing the computational cost and accuracy of the calculated results, and thus is very useful in the relevant calculations of various solvated electron systems and weakly bound anionic systems.

High-resolution three-dimensional imaging and analysis of rock falls in Yosemite valley, California

USGS Publications Warehouse

Stock, Gregory M.; Bawden, G.W.; Green, J.K.; Hanson, E.; Downing, G.; Collins, B.D.; Bond, S.; Leslar, M.

2011-01-01

We present quantitative analyses of recent large rock falls in Yosemite Valley, California, using integrated high-resolution imaging techniques. Rock falls commonly occur from the glacially sculpted granitic walls of Yosemite Valley, modifying this iconic landscape but also posing signifi cant potential hazards and risks. Two large rock falls occurred from the cliff beneath Glacier Point in eastern Yosemite Valley on 7 and 8 October 2008, causing minor injuries and damaging structures in a developed area. We used a combination of gigapixel photography, airborne laser scanning (ALS) data, and ground-based terrestrial laser scanning (TLS) data to characterize the rock-fall detachment surface and adjacent cliff area, quantify the rock-fall volume, evaluate the geologic structure that contributed to failure, and assess the likely failure mode. We merged the ALS and TLS data to resolve the complex, vertical to overhanging topography of the Glacier Point area in three dimensions, and integrated these data with gigapixel photographs to fully image the cliff face in high resolution. Three-dimensional analysis of repeat TLS data reveals that the cumulative failure consisted of a near-planar rock slab with a maximum length of 69.0 m, a mean thickness of 2.1 m, a detachment surface area of 2750 m2, and a volume of 5663 ?? 36 m3. Failure occurred along a surfaceparallel, vertically oriented sheeting joint in a clear example of granitic exfoliation. Stress concentration at crack tips likely propagated fractures through the partially attached slab, leading to failure. Our results demonstrate the utility of high-resolution imaging techniques for quantifying far-range (>1 km) rock falls occurring from the largely inaccessible, vertical rock faces of Yosemite Valley, and for providing highly accurate and precise data needed for rock-fall hazard assessment. ?? 2011 Geological Society of America.

Assessment of the posterior segment of the cat eye by optical coherence tomography (OCT).

PubMed

Gekeler, Florian; Gmeiner, Helmut; Völker, Michael; Sachs, Helmut; Messias, Andre; Eule, Corinna; Bartz-Schmidt, Karl Ulrich; Zrenner, Eberhart; Shinoda, Kei

2007-01-01

To assess the feasibility of optical coherence tomography (OCT) for examining the cat ocular fundus, to provide normative data on retinal thickness in different fundus regions, and to demonstrate selected surgically induced vitreoretinal pathologies in the cat. Forty-five eyes of 28 healthy domestic cats and two eyes of domestic cats that had undergone subretinal implantation surgery for a visual prosthesis were examined. An optical coherence tomograph (Zeiss-Humphrey) was used to examine the anesthetized animals. At least five vertical and five horizontal scans in regular distribution were recorded for each cat including (1) the peripapillary region, (2) the area centralis, and (3) the peripheral retina. Thickness was measured manually at five locations in each scan. Retinal thickness was compared in the three above-mentioned fundus regions, between eyes and between vertical and horizontal scans. OCT was additionally performed in animals with retinal detachment and a subretinal visual prosthesis. OCT measurements required only minimal adjustments of human settings and yielded high quality images. In comparison to humans intraretinal layers were more difficult to differentiate. Retinal thickness was highest in the peripapillary region (245 +/- 21 microm), followed by the peripheral retina (204 +/- 11 microm) and the area centralis (182 +/- 11 microm; all P < 0.0001). There was no statistically significant difference between right and left eye or between vertical and horizontal scans. OCT demonstrated retinal detachment, an iatrogenic break and a subretinal prosthetic device in high detail. Retinal thickness was measurable with high precision; values compare well to older histologic studies. OCT bears significant advantages over histology in enabling one to repeat measurements in living animals and thus allowing longitudinal studies. Various vitreoretinal pathologies common in feline eyes are detectable and quantifiable by OCT.

The detached haze layer in Titan's mesosphere: The formation process

NASA Astrophysics Data System (ADS)

Lavvas, P.; Yelle, R. V.; Vuitton, V.

2008-09-01

Cassini observations made by the Imaging Science Subsystem (ISS) [1] and by the UltraViolet Imaging Spectrometer (UVIS) [2,3] have revealed the presence of a detached haze layer in Titan's mesosphere at an altitude of 520 km. Analysis of the observed optical properties presented in the accompanying talk [5], suggests that the average size of particles in the detached layer is of ~40 nm, with an imaginary index k < 0.3 at 187.5 nm and a number density of ˜30 particles cm-3, while calculations of the sedimentation velocity of the haze particles coupled with the derived number density imply a mass flux of 1.9-3.2 × 10-14 g cm-2 s-1. This is approximately equal to the mass flux required to explain the main haze layer and suggests that the main haze layer in Titan's stratosphere is formed primarily by sedimentation and coagulation of particles in the detached layer [5,6]. The HASI data clearly show that the haze is coincident with a temperature maximum. This rules out condensation as the source of the detached haze. We have also considered a more complicated scenario in which the detached layer is caused by an increase in the density of condensation nuclei near 520 km. This is motivated by the fact that silicate micrometeorites ablate near 500 km [7,8]. Recondensation of the refractory vapor creates `smoke' particles that could serve as condensation nuclei. Combination of Pioneer measurements along with theoretical estimations for the particles velocity distribution, suggest a mass flux of ~10-17 g cm-2 s-1 at Saturn's region [9], while measurements from the Cassini Dust Analyser (CDA) suggest a similar magnitude at Titan's location [10]. These fluxes are ~3 orders of magnitude smaller than the lower limit of the estimated mass flux out of the detached haze layer, so meteorite ablation can not be the direct cause of the aerosol layer. However, if the ablated meteoritic material reforms 1 nm particles, the implied number flux would be 2.4 × 103 particles cm-2 s-1, which is of the right order of magnitude to explain the detached layer. This hypothesis requires that additional material condense on the meteoritic smoke particles. Unfortunately, the main photochemical products on Titan (HCN, C2H2, C2H6, etc.) do not condense at the temperature and pressure in the detached layer. The saturation mixing ratio for species present in Titan's mesosphere are shown in Fig. 1. The vapour pressure of each species is calculated assuming the HASI vertical temperature profile [4]. The species that come closest to condensing are H2O and C6N2. There is some water vapor present from ablation of icy micrometeorites in Titan's atmosphere, but the mole fraction corresponding to saturation vapor pressure of water at 520 km is 1.6 × 10-2, many orders of magnitude larger than expected [11]. Similarly, the mole fraction of C6N2 at 520 km is expected to be much smaller than the saturation value of 5 × 10-6 [12]. Hence, the growth of particles through condensation cannot explain the detached haze layer. Advection processes in the atmosphere have been related to the formation of the Voyager detached haze layer [13]. In this picture, meridional winds transport the haze particles polewards, constraining them at a specific altitude region, before depositing them at the pole, while the upwelling part of the circulation transports large particles from the main haze layer upwards, enhancing in this way the opacity of the detached haze layer. Yet, the meridional winds are estimated to be υ~3 cm s-1 in the region of the stratospheric zonal jet near 0.1 mbar based on CIRS measurements [14]. Assuming this value to hold in the region of the detached haze layer implies a horizontal motion characteristic time of H~R/v = 108 s. A 40 nm particle has a settling velocity of υ S~1 cm s-1 at 500 km, and the characteristic time to fall 20 km is only 2 × 106 s implying that the particles fall out of the region before they are transported to the pole. Thus, the dynamical explanation for the Voyager detached haze fails by more than a factor of 50 for the detached layer at 520 km. The inefficiency of the above processes to provide enough mass flux to generate the detached layer along with the large mass flux retrieved by the observations [5,6] suggest that haze is formed in Titan's thermosphere by high-energy radical and ion chemistry. In this case the presence of the detached layer could be an optical illusion effect due to the increase of particles' size, along with the decrease of their settling velocity with decreasing altitude. In order to investigate this effect we used a microphysical model [15], which has been extended to describe both spherical and fractal particle growth [16]. We assume a gaussian production profile centered at 800 km and with a column mass production of 4.5 × 10-14 g cm-2 s-1. The particles grow as spheres or fractals depending on the fractal dimension, Df, (Df=2 for fractals and 3 for spheres). Using only spherical particle growth provides a good fit to the extinction observed by UVIS at 187.5 nm [3] above the detached haze layer, while the modeled extinction drops faster than the observed extinction at altitudes below the detached layer (Fig. 2). By setting the transition altitude of spherical to fractal growth at 510 km, the generated fractal particles provide an excellent fit to the observed extinction profile below the detached layer suggesting that the particles present there are indeed of fractal structure. At the same time, the transition from spheres to fractals aggregates, generates a well pronounced minimum in the total simulated extinction, which provides a very good fit to the observed detached haze layer extinction profile [3]. In addition, the calculated mass flux at 520 km is 3.1 × 10-14 g cm-2 s-1, which is within the limits defined by the optical analysis of the detached layer [5,6]. Finally, the calculated monomer size of the particles forming the fractal aggregates is 57 nm, is good agreement with the 50 nm size retrieved by the DISR measurements [17]. Our simulation of Titan's haze particle evolution suggests that the presence of the detached haze layer is due to the transition in the growth of particles from spherical to fractal structure. Further investigation of the processes defining the growth of the particles is required in order to understand why the transition takes place at this region and how the particles produced at higher altitudes are defining the vertical haze opacity in Titan's atmosphere.

Initial hydration processes of magnesium chloride: size-selected anion photoelectron spectroscopy and ab initio calculations.

PubMed

Feng, Gang; Liu, Cheng-Wen; Zeng, Zhen; Hou, Gao-Lei; Xu, Hong-Guang; Zheng, Wei-Jun

2017-06-14

To understand the initial hydration processes of MgCl 2 , we measured photoelectron spectra of MgCl 2 (H 2 O) n - (n = 0-6) and conducted ab initio calculations on MgCl 2 (H 2 O) n - and their neutral counterparts up to n = 7. A dramatic drop in the vertical detachment energy (VDE) was observed upon addition of the first water molecule to bare MgCl 2 - . This large variation in VDE can be associated with the charge-transfer-to-solvent (CTTS) effect occurring in the MgCl 2 (H 2 O) n - clusters, as hydration induces transfer of the excess electron of MgCl 2 - to the water molecules. Investigation of the separation of Cl - -Mg 2+ ion pair shows that, in MgCl 2 (H 2 O) n - anions, breaking of the first Mg-Cl bond occurs at n = 4, while breaking of the second Mg-Cl bond takes place at n = 6. For neutral MgCl 2 (H 2 O) n clusters, breaking of the first Mg-Cl bond starts at n = 7.

Theoretical study on the spectroscopic properties of CO3(*-).nH2O clusters: extrapolation to bulk.

PubMed

Pathak, Arup K; Mukherjee, Tulsi; Maity, Dilip K

2008-10-24

Vertical detachment energies (VDE) and UV/Vis absorption spectra of hydrated carbonate radical anion clusters, CO(3)(*-).nH(2)O (n=1-8), are determined by means of ab initio electronic structure theory. The VDE values of the hydrated clusters are calculated with second-order Moller-Plesset perturbation (MP2) and coupled cluster theory using the 6-311++G(d,p) set of basis functions. The bulk VDE value of an aqueous carbonate radical anion solution is predicted to be 10.6 eV from the calculated weighted average VDE values of the CO(3)(*-).nH(2)O clusters. UV/Vis absorption spectra of the hydrated clusters are calculated by means of time-dependent density functional theory using the Becke three-parameter nonlocal exchange and the Lee-Yang-Parr nonlocal correlation functional (B3LYP). The simulated UV/Vis spectrum of the CO(3)(*-).8H(2)O cluster is in excellent agreement with the reported experimental spectrum for CO(3)(*-) (aq), obtained based on pulse radiolysis experiments.

Microhydration of cytosine and its radical anion: cytosine.(H2O)n (n=1-5).

PubMed

Kim, Sunghwan; Schaefer, Henry F

2007-02-14

Microhydration effects on cytosine and its radical anion have been investigated theoretically, by explicitly considering various structures of cytosine complexes with up to five water molecules. Each successive water molecule (through n=5) is bound by 7-10 kcal mol(-1) to the relevant cytosine complex. The hydration energies are uniformly higher for the analogous anion systems. While the predicted vertical detachment energy (VDE) of the isolated cytosine is only 0.48 eV, it is predicted to increase to 1.27 eV for the lowest-lying pentahydrate of cytosine. The adiabatic electron affinity (AEA) of cytosine was also found to increase from 0.03 to 0.61 eV for the pentahydrate, implying that the cytosine anion, while questionable in the gas phase, is bound in aqueous solution. Both the VDE and AEA values for cytosine are smaller than those of uracil and thymine for a given hydration number. These results are in qualitative agreement with available experimental results from photodetachment-photoelectron spectroscopy studies of Schiedt et al. [Chem. Phys. 239, 511 (1998)].

Microhydration of cytosine and its radical anion: Cytosine.(H2O)n (n=1-5)

NASA Astrophysics Data System (ADS)

Kim, Sunghwan; Schaefer, Henry F.

2007-02-01

Microhydration effects on cytosine and its radical anion have been investigated theoretically, by explicitly considering various structures of cytosine complexes with up to five water molecules. Each successive water molecule (through n =5) is bound by 7-10kcalmol-1 to the relevant cytosine complex. The hydration energies are uniformly higher for the analogous anion systems. While the predicted vertical detachment energy (VDE) of the isolated cytosine is only 0.48eV, it is predicted to increase to 1.27eV for the lowest-lying pentahydrate of cytosine. The adiabatic electron affinity (AEA) of cytosine was also found to increase from 0.03to0.61eV for the pentahydrate, implying that the cytosine anion, while questionable in the gas phase, is bound in aqueous solution. Both the VDE and AEA values for cytosine are smaller than those of uracil and thymine for a given hydration number. These results are in qualitative agreement with available experimental results from photodetachment-photoelectron spectroscopy studies of Schiedt et al. [Chem. Phys. 239, 511 (1998)].

Single Stage Tandem Mass Spectrometry Assignment of the C-5 Uronic Acid Stereochemistry in Heparan Sulfate Tetrasaccharides using Electron Detachment Dissociation

NASA Astrophysics Data System (ADS)

Agyekum, Isaac; Zong, Chengli; Boons, Geert-Jan; Amster, I. Jonathan

2017-09-01

The analysis of heparan sulfate (HS) glycosaminoglycans presents many challenges, due to the high degree of structural heterogeneity arising from their non-template biosynthesis. Complete structural elucidation of glycosaminoglycans necessitates the unambiguous assignments of sulfo modifications and the C-5 uronic acid stereochemistry. Efforts to develop tandem mass spectrometric-based methods for the structural analysis of glycosaminoglycans have focused on the assignment of sulfo positions. The present work focuses on the assignment of the C-5 stereochemistry of the uronic acid that lies closest to the reducing end. Prior work with electron-based tandem mass spectrometry methods, specifically electron detachment dissociation (EDD), have shown great promise in providing stereo-specific product ions, such as the B3 ´ -CO2, which has been found to distinguish glucuronic acid (GlcA) from iduronic acid (IdoA) in some HS tetrasaccharides. The previously observed diagnostic ions are generally not observed with 2- O-sulfo uronic acids or for more highly sulfated heparan sulfate tetrasaccharides. A recent study using electron detachment dissociation and principal component analysis revealed a series of ions that correlate with GlcA versus IdoA for a set of 2- O-sulfo HS tetrasaccharide standards. The present work comprehensively investigates the efficacy of these ions for assigning the C-5 stereochemistry of the reducing end uronic acid in 33 HS tetrasaccharides. A diagnostic ratio can be computed from the sum of the ions that correlate to GlcA to those that correlate to IdoA. [Figure not available: see fulltext.

Proceedings of the Electronics Manufacturing Seminar (14th Annual) Held in China Lake, California on 21-22 February 1990

DTIC Science & Technology

1990-02-01

Aging effects Aging of metalic surfaces Aqueous cleaning Circuit- card assembly Cleanability Closed-loop soldering Conformal coating Defect...5 Standard Electronic Circuit Card Assembly System ....................................... 7 Douglas Green Lockheed-Sanders Corp. Nashua, New...Facility Naval Weapons Center NAVIRSA Detachment 5 NWC TP 7066 EMPF TR 0010 STANDARD ELECTRONIC CIRCUTT CARD ASSEMBLY SYSTEM (SECAS PROJECT) by Douglas

Paleomagnetic quantification of upper-plate deformation during Miocene detachment faulting in the Mohave Mountains, Arizona

USGS Publications Warehouse

Pease, V.; Hillhouse, J.W.; Wells, R.E.

2005-01-01

Paleomagnetic data from Miocene (???20 Ma) volcanic rocks and dikes of west central Arizona reveal the tilt history of Proterozoic crystalline rocks in the hanging wall of the Chemehuevi-Whipple Mountains detachment fault. We obtained magnetization data from dikes and flows in two structural blocks encompassing Crossman Peak and Standard Wash in the Mohave Mountains. In the Crossman block the dike swarm records two components of primary magnetization: (1) CNH, a normal polarity, high-unblocking-temperature or high-coercivity component (inclination, I = 48.5??, declination, D = 6.4??), and (2) CRHm, a reversed polarity, high-temperature or high-coercivity component (I = -33.6??, D = 197.5??). Argon age spectra imply that the dikes have not been reheated above 300??C since their emplacement, and a baked-contact test suggests that the magnetization is likely to be Miocene in age. CRHm deviates from the expected direction of the Miocene axial dipole field and is best explained as a result of progressive tilting about the strike of the overlying andesite flows. These data suggest that the Crossman block was tilted 60?? to the southwest prior to intrusion of the vertical dike swarm, and the block continued to tilt during a magnetic field reversal to normal polarity (CNH). Miocene dikes in the Crossman block are roughly coplanar, so the younger dikes with normal polarity magnetization intruded along planes of weakness parallel to the earlier reversed polarity swarm. An alternative explanation involves CNH magnetization being acquired later during hydrothermal alteration associated with the final stages of dike emplacement. In the Standard Wash block, the primary component of magnetization is a dual-polarity, high-temperature or high-coercivity component (SWHl, I = 7.2??,D= 0.7??). To produce agreement between the expected Miocene magnetic direction and the SWH component requires (1) correcting for a 56?? tilt about the strike of flow bedding and (2) removing a counterclockwise vertical-axis rotation of 20??. The two rotations restore the Standard Wash dikes to vertical, make parallel the dike layering in the Crossman and Standard Wash blocks, and align the strikes of bedding in both blocks. Geologic mapping, geochemical evidence, and paleomagnetic data are consistent with the upper plate of the Mohave Mountains having tilted in response to formation of the underlying detachment fault.

A combined photoelectron spectroscopy and relativistic ab initio studies of the electronic structures of UFO and UFO(-).

PubMed

Roy, Soumendra K; Jian, Tian; Lopez, Gary V; Li, Wei-Li; Su, Jing; Bross, David H; Peterson, Kirk A; Wang, Lai-Sheng; Li, Jun

2016-02-28

The observation of the gaseous UFO(-) anion is reported, which is investigated using photoelectron spectroscopy and relativisitic ab initio calculations. Two strong photoelectron bands are observed at low binding energies due to electron detachment from the U-7sσ orbital. Numerous weak detachment bands are also observed due to the strongly correlated U-5f electrons. The electron affinity of UFO is measured to be 1.27(3) eV. High-level relativistic quantum chemical calculations have been carried out on the ground state and many low-lying excited states of UFO to help interpret the photoelectron spectra and understand the electronic structure of UFO. The ground state of UFO(-) is linear with an O-U-F structure and a (3)H4 spectral term derived from a U 7sσ(2)5fφ(1)5fδ(1) electron configuration, whereas the ground state of neutral UFO has a (4)H(7/2) spectral term with a U 7sσ(1)5fφ(1)5fδ(1) electron configuration. Strong electron correlation effects are found in both the anionic and neutral electronic configurations. In the UFO neutral, a high density of electronic states with strong configuration mixing is observed in most of the scalar relativistic and spin-orbit coupled states. The strong electron correlation, state mixing, and spin-orbit coupling of the electronic states make the excited states of UFO very challenging for accurate quantum chemical calculations.

A combined photoelectron spectroscopy and relativistic ab initio studies of the electronic structures of UFO and UFO-

NASA Astrophysics Data System (ADS)

Roy, Soumendra K.; Jian, Tian; Lopez, Gary V.; Li, Wei-Li; Su, Jing; Bross, David H.; Peterson, Kirk A.; Wang, Lai-Sheng; Li, Jun

2016-02-01

The observation of the gaseous UFO- anion is reported, which is investigated using photoelectron spectroscopy and relativisitic ab initio calculations. Two strong photoelectron bands are observed at low binding energies due to electron detachment from the U-7sσ orbital. Numerous weak detachment bands are also observed due to the strongly correlated U-5f electrons. The electron affinity of UFO is measured to be 1.27(3) eV. High-level relativistic quantum chemical calculations have been carried out on the ground state and many low-lying excited states of UFO to help interpret the photoelectron spectra and understand the electronic structure of UFO. The ground state of UFO- is linear with an O-U-F structure and a 3H4 spectral term derived from a U 7sσ25fφ15fδ1 electron configuration, whereas the ground state of neutral UFO has a 4H7/2 spectral term with a U 7sσ15fφ15fδ1 electron configuration. Strong electron correlation effects are found in both the anionic and neutral electronic configurations. In the UFO neutral, a high density of electronic states with strong configuration mixing is observed in most of the scalar relativistic and spin-orbit coupled states. The strong electron correlation, state mixing, and spin-orbit coupling of the electronic states make the excited states of UFO very challenging for accurate quantum chemical calculations.

Optogalvanic photodetachment spectroscopy

NASA Technical Reports Server (NTRS)

Mcdermid, I. S.; Webster, C. R.

1983-01-01

A new extension to optogalvanic spectroscopy, in which electrons detached from negative ions formed in the discharge are observed as a function of incident laser wavelength, has been developed. The determination of the electron affinities of I(-) and Cl(-) atomic ions is described. The potential of the technique for studying the spectroscopy of molecular negative ions is also discussed.

Aharonov-Bohm Effect in the Photodetachment Microscopy of Hydrogen Negative Ions in an Electric Field

NASA Astrophysics Data System (ADS)

Wang, Dehua

2014-09-01

The Aharonov-Bohm (AB) effect in the photodetachment microscopy of the H- ions in an electric field has been studied on the basis of the semiclassical theory. After the H- ion is irradiated by a laser light, they provide a coherent electron source. When the detached electron is accelerated by a uniform electric field, two trajectories of a detached electron which run from the source to the same point on the detector, will interfere with each other and lead to an interference pattern in the photodetachment microscopy. After the solenoid is electrified beside the H- ion, even though no Lorentz force acts on the electron outside the solenoid, the photodetachment microscopy interference pattern on the detector is changed with the variation in the magnetic flux enclosed by the solenoid. This is caused by the AB effect. Under certain conditions, the interference pattern reaches the macroscopic dimensions and could be observed in a direct AB effect experiment. Our study can provide some predictions for the future experimental study of the AB effect in the photodetachment microscopy of negative ions.

Investigation of plasma behavior during noble gas injection in the end-cell of GAMMA 10/PDX by using the multi-fluid code ‘LINDA’

NASA Astrophysics Data System (ADS)

Islam, M. S.; Nakashima, Y.; Hatayama, A.

2017-12-01

The linear divertor analysis with fluid model (LINDA) code has been developed in order to simulate plasma behavior in the end-cell of linear fusion device GAMMA 10/PDX. This paper presents the basic structure and simulated results of the LINDA code. The atomic processes of hydrogen and impurities have been included in the present model in order to investigate energy loss processes and mechanism of plasma detachment. A comparison among Ar, Kr and Xe shows that Xe is the most effective gas on the reduction of electron and ion temperature. Xe injection leads to strong reduction in the temperature of electron and ion. The energy loss terms for both the electron and the ion are enhanced significantly during Xe injection. It is shown that the major energy loss channels for ion and electron are charge-exchange loss and radiative power loss of the radiator gas, respectively. These outcomes indicate that Xe injection in the plasma edge region is effective for reducing plasma energy and generating detached plasma in linear device GAMMA 10/PDX.

The e[sup [minus

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

Holroyd, R.A.; Schwarz, H.A.; Stradowska, E.

The rate constants for attachment of excess electrons to 1,3-butadiene (k[sub a]) and detachment from the butadiene anion (k[sub d]) in n-hexane are reported. The equilibrium constant, K[sub eq] = k[sub a]/k[sub d], increases rapidly with pressure and decreases as the temperature increases. At -7[degree]C attachment is observed at 1 bar. At high pressures the attachment rate is diffusion controlled. The activation energy for detachment is about 21 kcal/mol; detachment is facilitated by the large entropy of activation. The reaction volumes for attachment range from -181 cm[sup 3]/mol at 400 bar to-122 cm[sup 3]/mol at 1500 bar and are largelymore » attributed to the electrostriction volume of the butadiene anion ([Delta][bar V][sub el]). Values of [Delta][bar V][sub el] calculated by a model, which includes a glassy shell of solvent molecules around the ion, are in agreement with experimental reaction volumes. The analysis indicates the partial molar volume of the electron in hexane is small and probably negative. It is shown that the entropies of reaction are closely related to the partial molar volumes of reaction. 22 refs., 5 figs., 5 tabs.« less

Double salt décollements: Effect of pinch-out overlapping in experimental thrust wedges

NASA Astrophysics Data System (ADS)

Santolaria, P.; Vendeville, B.; Graveleau, F.; Casas, A.; Soto, R.

2013-12-01

The presence of one or more evaporitic horizons acting as detachment levels in fold-and-thrust belts is common. Numerous works have dealt with the analysis of the role played by basal detachments on the deformation style of fold-and-thrust belts, but less attention has been paid to the interaction between two décollements and strain transfer between them. In this study, 10 sand-silicone analogue experiments with two detachment levels and different stratigraphic pinch-out configurations were carried out: the basal décollement was located hinterlandwards, and the upper one was located forelandwards, with or without geographic underlap or overlap. These geometrical arrangements simulate evaporites deposited in foreland basins progressively involved in shortening. To analyze their influence on the geometry and kinematics of thrust wedges, we tested successively the following parameters: i) the amount of vertical overlapping between the two décollement pinch-outs, ii) the total amount of shortening, and iii) the geometry of the intermediate décollement (pinch-out line parallel or oblique with respect to the pinch-out line of the basal décollement). All experiments were quantitatively monitored by carrying DEM (Digital Elevation Models) and PIV (Particle Image Velocimetry) measurements. All models had a similar style: (i) an inner domain, characterized by a thicker sand cover, with three forward verging thrusts rooted in the basal décollement, (ii) an outer domain with thinner sand cover, whose deformation pattern was characterized by 2 to 6 structures detaching on the upper décollement and (iii) a 'step zone' located between the inner and outer domains having varying geometry and kinematics. In longer-lived models, structures were reworked and salt migration deformed the early emplaced folds and thrusts. Our experimental results point out that the amount of vertical overlapping between the two décollement pinch outs is a first order parameter that conditions not only the geometry and deformation of the 'step zone', but also the geometry and kinematics of the entire thrust wedge. Comparison with the foreland fold-and-thrust belt from the Southeastern Pyrenees, where deformation is transferred from the Triassic evaporites to Eocene-Oligocene evaporitic horizons deposited in front of the advancing Pyrenean thrust sheets, supports the experimental results and validates their interpretation.

Detached Bridgman Growth of Germanium and Germanium-Silicon Alloy Crystals

NASA Technical Reports Server (NTRS)

Szofran, F. R.; Volz, M. P.; Schweizer, M.; Kaiser, N.; Cobb, S. D.; Motakef, S.; Vujisic, L. J.; Croell, A.; Dold, P.; Rose, M. Franklin (Technical Monitor)

2001-01-01

Earth based experiments on the science of detached crystal growth are being conducted on germanium and germanium-silicon alloys (2at% Si average composition) in preparation for a series of experiments aboard the International Space Station (ISS) to differentiate among proposed mechanisms contributing to detachment. Sessile drop measurements were first carried out for a large number of substrates made of potential ampoule materials to determine the contact angles and the surface tension as a function of temperature and composition. The process atmosphere and duration of the experiment (for some cases) were also found to have significant influence on the wetting angle. Growth experiments have used pyrolytic boron nitride (pBN) and fused silica ampoules with the majority of the detached results occurring predictably in the pBN. The contact angles were 173 deg (Ge) and 165 deg (GeSi) for pBN. For fused silica, the contact angle decreases to an equilibrium value with duration of measurement ranging from 150 to 117 deg (Ge), 129 to 100 deg (GeSi). Forming gas (Ar + 2% H2) and vacuum have been used in the growth ampoules. With gas in the ampoule, a variation of the temperature profile during growth has been used to control the pressure difference between the top of the melt and the volume below the melt caused by detachment of the growing crystal. The stability of detachment has been modeled and substantial insight has been gained into the reasons that detachment has most often been observed in reduced gravity but nonetheless has occurred randomly even there. An empirical model for the conditions necessary to achieve sufficient stability to maintain detached growth for extended periods has been developed and will be presented. Methods for determining the nature and extent of detachment include profilometry and optical and electron microscopy. This surface study is the subject of another presentation at this Congress. Results in this presentation will show that we have established the effects of different ampoule materials, temperature profiles, pressure differences, and silicon concentrations and that samples that are nearly completely detached can be grown repeatedly.

Surface heat loads on the ITER divertor vertical targets

NASA Astrophysics Data System (ADS)

Gunn, J. P.; Carpentier-Chouchana, S.; Escourbiac, F.; Hirai, T.; Panayotis, S.; Pitts, R. A.; Corre, Y.; Dejarnac, R.; Firdaouss, M.; Kočan, M.; Komm, M.; Kukushkin, A.; Languille, P.; Missirlian, M.; Zhao, W.; Zhong, G.

2017-04-01

The heating of tungsten monoblocks at the ITER divertor vertical targets is calculated using the heat flux predicted by three-dimensional ion orbit modelling. The monoblocks are beveled to a depth of 0.5 mm in the toroidal direction to provide magnetic shadowing of the poloidal leading edges within the range of specified assembly tolerances, but this increases the magnetic field incidence angle resulting in a reduction of toroidal wetted fraction and concentration of the local heat flux to the unshadowed surfaces. This shaping solution successfully protects the leading edges from inter-ELM heat loads, but at the expense of (1) temperatures on the main loaded surface that could exceed the tungsten recrystallization temperature in the nominal partially detached regime, and (2) melting and loss of margin against critical heat flux during transient loss of detachment control. During ELMs, the risk of monoblock edge melting is found to be greater than the risk of full surface melting on the plasma-wetted zone. Full surface and edge melting will be triggered by uncontrolled ELMs in the burning plasma phase of ITER operation if current models of the likely ELM ion impact energies at the divertor targets are correct. During uncontrolled ELMs in pre-nuclear deuterium or helium plasmas at half the nominal plasma current and magnetic field, full surface melting should be avoided, but edge melting is predicted.

New Insights into Mechanism of Surface Reactions of ZnO Nanorods During Electrons Beam Irradiation.

PubMed

Cho, Youngseung; Ji, Hyunjin; Kim, Hyoungsub; Yoon, Jinsuop; Choi, Byoungdeog

2018-09-01

This study provides new insight into mechanisms of ionic reactions on the surface of ZnO nanorod networks, which could result in enhanced performance in optical or molecular sensors. The current- voltage characteristics of ZnO nanorod network devices exhibit typical nonlinear behavior in air, which implies the formation of a Schottky barrier when metals are used as contacts. The conductance of the device increased significantly in vacuum, which can be explained by the desorption of hydroxyl groups at very low pressure. While physisorbed water or oxygen-related ions can detach from the ZnO surface during evacuation, exposure to high energy in the electron beam is believed to detach the chemisorbed anions of O- and O-2 from the surface of ZnO nanorods, which releases more electrons into the channel. The increase in available electrons enhances the conductance of the ZnO nanorods. Slow initialization of the conductance under ambient conditions indicates that the ionic re-adsorption is inactive under these conditions. Thus, the electron irradiation process can be used to reset the surface ionic molecules on metal oxide nano-structures by tuning the surface potential prior to the passivation process.

Continental Extensional Tectonics in the Basins and Ranges and Aegean Regions: A Review

NASA Astrophysics Data System (ADS)

Cemen, I.

2017-12-01

The Basins and Ranges of North America and the Aegean Region of Eastern Europe and Asia Minor have been long considered as the two best developed examples of continental extension. The two regions contain well-developed normal faults which were considered almost vertical in the 1950s and 1960s. By the mid 1980s, however, overwhelming field evidence emerged to conclude that the dip angle normal faults in the two regions may range from almost vertical to almost horizontal. This led to the discovery that high-grade metamorphic rocks could be brought to surface by the exhumation of mid-crustal rocks along major low-angle normal faults (detachment faults) which were previously either mapped as thrust faults or unconformity. Within the last three decades, our understanding of continental extensional tectonics in the Basins and Ranges and the Aegean Region have improved substantially based on fieldwork, geochemical analysis, analog and computer modeling, detailed radiometric age determinations and thermokinematic modelling. It is now widely accepted that a) Basin and Range extension is controlled by the movement along the San Andreas fault zone as the North American plate moved southeastward with respect to the northwestward movement of the Pacific plate; b) Aegean extension is controlled by subduction roll-back associated with the Hellenic subduction zone; and c) the two regions contain best examples of detachment faulting, extensional folding, and extensional basins. However, there are still many important questions of continental extensional tectonics in the two regions that remain poorly understood. These include determining a) precise amount and percentage of cumulative extension; b) role of strike-slip faulting in the extensional processes; c) exhumation history along detachment surfaces using multimethod geochronology; d) geometry and nature of extensional features in the middle and lower crust; e) the nature of upper mantle and asthenospheric flow; f) evolutions of sedimentary basins associated with dip-slip and strike-slip faults; g) seismic hazards; and i) economic significance of extensional basins.

Multivariate Analysis of Electron Detachment Dissociation and Infrared Multiphoton Dissociation Mass Spectra of Heparan Sulfate Tetrasaccharides Differing Only in Hexuronic acid Stereochemistry

NASA Astrophysics Data System (ADS)

Oh, Han Bin; Leach, Franklin E.; Arungundram, Sailaja; Al-Mafraji, Kanar; Venot, Andre; Boons, Geert-Jan; Amster, I. Jonathan

2011-03-01

The structural characterization of glycosaminoglycan (GAG) carbohydrates by mass spectrometry has been a long-standing analytical challenge due to the inherent heterogeneity of these biomolecules, specifically polydispersity, variability in sulfation, and hexuronic acid stereochemistry. Recent advances in tandem mass spectrometry methods employing threshold and electron-based ion activation have resulted in the ability to determine the location of the labile sulfate modification as well as assign the stereochemistry of hexuronic acid residues. To facilitate the analysis of complex electron detachment dissociation (EDD) spectra, principal component analysis (PCA) is employed to differentiate the hexuronic acid stereochemistry of four synthetic GAG epimers whose EDD spectra are nearly identical upon visual inspection. For comparison, PCA is also applied to infrared multiphoton dissociation spectra (IRMPD) of the examined epimers. To assess the applicability of multivariate methods in GAG mixture analysis, PCA is utilized to identify the relative content of two epimers in a binary mixture.

Study of near SOL decay lengths in ASDEX Upgrade under attached and detached divertor conditions

NASA Astrophysics Data System (ADS)

Sun, H. J.; Wolfrum, E.; Kurzan, B.; Eich, T.; Lackner, K.; Scarabosio, A.; Paradela Pérez, I.; Kardaun, O.; Faitsch, M.; Potzel, S.; Stroth, U.; the ASDEX Upgrade Team

2017-10-01

A database with attached, partially detached and completely detached divertors has been constructed in ASDEX Upgrade discharges in both H-mode and L-mode plasmas with Thomson Scattering data suitable for the analysis of the upstream SOL electron profiles. By comparing upstream temperature decay width, {λ }{Te,u}, with the scaling of the SOL power decay width, {λ }{q\\parallel e}, based on the downstream IR measurements, it is found that a simple relation based on classical electron conduction can relate {λ }{Te,u} and {λ }{q\\parallel e} well. The combined dataset can be described by both a single scaling and a separate scaling for H-modes and L-modes. For the single scaling, a strong inverse dependence of, {λ }{Te,u} on the separatrix temperature, {T}e,u, is found, suggesting the classical parallel Spitzer-Harm conductivity as dominant mechanism controlling the SOL width in both L-mode and H-mode over a large set of plasma parameters. This dependence on {T}e,u explains why, for the same global plasma parameters, {λ }{q\\parallel e} in L-mode is approximately twice that in H-mode and under detached conditions, the SOL upstream electron profile broadens when the density reaches a critical value. Comparing the derived scaling from experimental data with power balance, gives the cross-field thermal diffusivity as {χ }\\perp \\propto {T}e{1/2}/{n}e, consistent with earlier studies on Compass-D, JET and Alcator C-Mod. However, the possibility of the separate scalings for different regimes cannot be excluded, which gives results similar to those previously reported for the H-mode, but here the wider SOL width for L-mode plasmas is explained simply by the larger premultiplying coefficient. The relative merits of the two scalings in representing the data and their theoretical implications are discussed.

Theoretical investigations on the d-p hybridized aromaticity, photoelectron spectroscopy and neutral salts of the LaX2- (X=Al, Ga, In) clusters.

PubMed

Chen, Jing; Yang, Huan; Wang, Jing; Cheng, Shi-Bo

2018-05-30

We present an extensive density functional theory (DFT) calculations on the geometrical and electronic structures of the triatomic LaX 2 - (X=Al, Ga, In) clusters. Various trail structures and spin states have been attempted to determine the lowest-energy geometries of these La-doped metal clusters. The ground states of all three clusters are calculated to possess the trigonal structures with the singlet multiplicities. The calculations on molecular orbitals (MOs) and nucleus-independent chemical shift (NICS) values have been performed to examine the aromatic characteristics of the LaX 2 - (X=Al, Ga, In) clusters. The present calculations disclose that all these metal clusters are doubly aromatic, namely d-p hybridized σ and π aromaticity resulting from the effective overlap between the 5d atomic orbital of the La atom and the p orbitals of the IIIA group elements. Theoretical vertical detachment energies (VDEs) were also calculated to simulate the photoelectron spectra (PES) of the clusters. In addition, by adding the alkali cations (Li + and Na + ) into the LaX 2 - (X=Al, Ga, In) clusters, the geometries and electronic structures of the corresponding neutral salts have also been investigated to gain more insights in the potential of using these aromatic anions as building blocks. Copyright © 2018 Elsevier B.V. All rights reserved.

Time-resolved photoelectron imaging of iodide-nitromethane (I-·CH3NO2) photodissociation dynamics.

PubMed

Kunin, Alice; Li, Wei-Li; Neumark, Daniel M

2016-12-07

Femtosecond time-resolved photoelectron spectroscopy is used to probe the decay channels of iodide-nitromethane (I - ·CH 3 NO 2 ) binary clusters photoexcited at 3.56 eV, near the vertical detachment energy (VDE) of the cluster. The production of I - is observed, and its photoelectron signal exhibits a mono-exponential rise time of 21 ± 1 ps. Previous work has shown that excitation near the VDE of the I - ·CH 3 NO 2 complex transfers an electron from iodide to form a dipole-bound state of CH 3 NO 2 - that rapidly converts to a valence bound (VB) anion. The long appearance time for the I - fragment suggests that the VB anion decays by back transfer of the excess electron to iodide, reforming the I - ·CH 3 NO 2 anion and resulting in evaporation of iodide. Comparison of the measured lifetime to that predicted by RRKM theory suggests that the dissociation rate is limited by intramolecular vibrational energy redistribution in the re-formed anion between the high frequency CH 3 NO 2 vibrational modes and the much lower frequency intermolecular I - ·CH 3 NO 2 stretch and bends, the predominant modes involved in cluster dissociation to form I - . Evidence for a weak channel identified as HI + CH 2 NO 2 - is also observed.

Theoretical studies on the electronic structures and photoelectron spectra of tri-rhenium oxide clusters: Re3O(n)(-) and Re3O(n) (n=1-6).

PubMed

Zhou, Qi; Gong, Wei-Chao; Xie, Lu; Zheng, Cun-Gong; Zhang, Wei; Wang, Bin; Zhang, Yong-Fan; Huang, Xin

2014-01-03

Density functional theory (DFT) calculations are performed to study the structural and electronic properties of tri-rhenium oxide clusters Re3On(-/0) (n=1-6). Generalized Koopmans' theorem is applied to predict the vertical detachment energies (VDEs) and simulate the photoelectron spectra (PES). Theoretical calculations at the B3LYP level are carried out to search for the global minima for both the anions and the neutrals. For the anions, the first two O atoms prefer the same corner position of a Re3 triangle. Whereas, Re3O3(-) possesses a C2v symmetry with one bridging and two terminal O atoms. The next three O atoms (n=4-6) are adding sequentially on the basis of Re3O3(-) motif, i.e., adding one terminal O atom for Re3O4(-), one terminal and one bridging O atoms for Re3O5(-), and one terminal and two bridging O atoms for Re3O6(-), respectively. Their corresponding neutral species are similar to the anions in geometry except Re3O4 and Re3O5. Molecular orbital analyses are employed to investigate the chemical bonding and structural evolution in these tri-rhenium oxide clusters. Copyright © 2013 Elsevier B.V. All rights reserved.

Espisodic detachment of Martian crustal magnetic fields leading to bulk atmospheric plasma escape

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

Brain, D A; Baker, A H; Briggs, J

2009-06-02

We present an analysis of magnetic field and suprathermal electron measurements from the Mars Global Surveyor (MGS) spacecraft that reveals isolated magnetic structures filled with Martian atmospheric plasma located downstream from strong crustal magnetic fields with respect to the flowing solar wind. The structures are characterized by magnetic field enhancements and rotations characteristic of magnetic flux ropes, and characteristic ionospheric electron energy distributions with angular distributions distinct from surrounding regions. These observations indicate that significant amounts of atmosphere are intermittently being carried away from Mars by a bulk removal process: the top portions of crustal field loops are stretched throughmore » interaction with the solar wind and detach via magnetic reconnection. This process occurs frequently and may account for as much as 10% of the total present-day ion escape from Mars.« less

78 FR 18457 - Definition of Form I-94 To Include Electronic Format

Federal Register 2010, 2011, 2012, 2013, 2014

2013-03-27

... parole stamp in a foreign passport to the list of documents designated as evidence of alien registration... will create a Form I-94 in an electronic format based on passenger, passport and visa information DHS... inspection. The officer stamps the Form I-94 and the alien's passport, detaches the bottom portion of the...

Detachments in Shale: Controlling Characteristics on Fold-Thrust Belt Style

NASA Astrophysics Data System (ADS)

Hansberry, Rowan; King, Ros; Collins, Alan; Morley, Chris

2013-04-01

Fold-thrust belts occur across multiple tectonic settings where thin-skinned deformation is accommodated by one or more detachment zones, both basal and within the fold-thrust belt. These fold-thrust belts exhibit considerable variation in structural style and vergence depending on the characteristics (e.g. strength, thickness, and lithology) and number of detachment zones. Shale as a detachment lithology is intrinsically weaker than more competent silts and sands; however, it can be further weakened by high pore pressures, reducing resistance to sliding and; high temperatures, altering the rheology of the detachment. Despite the implications for petroleum exploration and natural hazard assessment the precise nature by which detachments in shale control and are involved in deformation in fold-thrust belts is poorly understood. Present-day active basal detachment zones are usually located in inaccessible submarine regions. Therefore, this project employs field observations and sample analysis of ancient, exhumed analogues to document the nature of shale detachments (e.g. thickness, lithology, dip and dip direction, deformational temperature and thrust propagation rates) at field sites in Thailand, Norway and New Zealand. X-ray diffraction analysis of illite crystallinity and oxygen stable isotopes analysis are used as a proxy for deformational temperature whilst electron-backscatter diffraction analysis is used to constrain microstructural deformational patterns. K-Ar dating of synkinematic clay fault gouges is being applied to date the final stages of activity on individual faults with a view to constraining thrust activation sequences. It is not possible to directly measure palaeo-data for some key detachment parameters, such as pore pressure and coefficients of friction. However, the use of critical taper wedge theory has been used to successfully infer internal and basal coefficients of friction and depth-normalized pore pressure within a wedge and at its base (e.g. Platt, 1986; Bilotti and Shaw, 2005; Morley, 2007). Therefore, through a mixture of field observations, sample analysis and theoretical analysis it will be possible to determine a full range of shale detachment parameters and their impact on the structural style of fold-thrust belts across a variety of settings. Recent work in Muak Lek, central Thailand has focused on a structural investigation of fold-thrust belt deformation of a passive margin sequence as a result of continent-continent collision during the Triassic Indosinian Orogeny. Exceptional outcropping of the detachment lithology is accessible in the Siam City Cement quarry allowing construction of sections detailing the deformational style across the detachment itself. The detachment forms complex, 3-dimensional duplex-like structures creating egg-carton geometries enveloping foliation surfaces in the zones of most intense strain. Up section strain decreases to discrete thrust imbricates of decametre scale. Samples of limestone and secondary calcite were collected through the sections for oxygen stable isotopes analysis which show a distinct pattern of isotopic fractionation across the main thrust and into the detachment. Results from this study give insights into the nature of shale detachments and the control on fold-thrust belt development.

CO adsorption on small Au{sub n} (n = 1–4) structures supported on hematite. II. Adsorption on the O-rich termination of α-Fe{sub 2}O{sub 3}(0001) surface

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

Pabisiak, Tomasz; Kiejna, Adam, E-mail: kiejna@ifd.uni.wroc.pl; Winiarski, Maciej J.

2016-01-28

The adsorption of small Au{sub n} (n = 1–4) nanostructures on oxygen terminated α-Fe{sub 2}O{sub 3}(0001) surface was investigated using density functional theory in the generalized gradient approximation of Perdew-Burke-Ernzerhof (PBE) form with Hubbard correction U, accounting for strong electron correlations (PBE+U). The structural, energetic, and electronic properties were examined for two classes of the adsorbed Au{sub n} nanostructures with vertical and flattened configurations. Similarly to the Fe-terminated α-Fe{sub 2}O{sub 3}(0001) surface considered in Part I, the flattened configurations were found energetically more favored than vertical ones. The binding of Au{sub n} to the O-terminated surface is much stronger thanmore » to the Fe-termination. The adsorption bonding energy of Au{sub n} and the work function of the Au{sub n}/α-Fe{sub 2}O{sub 3}(0001) systems decrease with the increased number of Au atoms in a structure. All of the adsorbed Au{sub n} structures are positively charged. The bonding of CO molecules to the Au{sub n} structures is distinctly stronger than on the Fe-terminated surface; however, it is weaker than the binding to the bare O-terminated surface. The CO molecule binds to the Au{sub n}/α-Fe{sub 2}O{sub 3}(0001) system through a peripheral Au atom partly detached from the Au{sub n} structure. The results of this work indicate that the most energetically favored sites for adsorption of a CO molecule on the Au{sub n}/α-Fe{sub 2}O{sub 3}(0001) systems are atoms in the Au{sup 0.5+} oxidation state.« less

Observation of Excited Quadrupole-Bound States in Cold Anions

NASA Astrophysics Data System (ADS)

Zhu, Guo-Zhu; Liu, Yuan; Wang, Lai-Sheng

2017-07-01

We report the first observation of an excited quadrupole-bound state (QBS) in an anion. High-resolution photoelectron imaging of cryogenically cooled 4-cyanophenoxide (4 CP- ) anions yields an electron detachment threshold of 24 927 cm-1 . The photodetachment spectrum reveals a resonant transition 20 cm-1 below the detachment threshold, which is attributed to an excited QBS of 4 CP- because neutral 4CP has a large quadrupole moment with a negligible dipole moment. The QBS is confirmed by observation of seventeen above-threshold resonances due to autodetachment from vibrational levels of the QBS.

Role of a reducing environment in disassembly of the herpesvirus tegument

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

Newcomb, William W.; Jones, Lisa M.; Dee, Alexander

2012-09-15

Initiation of infection by herpes family viruses involves a step in which most of the virus tegument becomes detached from the capsid. Detachment takes place in the host cell cytosol near the virus entry site and it is followed by dispersal of tegument proteins and disappearance of the tegument as a distinct entity. Here we describe the results of experiments designed to test the idea that the reducing environment of the cytosol may contribute to tegument detachment and disassembly. Non-ionic detergent was used to remove the membrane of purified herpes simplex virus under control and reducing conditions. The effects onmore » the tegument were then examined by SDS-PAGE and electron microscopy. Protein analysis demonstrated that most major tegument proteins were removed under both oxidizing and reducing conditions except for UL49 which required a reducing environment. It is proposed therefore that the reducing conditions in the cytosol are involved in removal of UL49 protein. Electron microscopic analysis revealed that capsids produced under oxidizing conditions contained a coating of protein that was absent in reduced virions and which correlated uniquely with the presence of UL49. This capsid-associated layer is suggested to be the location of UL49 in the extracted virion.« less

Detachment of CVD-grown graphene from single crystalline Ni films by a pure gas phase reaction

NASA Astrophysics Data System (ADS)

Zeller, Patrick; Henß, Ann-Kathrin; Weinl, Michael; Diehl, Leo; Keefer, Daniel; Lippmann, Judith; Schulz, Anne; Kraus, Jürgen; Schreck, Matthias; Wintterlin, Joost

2016-11-01

Despite great previous efforts there is still a high need for a simple, clean, and upscalable method for detaching epitaxial graphene from the metal support on which it was grown. We present a method based on a pure gas phase reaction that is free of solvents and polymer supports and avoids mechanical transfer steps. The graphene was grown on 150 nm thick, single crystalline Ni(111) films on Si(111) wafers with YSZ buffer layers. Its quality was monitored by using low energy electron diffraction and scanning tunneling microscopy. The gas phase etching uses a chemical transport reaction, the so-called Mond process, based on the formation of gaseous nickel tetracarbonyl in 1 bar of CO at 75 °C and by adding small amounts of sulfide catalysts. X-ray photoelectron spectroscopy, Raman spectroscopy and scanning electron microscopy were used to characterize the detached graphene. It was found that the method successfully removes the nickel from underneath the graphene layer, so that the graphene lies on the insulating oxide buffer layer. Small residual particles of nickel sulfide and cracks in the obtained graphene layer were identified. The defect concentrations were comparable to graphene samples obtained by wet chemical etching and by the bubbling transfer.

Noo Peroxy Isomer Exposed with Velocity-Map Imaging

NASA Astrophysics Data System (ADS)

Laws, Benjamin A.; Cavanagh, Steven J.; Lewis, Brenton R.; Gibson, Stephen T.

2016-06-01

O2, a toxic gas formed in most combustion processes, plays an important role in the Earth's atmosphere due to its role in the production of both photochemical smog and tropospheric ozone. The existence of the peroxy radial, NOO, has been proposed, both as a collision reaction intermediate, and as a negative-ion in some discharge sources, in order to account for extended tails seen in some photoelectron spectra. In this work a velocity-mapped image of NO2- photodetachment measured at 519 nm, shown, reveals high-energy electron structure, that persists at detachment energies lower than the electron affinity of ONO, 2.273 eV. {b} The central ring has the spectral signature of O^-, while the outer-ripples, that appear in character to be similar to NO- detachment, are, we propose due to the NOO- peroxy radical, which is also responsible for the presence of O-. The photoelectron spectrum resolves the vibrational structure to characterize the neutral peroxy radical. The identification is further supported by ab initio calculations. The photoelectron angular distributions associated with the peroxy radical have a negative anisotropy parameter, opposite in sign to detachment from ONO^-. K. M. Ervin and J. Ho and W. C. Lineberger, J. Phys. Chem. 92, 5405 (1988). doi:10.1021/j100330a017 Research supported by the ARC DP160102585.

TRIAGE of Irradiated Personnel

DTIC Science & Technology

1996-09-25

Vivo Electron Paramagnetic Resonance, Electron Spin Resonance (EPR, ESR) for In Vivo Dosimetry Under Field Conditions Dr. Harold M. Swartz Dartmouth...Force Medical Center Andrews Air Force Base, MD • Status and Limitations of Physical Dosimetry in the Field Environment David A. Schauer, LCDR, MSC...USN Naval Dosimetry Center Navy Environmental Health Center Detachment Bethesda, MD • NATO Policy and Guidance on Antiemetic Usage Robert Kehlet

Command Post Program Study. Volume 1 - Main Report

DTIC Science & Technology

1973-03-01

Field Manual 30-9, Military Intelligence Battalion - Field Am. Washington: March 1968. _ Field Manual 32-20, Electronic Warfare. Washington: 14...Mechanized). A-18 TOE 30-88T, Military Intelligence Support Detachment, Military Intelligence Battalion, Field Army. TOE 30-206T, Headquarters and... Field Manual 30-9, Military Intelligence Battalion - Field Army. Washington: March 1968. _ Field Manual 32-20, Electronic Warfare. Washington: 14

Electron Detachment Dissociation (EDD) of Fluorescently Labeled Sialylated Oligosaccharides

PubMed Central

Zhou, Wen; Håkansson, Kristina

2012-01-01

We explored the application of electron detachment dissociation (EDD) and infrared multiphoton dissociation (IRMPD) tandem mass spectrometry to fluorescently labeled sialylated oligosaccharides. Standard sialylated oligosaccharides and a sialylated N-linked glycan released from human transferrin were investigated. EDD yielded extensive glycosidic cleavages and cross-ring cleavages in all cases studied, consistently providing complementary structural information compared to IRMPD. Neutral losses and satellite ions such as C – 2H ions were also observed following EDD. In addition, we examined the influence of different fluorescent labels. The acidic label 2-aminobenzoic acid (2-AA) enhanced signal abundance in negative-ion mode. However, few cross-ring fragments were observed for 2-AA labeled oligosaccharides. The neutral label 2-aminobenzamide (2-AB) resulted in more cross-ring cleavages compared to 2-AA labeled species, but not as extensive fragmentation as for native oligosaccharides, likely resulting from altered negative charge locations from introduction of the fluorescent tag. PMID:22120881

The relief formed by the descent phenomenon in the north-east part of Kosova.

PubMed

Bulliqi, Shpejtim; Isufi, Florim; Ramadani, Ibrahim; Gashi, Gani

2012-04-01

In the diverse relief of north-east part of Kosova a relatively wide range occupies the relief modelled by the descent phenomenon, which is conditioned by morph-structural and climatic factors quite suitable for their development. The morphogenesis activity of descent phenomenon is conditioned by the types of rocks, tectonic process of this region and climatic conditions. These factors condition horizontal and vertical relief fragmentation, slope, especially in Gollaku mountains and in SE part of Kopaonik mountain. Along the tectonic descents, the steepness is detaching and the detaching lines consisting of magmatic rocks show overthrows, demolitions and stony torrents, but the Teri gene composition formations are modelled by sliding and muddy torrents, depending upon the presence of clayey and alevrolite belts on these Teri gene ones. The impact of factors and conditions on the relief of this part, the phenomena like demolitions, overthrows, sliding, muddy torrents, stony torrents, etc, operate here, which play an important morphological role in the modelling of relief.

Study of adhesion of vertically aligned carbon nanotubes to a substrate by atomic-force microscopy

NASA Astrophysics Data System (ADS)

Ageev, O. A.; Blinov, Yu. F.; Il'ina, M. V.; Il'in, O. I.; Smirnov, V. A.; Tsukanova, O. G.

2016-02-01

The adhesion to a substrate of vertically aligned carbon nanotubes (VA CNT) produced by plasmaenhanced chemical vapor deposition has been experimentally studied by atomic-force microscopy in the current spectroscopy mode. The longitudinal deformation of VA CNT by applying an external electric field has been simulated. Based on the results, a technique of determining VA CNT adhesion to a substrate has been developed that is used to measure the adhesion strength of connecting VA CNT to a substrate. The adhesion to a substrate of VA CNT 70-120 nm in diameter varies from 0.55 to 1.19 mJ/m2, and the adhesion force from 92.5 to 226.1 nN. When applying a mechanical load, the adhesion strength of the connecting VA CNT to a substrate is 714.1 ± 138.4 MPa, and the corresponding detachment force increases from 1.93 to 10.33 μN with an increase in the VA CNT diameter. As an external electric field is applied, the adhesion strength is almost doubled and is 1.43 ± 0.29 GPa, and the corresponding detachment force is changed from 3.83 to 20.02 μN. The results can be used in the design of technological processes of formation of emission structures, VA CNT-based elements for vacuum microelectronics and micro- and nanosystem engineering, and also the methods of probe nanodiagnostics of VA CNT.

Heat budget of ionospheric electrons

NASA Technical Reports Server (NTRS)

Prasad, S. S.; Schneck, L. J.

1976-01-01

Heat input calculations were detached from solar extreme UV data and monatomic oxygen densities were derived from simultaneously measured data sets (ion composition 146-191 km) in a study of the heat budget of ionosphere electrons. Earlier inferences that cooling predominates over heating are supported. A search for additional heat sources or a revision of the cooling rates is recommended, by way of balancing the heat budget. Importance is attached to electron cooling by fine structure excitation of monatomic oxygen.

Slab detachment under the Eastern Alps seen by seismic anisotropy

PubMed Central

Qorbani, Ehsan; Bianchi, Irene; Bokelmann, Götz

2015-01-01

We analyze seismic anisotropy for the Eastern Alpine region by inspecting shear-wave splitting from SKS and SKKS phases. The Eastern Alpine region is characterized by a breakdown of the clear mountain-chain-parallel fast orientation pattern that has been previously documented for the Western Alps and for the western part of the Eastern Alps. The main interest of this paper is a more detailed analysis of the anisotropic character of the Eastern Alps, and the transition to the Carpathian–Pannonian region. SK(K)S splitting measurements reveal a rather remarkable lateral change in the anisotropy pattern from the west to the east of the Eastern Alps with a transition area at about 12°E. We also model the backazimuthal variation of the measurements by a vertical change of anisotropy. We find that the eastern part of the study area is characterized by the presence of two layers of anisotropy, where the deeper layer has characteristics similar to those of the Central Alps, in particular SW–NE fast orientations of anisotropic axes. We attribute the deeper layer to a detached slab from the European plate. Comparison with tomographic studies of the area indicates that the detached slab might possibly connect with the lithosphere that is still in place to the west of our study area, and may also connect with the slab graveyard to the East, at the depth of the upper mantle transition zone. On the other hand, the upper layer has NW–SE fast orientations coinciding with a low-velocity layer which is found above a more-or-less eastward dipping high-velocity body. The anisotropy of the upper layer shows large-scale NW–SE fast orientation, which is consistent with the presence of asthenospheric flow above the detached slab foundering into the deeper mantle. PMID:25843968

Slab detachment under the Eastern Alps seen by seismic anisotropy

NASA Astrophysics Data System (ADS)

Qorbani, Ehsan; Bianchi, Irene; Bokelmann, Götz

2015-01-01

We analyze seismic anisotropy for the Eastern Alpine region by inspecting shear-wave splitting from SKS and SKKS phases. The Eastern Alpine region is characterized by a breakdown of the clear mountain-chain-parallel fast orientation pattern that has been previously documented for the Western Alps and for the western part of the Eastern Alps. The main interest of this paper is a more detailed analysis of the anisotropic character of the Eastern Alps, and the transition to the Carpathian-Pannonian region. SK(K)S splitting measurements reveal a rather remarkable lateral change in the anisotropy pattern from the west to the east of the Eastern Alps with a transition area at about 12°E. We also model the backazimuthal variation of the measurements by a vertical change of anisotropy. We find that the eastern part of the study area is characterized by the presence of two layers of anisotropy, where the deeper layer has characteristics similar to those of the Central Alps, in particular SW-NE fast orientations of anisotropic axes. We attribute the deeper layer to a detached slab from the European plate. Comparison with tomographic studies of the area indicates that the detached slab might possibly connect with the lithosphere that is still in place to the west of our study area, and may also connect with the slab graveyard to the East, at the depth of the upper mantle transition zone. On the other hand, the upper layer has NW-SE fast orientations coinciding with a low-velocity layer which is found above a more-or-less eastward dipping high-velocity body. The anisotropy of the upper layer shows large-scale NW-SE fast orientation, which is consistent with the presence of asthenospheric flow above the detached slab foundering into the deeper mantle.

Reactions of small negative ions with O2(a 1[Delta]g) and O2(X 3[Sigma]g-)

NASA Astrophysics Data System (ADS)

Midey, Anthony; Dotan, Itzhak; Seeley, J. V.; Viggiano, A. A.

2009-02-01

The rate constants and product ion branching ratios were measured for the reactions of various small negative ions with O2(X 3[Sigma]g-) and O2(a 1[Delta]g) in a selected ion flow tube (SIFT). Only NH2- and CH3O- were found to react with O2(X) and both reactions were slow. CH3O- reacted by hydride transfer, both with and without electron detachment. NH2- formed both OH-, as observed previously, and O2-, the latter via endothermic charge transfer. A temperature study revealed a negative temperature dependence for the former channel and Arrhenius behavior for the endothermic channel, resulting in an overall rate constant with a minimum at 500 K. SF6-, SF4-, SO3- and CO3- were found to react with O2(a 1[Delta]g) with rate constants less than 10-11 cm3 s-1. NH2- reacted rapidly with O2(a 1[Delta]g) by charge transfer. The reactions of HO2- and SO2- proceeded moderately with competition between Penning detachment and charge transfer. SO2- produced a SO4- cluster product in 2% of reactions and HO2- produced O3- in 13% of the reactions. CH3O- proceeded essentially at the collision rate by hydride transfer, again both with and without electron detachment. These results show that charge transfer to O2(a 1[Delta]g) occurs readily if the there are no restrictions on the ion beyond the reaction thermodynamics. The SO2- and HO2- reactions with O2(a) are the only known reactions involving Penning detachment besides the reaction with O2- studied previously [R.S. Berry, Phys. Chem. Chem. Phys., 7 (2005) 289-290].

Developing physics basis for the snowflake divertor in the DIII-D tokamak

NASA Astrophysics Data System (ADS)

Soukhanovskii, V. A.; Allen, S. L.; Fenstermacher, M. E.; Lasnier, C. J.; Makowski, M. A.; McLean, A. G.; Meyer, W. H.; Ryutov, D. D.; Kolemen, E.; Groebner, R. J.; Hyatt, A. W.; Leonard, A. W.; Osborne, T. H.; Petrie, T. W.; Watkins, J.

2018-03-01

Recent DIII-D results demonstrate that the snowflake (SF) divertor geometry (see standard divertor) enables significant manipulation of divertor heat transport for heat spreading and reduction in attached and radiative divertor regimes, between and during edge localized modes (ELMs), while maintaining good H-mode confinement. Snowflake divertor configurations have been realized in the DIII-D tokamak for several seconds in H-mode discharges with heating power P_NBI ≤slant 4 -5 MW and a range of plasma currents I_p=0.8-1.2 MA. In this work, inter-ELM transport and radiative SF divertor properties are studied. Significant impact of geometric properties on SOL and divertor plasma parameters, including increased poloidal magnetic flux expansion, divertor magnetic field line length and divertor volume, is confirmed. In the SF-minus configuration, heat deposition is affected by the geometry, and peak divertor heat fluxes are significantly reduced. In the SF-plus and near-exact SF configurations, divertor peak heat flux reduction and outer strike point heat flux profile broadening are observed. Inter-ELM sharing of power and particle fluxes between the main and additional snowflake divertor strike points has been demonstrated. The additional strike points typically receive up to 10-15% of total outer divertor power. Measurements of electron pressure and poloidal beta βp support the theoretically proposed churning mode that is driven by toroidal curvature and vertical pressure gradient in the weak poloidal field region. A comparison of the 4-4.5 MW NBI-heated H-mode plasmas with radiative SF divertor and the standard radiative divertor (both induced with additional gas puffing) shows a nearly complete power detachment and broader divertor radiated power distribution in the SF, as compared to a partial detachment and peaked localized radiation in the standard divertor. However, insignificant difference in the detachment onset w.r.t. density between the SF and the standard divertor was found. The results complement the initial SF divertor studies conducted in high-power H-mode discharges in the NSTX and DIII-D tokamaks, and, along with snowflake divertor results from TCV and other tokamaks, contribute to the physics basis of the SF divertor as a power exhaust concept for future high power density tokamaks.

Rockfall monitoring by Terrestrial Laser Scanning - case study of the basaltic rock face at Castellfollit de la Roca (Catalonia, Spain)

NASA Astrophysics Data System (ADS)

Abellán, A.; Vilaplana, J. M.; Calvet, J.; García-Sellés, D.; Asensio, E.

2011-03-01

This case study deals with a rock face monitoring in urban areas using a Terrestrial Laser Scanner. The pilot study area is an almost vertical, fifty meter high cliff, on top of which the village of Castellfollit de la Roca is located. Rockfall activity is currently causing a retreat of the rock face, which may endanger the houses located at its edge. TLS datasets consist of high density 3-D point clouds acquired from five stations, nine times in a time span of 22 months (from March 2006 to January 2008). The change detection, i.e. rockfalls, was performed through a sequential comparison of datasets. Two types of mass movement were detected in the monitoring period: (a) detachment of single basaltic columns, with magnitudes below 1.5 m3 and (b) detachment of groups of columns, with magnitudes of 1.5 to 150 m3. Furthermore, the historical record revealed (c) the occurrence of slab failures with magnitudes higher than 150 m3. Displacements of a likely slab failure were measured, suggesting an apparent stationary stage. Even failures are clearly episodic, our results, together with the study of the historical record, enabled us to estimate a mean detachment of material from 46 to 91.5 m3 year-1. The application of TLS considerably improved our understanding of rockfall phenomena in the study area.

Computational study on the molecular structures and photoelectron spectra of bimetallic oxide clusters MW2O9(-/0) (M=V, Nb, Ta).

PubMed

Chen, Wen-Jie; Zhang, Chang-Fu; Zhang, Xian-Hui; Zhang, Yong-Fan; Huang, Xin

2013-05-15

Density functional theory (DFT) and coupled cluster theory (CCSD(T)) calculations are carried out to investigate the electronic and structural properties of a series of bimetallic oxide clusters MW2O9(-/0) (M=V, Nb, Ta). Generalized Koopmans' theorem is applied to predict the vertical detachment energies (VDEs) and simulate the photoelectron spectra (PES). Theoretical calculations at the B3LYP level yield singlet and doublet ground states for the bimetallic anionic and neutral clusters, respectively. All the clusters present the six-membered ring structures with different symmetries, except that the TaW2O9(-) cluster shows a chained style with a penta-coordinated tantalum atom. Spin density analyses reveal oxygen radical species in all neutral clusters, consistent with their structural characteristics. Moreover, additional calculations are performed to study the oxidation reaction of CO molecule with the W3O9(+) cation and the isoelectronic VW2O9 cluster, and results indicate that the introduction of vanadium at tungsten site can efficiently improve the oxidation reactivity. Copyright © 2013 Elsevier B.V. All rights reserved.

Experimental and theoretical investigation of three-dimensional nitrogen-doped aluminum clusters AI 8N - and AI 8N

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

Wang, Leiming; Huang, Wei; Wang, Lai S.

The structure and electronic properties of the Al 8N - and Al 8N clusters were investigated by combined photoelectron spectroscopy and ab initio studies. Congested photoelectron spectra were observed and experimental evidence was obtained for the presence of multiple isomers for Al 8N - Global minimum searches revealed several structures for Al 8N - with close energies. The calculated vertical detachment energies of the two lowest-lying isomers, which are of C 2v and C s symmetry, respectively, were shown to agree well with the experimental data. Unlike the three-dimensional structures of Al 6N - and Al 7N -, in whichmore » the dopant N atom has a high coordination number of 6,the dopant N atom in the two low-lying isomers of Al 8N - has a lower coordination number of 4 and 5, respectively. The competition between the Al–Al and Al–N interactions are shown to determine the global minimum structures of the doped aluminum clusters and results in the structural diversity for both Al 8N - and Al8N. © 2009 American Institute of Physics« less

Decay dynamics of nascent acetonitrile and nitromethane dipole-bound anions produced by intracluster charge-transfer

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

Yandell, Margaret A.; King, Sarah B.; Neumark, Daniel M., E-mail: dneumark@berkeley.edu

2014-05-14

Decay dynamics of nascent dipole bound states of acetonitrile and nitromethane are examined using time-resolved photoelectron imaging of iodide-acetonitrile (I{sup −}·CH{sub 3}CN) and iodide-nitromethane (I{sup −}·CH{sub 3}NO{sub 2}) complexes. Dipole-bound anions are created by UV-initiated electron transfer to the molecule of interest from the associated iodide ion at energies just below the vertical detachment energy of the halide-molecule complex. The acetonitrile anion is observed to decay biexponentially with time constants in the range of 4–900 ps. In contrast, the dipole bound state of nitromethane decays rapidly over 400 fs to form the valence bound anion. The nitromethane valence anion speciesmore » then decays biexponentially with time constants of 2 ps and 1200 ps. The biexponential decay dynamics in acetonitrile are interpreted as iodine atom loss and autodetachment from the excited dipole-bound anion, followed by slower autodetachment of the relaxed metastable ion, while the dynamics of the nitromethane system suggest that a dipole-bound anion to valence anion transition proceeds via intramolecular vibrational energy redistribution to nitro group modes in the vicinity of the iodine atom.« less

Decay dynamics of nascent acetonitrile and nitromethane dipole-bound anions produced by intracluster charge-transfer.

PubMed

Yandell, Margaret A; King, Sarah B; Neumark, Daniel M

2014-05-14

Decay dynamics of nascent dipole bound states of acetonitrile and nitromethane are examined using time-resolved photoelectron imaging of iodide-acetonitrile (I(-)·CH3CN) and iodide-nitromethane (I(-)·CH3NO2) complexes. Dipole-bound anions are created by UV-initiated electron transfer to the molecule of interest from the associated iodide ion at energies just below the vertical detachment energy of the halide-molecule complex. The acetonitrile anion is observed to decay biexponentially with time constants in the range of 4-900 ps. In contrast, the dipole bound state of nitromethane decays rapidly over 400 fs to form the valence bound anion. The nitromethane valence anion species then decays biexponentially with time constants of 2 ps and 1200 ps. The biexponential decay dynamics in acetonitrile are interpreted as iodine atom loss and autodetachment from the excited dipole-bound anion, followed by slower autodetachment of the relaxed metastable ion, while the dynamics of the nitromethane system suggest that a dipole-bound anion to valence anion transition proceeds via intramolecular vibrational energy redistribution to nitro group modes in the vicinity of the iodine atom.

Effects of microsolvation on uracil and its radical anion: Uracil.(H2O)n (n=1-5)

NASA Astrophysics Data System (ADS)

Kim, Sunghwan; Schaefer, Henry F.

2006-10-01

Microsolvation effects on the stabilities of uracil and its anion have been investigated by explicitly considering the structures of complexes of uracil with up to five water molecules at the B3LYP /DZP++ level of theory. For all five systems, the global minimum of the neutral cluster has a different equilibrium geometry from that of the radical anion. Both the vertical detachment energy (VDE) and adiabatic electron affinity (AEA) of uracil are predicted to increase gradually with the number of hydrating molecules, qualitatively consistent with experimental results from a photodetachment-photoelectron spectroscopy study [J. Schiedt et al., Chem. Phys. 239, 511 (1998)]. The trend in the AEAs implies that while the conventional valence radical anion of uracil is only marginally bound in the gas phase, it will form a stable anion in aqueous solution. The gas-phase AEA of uracil (0.24eV) was higher than that of thymine by 0.04eV and this gap was not significantly affected by microsolvation. The largest AEA is that predicted for uracil•(H2O)5, namely, 0.96eV. The VDEs range from 0.76to1.78eV.

Effects of microsolvation on uracil and its radical anion: uracil(H2O)n (n = 1-5).

PubMed

Kim, Sunghwan; Schaefer, Henry F

2006-10-14

Microsolvation effects on the stabilities of uracil and its anion have been investigated by explicitly considering the structures of complexes of uracil with up to five water molecules at the B3LYPDZP++ level of theory. For all five systems, the global minimum of the neutral cluster has a different equilibrium geometry from that of the radical anion. Both the vertical detachment energy (VDE) and adiabatic electron affinity (AEA) of uracil are predicted to increase gradually with the number of hydrating molecules, qualitatively consistent with experimental results from a photodetachment-photoelectron spectroscopy study [J. Schiedt et al., Chem. Phys. 239, 511 (1998)]. The trend in the AEAs implies that while the conventional valence radical anion of uracil is only marginally bound in the gas phase, it will form a stable anion in aqueous solution. The gas-phase AEA of uracil (0.24 eV) was higher than that of thymine by 0.04 eV and this gap was not significantly affected by microsolvation. The largest AEA is that predicted for uracil(H2O)5, namely, 0.96 eV. The VDEs range from 0.76 to 1.78 eV.

Hydrogen bonding in microsolvation: photoelectron imaging and theoretical studies on Au(x)(-)-(H2O)(n) and Au(x)(-)-(CH3OH)(n) (x = 1, 2; n = 1, 2) complexes.

PubMed

Wu, Xia; Tan, Kai; Tang, Zichao; Lu, Xin

2014-03-14

We have combined photoelectron velocity-map imaging (VMI) spectroscopy and theoretical calculations to elucidate the geometry and energy properties of Aux(-)(Solv)n clusters with x = 1, 2; n = 1, 2; and Solv = H2O and CH3OH. Besides the blue-shifted vertical electron detachment energies (VDEs) of the complexes Au1,2(-)(Solv)n with the increase of the solvation number (n), we independently probed two distinct Au(-)(CH3OH)2 isomers, which combined with MP2/aug-cc-pVTZ(pp) calculations represent a competition between O···H-O hydrogen bonds (HBs) and Au···H-O nonconventional hydrogen bonds (NHBs). Complementary calculations provide the total binding energies of the low-energy isomers. Moreover, the relationship between the total binding energies and total VDEshift is discussed. We found that the Au1,2(-) anions exhibit halide-analogous behavior in microsolvation. These findings also demonstrate that photoelectron velocity map imaging spectroscopy with the aid of the ab initio calculations is an effective tool for investigating weak-interaction complexes.

Bacterial adhesion force quantification by fluidic force microscopy

NASA Astrophysics Data System (ADS)

Potthoff, Eva; Ossola, Dario; Zambelli, Tomaso; Vorholt, Julia A.

2015-02-01

Quantification of detachment forces between bacteria and substrates facilitates the understanding of the bacterial adhesion process that affects cell physiology and survival. Here, we present a method that allows for serial, single bacterial cell force spectroscopy by combining the force control of atomic force microscopy with microfluidics. Reversible bacterial cell immobilization under physiological conditions on the pyramidal tip of a microchanneled cantilever is achieved by underpressure. Using the fluidic force microscopy technology (FluidFM), we achieve immobilization forces greater than those of state-of-the-art cell-cantilever binding as demonstrated by the detachment of Escherichia coli from polydopamine with recorded forces between 4 and 8 nN for many cells. The contact time and setpoint dependence of the adhesion forces of E. coli and Streptococcus pyogenes, as well as the sequential detachment of bacteria out of a chain, are shown, revealing distinct force patterns in the detachment curves. This study demonstrates the potential of the FluidFM technology for quantitative bacterial adhesion measurements of cell-substrate and cell-cell interactions that are relevant in biofilms and infection biology.Quantification of detachment forces between bacteria and substrates facilitates the understanding of the bacterial adhesion process that affects cell physiology and survival. Here, we present a method that allows for serial, single bacterial cell force spectroscopy by combining the force control of atomic force microscopy with microfluidics. Reversible bacterial cell immobilization under physiological conditions on the pyramidal tip of a microchanneled cantilever is achieved by underpressure. Using the fluidic force microscopy technology (FluidFM), we achieve immobilization forces greater than those of state-of-the-art cell-cantilever binding as demonstrated by the detachment of Escherichia coli from polydopamine with recorded forces between 4 and 8 nN for many cells. The contact time and setpoint dependence of the adhesion forces of E. coli and Streptococcus pyogenes, as well as the sequential detachment of bacteria out of a chain, are shown, revealing distinct force patterns in the detachment curves. This study demonstrates the potential of the FluidFM technology for quantitative bacterial adhesion measurements of cell-substrate and cell-cell interactions that are relevant in biofilms and infection biology. Electronic supplementary information (ESI) available: Video S1. Detachment of a S. pyogenes cell chain from glass substrate. The cantilever is approached on the outermost adherent cell of a chain and four bacteria were then sequentially detached. The sequential cell detachment suddenly stopped after four bacteria. This possibly occurred because bacteria-glass interactions became too strong or the maximal probe retraction was reached. The cells spontaneously detached from the cantilever flipping back on the surface. Fig. S1. (A) Adhesion force-distance and (B) adhesion force-detaching work correlation of E.coli on PLL for setpoints of 1 and 10 nN. Circle: 1 nN setpoint, square: 10 nN. See DOI: 10.1039/c4nr06495j

Strong electron correlation in UO{sub 2}{sup −}: A photoelectron spectroscopy and relativistic quantum chemistry study

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

Li, Wei-Li; Jian, Tian; Lopez, Gary V.

2014-03-07

The electronic structures of actinide systems are extremely complicated and pose considerable challenges both experimentally and theoretically because of significant electron correlation and relativistic effects. Here we report an investigation of the electronic structure and chemical bonding of uranium dioxides, UO{sub 2}{sup −} and UO{sub 2}, using photoelectron spectroscopy and relativistic quantum chemistry. The electron affinity of UO{sub 2} is measured to be 1.159(20) eV. Intense detachment bands are observed from the UO{sub 2}{sup −} low-lying (7sσ{sub g}){sup 2}(5fϕ{sub u}){sup 1} orbitals and the more deeply bound O2p-based molecular orbitals which are separated by a large energy gap from themore » U-based orbitals. Surprisingly, numerous weak photodetachment transitions are observed in the gap region due to extensive two-electron transitions, suggesting strong electron correlations among the (7sσ{sub g}){sup 2}(5fϕ{sub u}){sup 1} electrons in UO{sub 2}{sup −} and the (7sσ{sub g}){sup 1}(5fϕ{sub u}){sup 1} electrons in UO{sub 2}. These observations are interpreted using multi-reference ab initio calculations with inclusion of spin-orbit coupling. The strong electron correlations and spin-orbit couplings generate orders-of-magnitude more detachment transitions from UO{sub 2}{sup −} than expected on the basis of the Koopmans’ theorem. The current experimental data on UO{sub 2}{sup −} provide a long-sought opportunity to arbitrating various relativistic quantum chemistry methods aimed at handling systems with strong electron correlations.« less

Bacteriophage PRD1 batch experiments to study attachment, detachment and inactivation processes

NASA Astrophysics Data System (ADS)

Sadeghi, Gholamreza; Schijven, Jack F.; Behrends, Thilo; Hassanizadeh, S. Majid; van Genuchten, Martinus Th.

2013-09-01

Knowledge of virus removal in subsurface environments is pivotal for assessing the risk of viral contamination of water resources and developing appropriate protection measures. Columns packed with sand are frequently used to quantify attachment, detachment and inactivation rates of viruses. Since column transport experiments are very laborious, a common alternative is to perform batch experiments where usually one or two measurements are done assuming equilibrium is reached. It is also possible to perform kinetic batch experiments. In that case, however, it is necessary to monitor changes in the concentration with time. This means that kinetic batch experiments will be almost as laborious as column experiments. Moreover, attachment and detachment rate coefficients derived from batch experiments may differ from those determined using column experiments. The aim of this study was to determine the utility of kinetic batch experiments and investigate the effects of different designs of the batch experiments on estimated attachment, detachment and inactivation rate coefficients. The experiments involved various combinations of container size, sand-water ratio, and mixing method (i.e., rolling or tumbling by pivoting the tubes around their horizontal or vertical axes, respectively). Batch experiments were conducted with clean quartz sand, water at pH 7 and ionic strength of 20 mM, and using the bacteriophage PRD1 as a model virus. Values of attachment, detachment and inactivation rate coefficients were found by fitting an analytical solution of the kinetic model equations to the data. Attachment rate coefficients were found to be systematically higher under tumbling than under rolling conditions because of better mixing and more efficient contact of phages with the surfaces of the sand grains. In both mixing methods, more sand in the container yielded higher attachment rate coefficients. A linear increase in the detachment rate coefficient was observed with increased solid-water ratio using tumbling method. Given the differences in the attachment rate coefficients, and assuming the same sticking efficiencies since chemical conditions of the batch and column experiments were the same, our results show that collision efficiencies of batch experiments are not the same as those of column experiments. Upscaling of the attachment rate from batch to column experiments hence requires proper understanding of the mixing conditions. Because batch experiments, in which the kinetics are monitored, are as laborious as column experiments, there seems to be no major advantage in performing batch instead of column experiments.

Endoscopic Rectus Abdominis and Prepubic Aponeurosis Repairs for Treatment of Athletic Pubalgia.

PubMed

Matsuda, Dean K; Matsuda, Nicole A; Head, Rachel; Tivorsak, Tanya

2017-02-01

Review of the English orthopaedic literature reveals no prior report of endoscopic repair of rectus abdominis tears and/or prepubic aponeurosis detachment. This technical report describes endoscopic reattachment of an avulsed prepubic aponeurosis and endoscopic repair of a vertical rectus abdominis tear immediately after endoscopic pubic symphysectomy for coexistent recalcitrant osteitis pubis as a single-stage outpatient surgery. Endoscopic rectus abdominis repair and prepubic aponeurosis repair are feasible surgeries that complement endoscopic pubic symphysectomy for patients with concurrent osteitis pubis and expand the less invasive options for patients with athletic pubalgia.

Space Shuttle Project

NASA Image and Video Library

1972-03-07

This early chart conceptualizes the use of two parallel Solid Rocket Motor Boosters in conjunction with three main engines to launch the proposed Space Shuttle to orbit. At approximately twenty-five miles altitude, the boosters would detach from the Orbiter and parachute back to Earth where they would be recovered and refurbished for future use. The Shuttle was designed as NASA's first reusable space vehicle, launching vertically like a spacecraft and landing on runways like conventional aircraft. Marshall Space Flight Center had management responsibility for the Shuttle's propulsion elements, including the Solid Rocket Boosters.

Vertical Distribution of Dust and Water Ice Aerosols from CRISM Limb-geometry Observations

NASA Technical Reports Server (NTRS)

Smith, Michael Doyle; Wolff, Michael J.; Clancy, Todd; Kleinbohl, Armin; Murchie, Scott L.

2013-01-01

[1] Near-infrared spectra taken in a limb-viewing geometry by the Compact Reconnaissance Imaging Spectrometer for Mars (CRISM) on board the Mars Reconnaissance Orbiter provide a useful tool for probing atmospheric structure. Specifically, the observed radiance as a function of wavelength and height above the limb enables the vertical distribution of both dust and water ice aerosols to be retrieved. More than a dozen sets of CRISM limb observations have been taken so far providing pole-to-pole cross sections, spanning more than a full Martian year. Radiative transfer modeling is used to model the observations taking into account multiple scattering from aerosols and the spherical geometry of the limb observations. Both dust and water ice vertical profiles often show a significant vertical structure for nearly all seasons and latitudes that is not consistent with the well-mixed or Conrath-v assumptions that have often been used in the past for describing aerosol vertical profiles for retrieval and modeling purposes. Significant variations are seen in the retrieved vertical profiles of dust and water ice aerosol as a function of season. Dust typically extends to higher altitudes (approx. 40-50km) during the perihelion season than during the aphelion season (<20km), and the Hellas region consistently shows more dust mixed to higher altitudes than other locations. Detached water ice clouds are common, and water ice aerosols are observed to cap the dust layer in all seasons.

Density functional theory study on the ionization potentials and electron affinities of thymine-formamide complexes

NASA Astrophysics Data System (ADS)

Sun, Haitao; Tang, Ke; Li, Yanmin; Su, Chunfang; Zhou, Zhengyu; Wang, Zhizhong

The effect of hydrogen bond interactions on ionization potentials (IPs) and electron affinities (EAs) of thymine-formamide complexes (T-F) have been investigated employing the density functional theory B3LYP at 6-311++G(d, p) basis set level. All complexes experience a geometrical change on either electron detachment or attachment, and the change might be facilitated or hindered according to the strength of the hydrogen-bonding interaction involved. The strength of hydrogen bonds presents an opposite changing trend on the two processes. A more important role that H-bonding interaction plays in the process of electron attachment than in the process of electron detachment can be seen by a comparison of the IPs and EAs of complexes with that of isolated thymine. Futhermore, the EAs of isolated thymine are in good agreement with the experimental values (AEA is 0.79 eV, VEA is -0.29 eV [Wetmore et al., Chem Phys Lett 2000, 322, 129]). The calculated total NPA charge distributions reveal that nearly all the negative charges locate on thymine monomer in the anions and even in the cationic states, there are a few negative charges on thymine monomer. An analysis of dissociation energies predicts the processes T-F+→ T++ F and T-F- → T- + F to be the most energetically favorable for T-F+ and T-F-, respectively. Content:text/plain; charset="UTF-8"

Negative ion kinetics in RF glow discharges

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

Gottscho, R.A.; Gacbe, C.E.

1986-04-01

Using temporally and spatially resolved laser spectroscopy, the authors have determined the identities, approximate concentrations, effects on the local field, and kinetics of formation and loss of negative ions in RF discharges. CI/sup -/ and BCI/sub 3//sup -/ are the dominant negative ions found in low-frequency discharges through CI/sub 2/ and BCI/sub 3/, respectively. The electron affinity for CI is measured to be 3.6118 +- 0.0005 eV. Negative ion kinetics are strongly affected by application of the RF field. Formation of negative ions by attachment of slow electrons in RF discharges is governed by the extent and duration of electronmore » energy relaxation. Similarly, destruction of negative ions by collisional detachment and field extraction is dependent upon ion energy modulation. Thus, at low frequency, the anion density peaks at the beginning of the anodic and cathodic half-cycles after electrons have attached but before detachment and extraction have had time to occur. At higher frequencies, electrons have insufficient time to attach before they are reheated and the instantaneous anion density in the sheath is greatly reduced. When the negative ion density is comparable to the positive ion density, the plasma potential is observed to lie below the anode potential, double layers form between sheath and plasma, and anions and electrons are accelerated by large sheath fields to electrode surfaces.« less

On the Measurement of Electron Temperature by Single Langmuir Probes in High Recycling Divertors

NASA Astrophysics Data System (ADS)

Pitts, Richard; Horacek, Jan; Loarte, Alberto

2000-10-01

Under high recycling and detached conditions, divertor Langmuir probes often yield a significantly higher value of Te than expected. The influence of plasma turbulence and the effect of fast electrons/plasma collisionality are two reasons why this might occur. We concentrate on these two candidates, with particular reference to observations on the TCV tokamak. A systematic study of the effects of noise on simulated probe characteristics at low T_e, shows that the asymmetric, exponential nature of the characteristic favours electron collection such that fluctuations in Vf alone actually tend to reduce the derived Te from that which would otherwise be found. We have also studied the effects of correlated density and potential fluctuations, finding no effect on the fitted T_e. The sheath potential fall energetically filters electrons such that at high densities, the probe measured Te may be characteristic of hotter, more distant zones in the plasma. We use model parallel field profiles of Te and ne generated from B2-Eirene simulations of TCV discharges as input to the analytic theory of Wesson [1] to show how a divertor plate measurement of Te in TCV can exceed the expected value by factors of up to 6 as detachment is approached. [1] J. A. Wesson, Plasma Phys. and Contr. Fusion 37 (1995) 1459

Using structures of the August 24, 2016 Amatrice earthquake affected area as seismoscopes for assessing ground motion characteristics and parameters of the main shock and its largest aftershocks

NASA Astrophysics Data System (ADS)

Carydis, Panayotis; Lekkas, Efthymios; Mavroulis, Spyridon

2017-04-01

On August 24, 2016 an Mw 6.0 earthquake struck Central Apennines (Italy) resulting in 299 fatalities, 388 injuries and about 3000 homeless in Amatrice wider area. Normal faulting surface ruptures along the western slope of Mt Vettore along with provided focal mechanisms demonstrated a NW-SE striking and SE dipping causative normal fault. The dominant building types in the affected area are unreinforced masonry (URM) and reinforced concrete (RC) buildings. Based on our macroseismic survey in the affected area immediately after the earthquake, RC buildings suffered non-structural damage including horizontal cracking of infill and internal partition walls, detachment of infill walls from the surrounding RC frame and detachment of large plaster pieces from infill walls as well as structural damage comprising soft story failure, symmetrical buckling of rods, compression damage at midheight of columns and bursting of over-stressed columns resulting in partial or total collapse. Damage in RC buildings was due to poor quality of concrete, inadequacy of reinforcement, inappropriate foundation close to the edge of slopes leading to differential settlements, poor workmanship and the destructive effect of vertical ground motions. Damage in URM buildings ranged from cracks and detachment of large plaster pieces from load-bearing walls to destruction due to poor workmanship with randomly placed materials bound by low-strength mortars, the effect of the vertical ground motion, inadequate repair and/or strengthening after previous earthquakes as well as inadequate interventions, additions and extensions to older URM buildings. During field surveying, the authors had the opportunity to observe damage induced not only by the main shock but also by its largest aftershocks (Mw 4.5-5.3) during the first three days of the aftershock sequence (August 24-26). Bearing in mind that: (a) soil conditions in foundations of the affected villages were more or less similar, (b) building damage induced by the studied earthquakes indicated the predominant effect of the vertical ground motion on buildings based on already reported building damage induced by recent destructive events in the Mediterranean region, (c) the conventional dynamic parameters of buildings did not play a significant role in their seismic response against the vertical component, due to its impact type of loading, (d) structures and materials presented similar response to ground motions almost independent from type and existing quality, and carried memories from previous large shocks of this sequence, (e) the main shock and its largest aftershocks caused building damage including spatial homothetic motions that reached statistically significant levels, it is concluded that the main shock and its largest aftershocks had similar focal mechanism parameters (normal faulting), were shallow events and were near-field earthquakes with short duration but high amplitude and the vertical component of the earthquakes' ground motion has prevailed. The aforementioned approach based solely on macroseismic observations was applied in the case of the 1755 Great Lisbon earthquake in order to determine its mechanism and epicenter location. Thus, it is suggested that the aforementioned methodology can be applied either in past historic earthquakes or complementarily in cases when the available seismological data are insufficient.

Impurity ion flow and temperature measured in a detached divertor with externally applied non-axisymmetric fields on DIII-D

DOE PAGES

Briesemeister, A. R.; Isler, R. C.; Allen, S. L.; ...

2014-11-15

In this study, externally applied non-axisymmetric magnetic fields are shown to have little effect on the impurity ion flow velocity and temperature as measured by the multichord divertor spectrometer in the DIII-D divertor for both attached and detached conditions. These experiments were performed in H-mode plasmas with the grad-B drift toward the target plates, with and without n = 3 resonant magnetic perturbations (RMPs). The flow velocity in the divertor is shown to change by as much as 30% when deuterium gas puffing is used to create detachment of the divertor plasma. No measurable changes in the C III flowmore » were observed in response to the RMP fields for the conditions used in this work. Images of the C III emission are used along with divertor Thomson scattering to show that the local electron and C III temperatures are equilibrated for the conditions shown.« less

The disappearance and reappearance of Titan's detached haze layer

NASA Astrophysics Data System (ADS)

West, Robert; Rannou, Pascal; Lavvas, Panayotis; Seignovert, Benoit; Turtle, Elizabeth P.; Perry, Jason; Ovanessian, Aida; Roy, Mou

2016-10-01

Titan's extended haze is a prominent and long-lived feature of the atmosphere that encompasses a rich variety of chemical, dynamical and microphysical processes operating over a wide range of temporal and spatial scales. The so-called 'detached' haze layer is easily seen in high-resolution short-wave (near-UV and blue wavelengths) images and is a consequence of a nearly global (outside of the winter polar hood region) layer depleted in aerosol content. It was first seen near 350 Km altitude in Voyager images (Rages and Pollack, 1983) and later observed by the Cassini ISS cameras (Porco et al., 2005; West et al., 2010) and UV stellar occultation profiles (Koskinen et al. 2011). A series of Cassini images from 2009 to 2010 revealed what appears to be a seasonally related altitude variation with remarkable regularity (comparing the Voyager and Cassini images). The drop in altitude is most rapid at equinox. Here we report on images of the upper haze layer over the period 2012 to early 2016. In the early part of this period the detached haze continued to drop in altitude and disappeared. There was no evidence for it beginning late in 2012 and extending to early 2016 when it was again detected with very low contrast at an altitude near 500 Km. We document this behavior and examine the evolution of the haze as functions of both latitude and time. These new details put additional constraints on models that attempt to account for the existence of the detached layer. Part of this work was done by the Jet Propulsion Laboratory, California Institute of Technology. References: Rages, K., and J. B. Pollack (1983), Vertical distribution of scattering hazes in Titan's upper atmosphere, Icarus, 55, 50-62, doi:10.1016/0019-1035 (83)90049-0; Porco, C. C. et al., Imaging Titan from the Cassini Spacecraft, Nature 434, 159-168 (2005); West, R. A. et al., The evolution of Titans detached haze layer near equinox in 2009", Geophys. Res. Lett. 38, L06204, doi:10.1029/2011GL046843, 2011; Koskinen T.T., et al., The mesosphere and lower thermosphere of Titan revealed by Cassini/UVIS stellar occultations, Icarus 216 507534, 2011.

Vertical muscle transposition with silicone band belting in VI nerve palsy

PubMed Central

Freitas, Cristina

2016-01-01

A woman aged 60 years developed a Millard-Gubler syndrome after a diagnosis of a cavernous angioma in the median and paramedian areas of the pons. In this context, she presented a right VI nerve palsy, right conjugate gaze palsy, facial palsy and left hemiparesis. To improve the complete VI nerve palsy, we planned a modified transposition approach, in which procedure we made a partial transposition of vertical rectus with a silicone band that was fixated posteriorly. After the procedure, the patient gained the ability to slightly abduct the right eye. We found no compensatory torticollis in the primary position of gaze. There was also an improvement of elevation and depression movements of the right eye. We obtained satisfactory results with a theoretically reversible technique, which is adjustable intraoperatively with no need of muscle detachment, preventing anterior segment ischaemia and allowing simultaneous recession of the medial rectus muscles, if necessary. PMID:27974341

A detached eddy simulation model for the study of lateral separation zones along a large canyon-bound river

NASA Astrophysics Data System (ADS)

Alvarez, Laura V.; Schmeeckle, Mark W.; Grams, Paul E.

2017-01-01

Lateral flow separation occurs in rivers where banks exhibit strong curvature. In canyon-bound rivers, lateral recirculation zones are the principal storage of fine-sediment deposits. A parallelized, three-dimensional, turbulence-resolving model was developed to study the flow structures along lateral separation zones located in two pools along the Colorado River in Marble Canyon. The model employs the detached eddy simulation (DES) technique, which resolves turbulence structures larger than the grid spacing in the interior of the flow. The DES-3D model is validated using Acoustic Doppler Current Profiler flow measurements taken during the 2008 controlled flood release from Glen Canyon Dam. A point-to-point validation using a number of skill metrics, often employed in hydrological research, is proposed here for fluvial modeling. The validation results show predictive capabilities of the DES model. The model reproduces the pattern and magnitude of the velocity in the lateral recirculation zone, including the size and position of the primary and secondary eddy cells, and return current. The lateral recirculation zone is open, having continuous import of fluid upstream of the point of reattachment and export by the recirculation return current downstream of the point of separation. Differences in magnitude and direction of near-bed and near-surface velocity vectors are found, resulting in an inward vertical spiral. Interaction between the recirculation return current and the main flow is dynamic, with large temporal changes in flow direction and magnitude. Turbulence structures with a predominately vertical axis of vorticity are observed in the shear layer becoming three-dimensional without preferred orientation downstream.

Divertor heat flux mitigation in the National Spherical Torus Experimenta)

NASA Astrophysics Data System (ADS)

Soukhanovskii, V. A.; Maingi, R.; Gates, D. A.; Menard, J. E.; Paul, S. F.; Raman, R.; Roquemore, A. L.; Bell, M. G.; Bell, R. E.; Boedo, J. A.; Bush, C. E.; Kaita, R.; Kugel, H. W.; Leblanc, B. P.; Mueller, D.; NSTX Team

2009-02-01

Steady-state handling of divertor heat flux is a critical issue for both ITER and spherical torus-based devices with compact high power density divertors. Significant reduction of heat flux to the divertor plate has been achieved simultaneously with favorable core and pedestal confinement and stability properties in a highly shaped lower single null configuration in the National Spherical Torus Experiment (NSTX) [M. Ono et al., Nucl. Fusion 40, 557 2000] using high magnetic flux expansion at the divertor strike point and the radiative divertor technique. A partial detachment of the outer strike point was achieved with divertor deuterium injection leading to peak flux reduction from 4-6MWm-2to0.5-2MWm-2 in small-ELM 0.8-1.0MA, 4-6MW neutral beam injection-heated H-mode discharges. A self-consistent picture of the outer strike point partial detachment was evident from divertor heat flux profiles and recombination, particle flux and neutral pressure measurements. Analytic scrape-off layer parallel transport models were used for interpretation of NSTX detachment experiments. The modeling showed that the observed peak heat flux reduction and detachment are possible with high radiated power and momentum loss fractions, achievable with divertor gas injection, and nearly impossible to achieve with main electron density, divertor neutral density or recombination increases alone.

Release of Particulate Iron Sulfide during Shale-Fluid Interaction.

PubMed

Kreisserman, Yevgeny; Emmanuel, Simon

2018-01-16

During hydraulic fracturing, a technique often used to extract hydrocarbons from shales, large volumes of water are injected into the subsurface. Although the injected fluid typically contains various reagents, it can become further contaminated by interaction with minerals present in the rocks. Pyrite, which is common in organic-rich shales, is a potential source of toxic elements, including arsenic and lead, and it is generally thought that for these elements to become mobilized, pyrite must first dissolve. Here, we use atomic force microscopy and environmental scanning electron microscopy to show that during fluid-rock interaction, the dissolution of carbonate minerals in Eagle Ford shale leads to the physical detachment, and mobilization, of embedded pyrite grains. In experiments carried out over a range of pH, salinity, and temperature we found that in all cases pyrite particles became detached from the shale surfaces. On average, the amount of pyrite detached was equivalent to 6.5 × 10 -11 mol m -2 s -1 , which is over an order of magnitude greater than the rate of pyrite oxidation expected under similar conditions. This result suggests that mechanical detachment of pyrite grains could be an important pathway for the mobilization of arsenic in hydraulic fracturing operations and in groundwater systems containing shales.

Electron detachment dissociation of fluorescently labeled sialylated oligosaccharides.

PubMed

Zhou, Wen; Håkansson, Kristina

2011-12-01

We explored the application of electron detachment dissociation (EDD) and infrared multiphoton dissociation (IRMPD) tandem mass spectrometry to fluorescently labeled sialylated oligosaccharides. Standard sialylated oligosaccharides and a sialylated N-linked glycan released from human transferrin were investigated. EDD yielded extensive glycosidic cleavages and cross-ring cleavages in all cases studied, consistently providing complementary structural information compared with infrared multiphoton dissociation. Neutral losses and satellite ions such as C-2H ions were also observed following EDD. In addition, we examined the influence of different fluorescent labels. The acidic label 2-aminobenzoic acid (2-AA) enhanced signal abundance in negative-ion mode. However, few cross-ring fragments were observed for 2-AA-labeled oligosaccharides. The neutral label 2-aminobenzamide (2-AB) resulted in more cross-ring cleavages compared with 2-AA-labeled species, but not as extensive fragmentation as for native oligosaccharides, likely resulting from altered negative charge locations from introduction of the fluorescent tag. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Reactions of O- with D2 at temperatures below 300 K

NASA Astrophysics Data System (ADS)

Plašil, Radek; Tran, Thuy D.; Roučka, Štěpán; Rednyk, Serhiy; Kovalenko, Artem; Jusko, Pavol; Mulin, Dmytro; Zymak, Illia; Dohnal, Petr; Glosík, Juraj

2017-11-01

The reaction of O- anions with molecular deuterium D2 has been studied experimentally using a cryogenic 22-pole radiofrequency ion trap. Two reaction channels were observed. In the associative detachment D2O and an electron are formed and for atom transfer formation OD- + D was observed. The rate coefficients of the reactions have been determined at temperatures below 300 K. The reaction rate coefficient k 1 of the associative detachment increases with decreasing temperature from k 1(300 K) = 0.5 × 10-9 cm3 s-1 at 300 K up to k 1(70 K) = 1.2 × 10-9 cm3 s-1 at 70 K both with 30 % overall uncertainty.

Harnessing the self-harvesting capability of benthic cyanobacteria for use in benthic photobioreactors

PubMed Central

2011-01-01

Benthic species of algae and cyanobacteria (i.e., those that grow on surfaces), may provide potential advantages over planktonic species for some commercial-scale biotechnological applications. A multitude of different designs of photobioreactor (PBR) are available for growing planktonic species but to date there has been little research on PBR for benthic algae or cyanobacteria. One notable advantage of some benthic cyanobacterial species is that during their growth cycle they become positively buoyant, detach from the growth surface and form floating mats. This 'self-harvesting' capability could be advantageous in commercial PBRs as it would greatly reduce dewatering costs. In this study we compared the growth rates and efficiency of 'self-harvesting' among three species of benthic cyanobacteria; Phormidium autumnale; Phormidium murrayi and Planktothrix sp.. Phormidium autumnale produced the greatest biomass and formed cohesive mats once detached. Using this strain and an optimised MLA media, a variety of geometries of benthic PBRs (bPBRs) were trialed. The geometry and composition of growth surface had a marked effect on cyanobacterial growth. The highest biomass was achieved in a bPBR comprising of a vertical polyethylene bag with loops of silicone tubing to provide additional growth surfaces. The productivity achieved in this bPBR was a similar order of magnitude as planktonic species, with the additional advantage that towards the end of the exponential phase the bulk of the biomass detached forming a dense mat at the surface of the medium. PMID:21906375

Existence, stability, and nonlinear dynamics of detached Bridgman growth states under zero gravity

NASA Astrophysics Data System (ADS)

Yeckel, Andrew; Derby, Jeffrey J.

2011-01-01

A thermocapillary model is used to study the existence, stability, and nonlinear dynamics of detached melt crystal growth in a vertical Bridgman system under zero gravity conditions. The model incorporates time-dependent heat, mass, and momentum transport, and accounts for temperature-dependent surface tension effects at the menisci bounding the melt. The positions of the menisci and phase-change boundary are computed to satisfy the conservation laws rigorously. A rich bifurcation structure in gap width versus pressure difference is uncovered, demarcating conditions under which growth with a stable gap is feasible. Thermal effects shift the bifurcation diagram to a slightly different pressure range, but do not alter its general structure. Necking and freeze-off are shown to be two different manifestations of the same instability mechanism. Supercooling of melt at the meniscus and low thermal gradients in the melt ahead of the crystal-melt-gas triple phase line, either of which may be destabilizing, are both observed under some conditions. The role of wetting and growth angles in dynamic shape stability is clarified.

Different Conformations of 2'-Deoxycytidine in the Gas and Solid Phases: Competition between Intra- and Intermolecular Hydrogen Bonds.

PubMed

Ling, Sanliang; Gutowski, Maciej

2016-10-06

Computational results have been reported for 2'-deoxycytidine (dC), its gas phase isomers, tautomers, and their conformers, as well as for the crystalline phase. In addition to the neutral gas phase molecules, we have also considered associated radical anions and cations. The structural calculations were performed at the density functional and MP2 levels of theory. Vertical electron ionization energies and excess electron binding energies were determined using electron propagator theory. The α-anomer proved to be more stable by a fraction of kcal/mol than the biologically relevant canonical β-anomer. The conformational space of canonical dC has been systematically probed. dC in the crystalline phase or DNA structures favors canonical anti conformations. These structures were used in past computational studies to model gas phase characteristics of dC. Our findings indicate, however, that the gas phase dC favors syn conformations. It has repercussions for earlier interpretations of gas phase experimental results based on these computational results. The thermodynamic dominance of syn conformations results from the formation of an intramolecular O5'-H13···O2 hydrogen bond. The IR spectra of the most stable syn and anti canonical conformers differ markedly in the region of frequencies corresponding to NH/OH stretching modes. The MP2 value of deprotonation enthalpy of dC of 1411.7 kJ/mol is in very good agreement with the experimental value of 1409 ± 2.5 kJ/mol. The most stable valence anions are characterized by electron vertical detachment energies (VDE) in the 0.8-1.0 eV range, in good agreement with the experimental VDE of 0.87 eV. The barrier for the glycosidic bond cleavage is significant in the neutral canonical dC, 40.0 kcal/mol, and it is reduced to 22 and 16 kcal/mol for the anionic and cationic radicals of dC, respectively. The cleavage reaction is exothermic by 4 kcal/mol for dC - and endothermic by 7 and 9 kcal/mol for dC + and dC, respectively. We decomposed the crystal cohesive energy into repulsive one-body terms associated with the syn-anti conformational changes, and the attractive intermolecular interaction term. We exposed that the syn-anti conformational changes are very favorable for intermolecular interactions; in particular they make the imino-amino side of the cytosine residue accessible to intermolecular interactions.

Extracellular Electron Uptake: Among Autotrophs and Mediated by Surfaces.

PubMed

Tremblay, Pier-Luc; Angenent, Largus T; Zhang, Tian

2017-04-01

Autotrophic microbes can acquire electrons from solid donors such as steel, other microbial cells, or electrodes. Based on this feature, bioprocesses are being developed for the microbial electrosynthesis (MES) of useful products from the greenhouse gas CO 2 . Extracellular electron-transfer mechanisms involved in the acquisition of electrons from metals by electrical microbially influenced corrosion (EMIC), from other living cells by interspecies electron transfer (IET), or from an electrode during MES rely on: (i) mediators such as H 2 ; (ii) physical contact through electron-transfer proteins; or (iii) mediator-generating enzymes detached from cells. This review explores the interactions of autotrophs with solid electron donors and their importance in nature and for biosustainable technologies. Copyright © 2016 Elsevier Ltd. All rights reserved.

Suprathermal electron energy distribution within the dayside Venus ionosphere

NASA Technical Reports Server (NTRS)

Knudsen, W. C.; Miller, K. L.; Spenner, K.; Novak, V.; Michelson, P. F.; Whitten, R. C.

1980-01-01

The suprathermal electron energy distribution for the dayside ionosphere has been derived from data returned by the Pioneer-Venus orbiter retarding potential analyzer. The shape and magnitude of the spectrum are consistent with the assumption that solar EUV radiation is the only significant source. The magnitude of the spectrum and its variation with altitude suggest that significant vertical transport occurs, with the electrons being lost through the ionopause. In turn, significant vertical transport suggests that the effective vertical electron heat conductivity may be comparable to the field-free value. The heat input to the thermal electron gas from the measured suprathermal electron flux is too small by a factor of at least five to maintain the observed electron temperature profile if the electron thermal conductivity is assumed to be close to the field-free value. It is thus inferred that most of the heat is supplied by the solar wind.

Next Generation Energetic Materials: New Cluster Hydrides and Metastable Alloys of Aluminum in Very Low Oxidation States

DTIC Science & Technology

2016-10-01

in the spectrum is the vertical detachment energy, VDE , which reflects the maximum Franck-Condon overlap between the wave functions of the anion’s...i.e., its estimated EA value. Table I presents both calculated and measured values of VDE and of ADE/EA. Below, the five designated cluster anion...Focusing on the lower energy transition, the calculated values of ADE and VDE for isomers 1 (1.20 eV and 1.63 eV), 2 (1.18 eV and 1.47 eV), and 3

Photoelectron spectroscopy of B4O4-: Dual 3c-4e π hyperbonds and rhombic 4c-4e o-bond in boron oxide clusters

NASA Astrophysics Data System (ADS)

Tian, Wen-Juan; Zhao, Li-Juan; Chen, Qiang; Ou, Ting; Xu, Hong-Guang; Zheng, Wei-Jun; Zhai, Hua-Jin; Li, Si-Dian

2015-04-01

Gas-phase anion photoelectron spectroscopy (PES) is combined with global structural searches and electronic structure calculations at the hybrid Becke 3-parameter exchange functional and Lee-Yang-Parr correlation functional (B3LYP) and single-point coupled-cluster with single, double, and perturbative triple excitations (CCSD(T)) levels to probe the structural and electronic properties and chemical bonding of the B4O40/- clusters. The measured PES spectra of B4O4- exhibit a major band with the adiabatic and vertical detachment energies (ADE and VDE) of 2.64 ± 0.10 and 2.81 ± 0.10 eV, respectively, as well as a weak peak with the ADE and VDE of 1.42 ± 0.08 and 1.48 ± 0.08 eV. The former band proves to correspond to the Y-shaped global minimum of Cs B4O4- (2A″), with the calculated ADE/VDE of 2.57/2.84 eV at the CCSD(T) level, whereas the weak band is associated with the second lowest-energy, rhombic isomer of D2h B4O4- (2B2g) with the predicted ADE/VDE of 1.43/1.49 eV. Both anion structures are planar, featuring a B atom or a B2O2 core bonded with terminal BO and/or BO2 groups. The same Y-shaped and rhombic structures are also located for the B4O4 neutral cluster, albeit with a reversed energy order. Bonding analyses reveal dual three-center four-electron (3c-4e) π hyperbonds in the Y-shaped B4O40/- clusters and a four-center four-electron (4c-4e) π bond, that is, the so-called o-bond in the rhombic B4O40/- clusters. This work is the first experimental study on a molecular system with an o-bond.

Bacteriophage PRD1 batch experiments to study attachment, detachment and inactivation processes.

PubMed

Sadeghi, Gholamreza; Schijven, Jack F; Behrends, Thilo; Hassanizadeh, S Majid; van Genuchten, Martinus Th

2013-09-01

Knowledge of virus removal in subsurface environments is pivotal for assessing the risk of viral contamination of water resources and developing appropriate protection measures. Columns packed with sand are frequently used to quantify attachment, detachment and inactivation rates of viruses. Since column transport experiments are very laborious, a common alternative is to perform batch experiments where usually one or two measurements are done assuming equilibrium is reached. It is also possible to perform kinetic batch experiments. In that case, however, it is necessary to monitor changes in the concentration with time. This means that kinetic batch experiments will be almost as laborious as column experiments. Moreover, attachment and detachment rate coefficients derived from batch experiments may differ from those determined using column experiments. The aim of this study was to determine the utility of kinetic batch experiments and investigate the effects of different designs of the batch experiments on estimated attachment, detachment and inactivation rate coefficients. The experiments involved various combinations of container size, sand-water ratio, and mixing method (i.e., rolling or tumbling by pivoting the tubes around their horizontal or vertical axes, respectively). Batch experiments were conducted with clean quartz sand, water at pH 7 and ionic strength of 20 mM, and using the bacteriophage PRD1 as a model virus. Values of attachment, detachment and inactivation rate coefficients were found by fitting an analytical solution of the kinetic model equations to the data. Attachment rate coefficients were found to be systematically higher under tumbling than under rolling conditions because of better mixing and more efficient contact of phages with the surfaces of the sand grains. In both mixing methods, more sand in the container yielded higher attachment rate coefficients. A linear increase in the detachment rate coefficient was observed with increased solid-water ratio using tumbling method. Given the differences in the attachment rate coefficients, and assuming the same sticking efficiencies since chemical conditions of the batch and column experiments were the same, our results show that collision efficiencies of batch experiments are not the same as those of column experiments. Upscaling of the attachment rate from batch to column experiments hence requires proper understanding of the mixing conditions. Because batch experiments, in which the kinetics are monitored, are as laborious as column experiments, there seems to be no major advantage in performing batch instead of column experiments. Copyright © 2013 Elsevier B.V. All rights reserved.

Integration of Histology Lectures and Practical Teaching in China

ERIC Educational Resources Information Center

Lu, Xiaoye; Cheng, Xin; Li, Ke; Lee, Kenneth Ka Ho; Yang, Xuesong

2016-01-01

Objectives: Human histology is a discipline concerning the study of microscopic structures of human tissues and organs--with the aid of light or electron microscopes. Traditional teaching of histology is composed of two separated components, theory and practice. The main disadvantage with traditional histology teaching is the detachment of theory…

Direct measurement of the thermal rate coefficient for electron attachment to ozone in the gas phase, 300-550 K: implications for the ionosphere.

PubMed

Van Doren, Jane M; Miller, Thomas M; Williams, Skip; Viggiano, A A

2003-11-28

Attachment of thermal electrons to O3 was studied in 133 Pa He between 300-550 K; the process is extremely inefficient. The rate coefficient increases sharply with temperature from 0.9 to 5 x 10(-11) cm(3) s(-1) (+/-30%) and comparison to kinetic energy measurements suggests internal energy can drive the reaction. These determinations account for competing processes of diffusion, recombination, and electron detachment reactions, and imply that no significant zero-energy resonance cross section exists, contradicting recent electron-beam results that call for substantial revision of ionospheric models.

Local ensemble transform Kalman filter for ionospheric data assimilation: Observation influence analysis during a geomagnetic storm event

NASA Astrophysics Data System (ADS)

Durazo, Juan A.; Kostelich, Eric J.; Mahalov, Alex

2017-09-01

We propose a targeted observation strategy, based on the influence matrix diagnostic, that optimally selects where additional observations may be placed to improve ionospheric forecasts. This strategy is applied in data assimilation observing system experiments, where synthetic electron density vertical profiles, which represent those of Constellation Observing System for Meteorology, Ionosphere, and Climate/Formosa satellite 3, are assimilated into the Thermosphere-Ionosphere-Electrodynamics General Circulation Model using the local ensemble transform Kalman filter during the 26 September 2011 geomagnetic storm. During each analysis step, the observation vector is augmented with five synthetic vertical profiles optimally placed to target electron density errors, using our targeted observation strategy. Forecast improvement due to assimilation of augmented vertical profiles is measured with the root-mean-square error (RMSE) of analyzed electron density, averaged over 600 km regions centered around the augmented vertical profile locations. Assimilating vertical profiles with targeted locations yields about 60%-80% reduction in electron density RMSE, compared to a 15% average reduction when assimilating randomly placed vertical profiles. Assimilating vertical profiles whose locations target the zonal component of neutral winds (Un) yields on average a 25% RMSE reduction in Un estimates, compared to a 2% average improvement obtained with randomly placed vertical profiles. These results demonstrate that our targeted strategy can improve data assimilation efforts during extreme events by detecting regions where additional observations would provide the largest benefit to the forecast.

Upgraded divertor Thomson scattering system on DIII-D

NASA Astrophysics Data System (ADS)

Glass, F.; Carlstrom, T. N.; Du, D.; McLean, A. G.; Taussig, D. A.; Boivin, R. L.

2016-11-01

A design to extend the unique divertor Thomson scattering system on DIII-D to allow measurements of electron temperature and density in high triangularity plasmas is presented. Access to this region is selectable on a shot-by-shot basis by redirecting the laser beam of the existing divertor Thomson system inboard — beneath the lower floor using a moveable, high-damage threshold, in-vacuum mirror — and then redirecting again vertically. The currently measured divertor region remains available with this mirror retracted. Scattered light is collected from viewchords near the divertor floor using in-vacuum, high temperature optical elements and relayed through the port window, before being coupled into optical fiber bundles. At higher elevations from the floor, measurements are made by dynamically re-focusing the existing divertor system collection optics. Nd:YAG laser timing, analysis of the scattered light spectrum via polychromators, data acquisition, and calibration are all handled by existing systems or methods of the current multi-pulse Thomson scattering system. Existing filtered polychromators with 7 spectral channels are employed to provide maximum measurement breadth (Te in the range of 0.5 eV-2 keV, ne in the range of 5 × 1018-1 × 1021 m3) for both low Te in detachment and high Te measurement up beyond the separatrix.

Upgraded divertor Thomson scattering system on DIII-D.

PubMed

Glass, F; Carlstrom, T N; Du, D; McLean, A G; Taussig, D A; Boivin, R L

2016-11-01

A design to extend the unique divertor Thomson scattering system on DIII-D to allow measurements of electron temperature and density in high triangularity plasmas is presented. Access to this region is selectable on a shot-by-shot basis by redirecting the laser beam of the existing divertor Thomson system inboard - beneath the lower floor using a moveable, high-damage threshold, in-vacuum mirror - and then redirecting again vertically. The currently measured divertor region remains available with this mirror retracted. Scattered light is collected from viewchords near the divertor floor using in-vacuum, high temperature optical elements and relayed through the port window, before being coupled into optical fiber bundles. At higher elevations from the floor, measurements are made by dynamically re-focusing the existing divertor system collection optics. Nd:YAG laser timing, analysis of the scattered light spectrum via polychromators, data acquisition, and calibration are all handled by existing systems or methods of the current multi-pulse Thomson scattering system. Existing filtered polychromators with 7 spectral channels are employed to provide maximum measurement breadth (T e in the range of 0.5 eV-2 keV, n e in the range of 5 × 10 18 -1 × 10 21 m 3 ) for both low T e in detachment and high T e measurement up beyond the separatrix.

Comparative study of dental enamel loss after debonding braces by analytical scanning electron microscopy (SEM).

PubMed

Rodríguez-Chávez, Jacqueline Adelina; Arenas-Alatorre, Jesús; Belio-Reyes, Irma Araceli

2017-07-01

Clinical procedures when shear forces are applied to brackets suggest adhesion forces between 2.8 and 10.0 MPa as appropriate. In this study dental enamel was evaluated by scanning electron microscopy (SEM) before and after removing the brackets. Thirty bicuspids (previous prophylaxis) with metallic brackets (Roth Inovation 0.022 GAC), Transbond Plus SEP 3M Unitek adhesive and Transbond XT 3M resin were used. The samples were preserved to 37°C during 24 hr and submited to tangential forces with the Instron Universal machine 1.0 mm/min speed load strength resistance debonding. Also the Adhesive Remanent Index (ARI) test was made, evaluating the bracket base and the bicuspid surface. All the bracket SEM images were processed with AutoCAD to determine the enamel detached area. The average value was 6.86 MPa (SD ± 3.2 MPa). ARI value 1= 63.3%, value 2= 20%, value 3= 13.3% and 33% presented value 0. All those samples with dental enamel loss, presented different situations as fractures, ledges, horizontal, and vertical loss in some cases, and some scratch lines. There is no association between the debonding resistance and enamel presence. Less than half of the remanent adhesive on the dental enamel was present in most of the samples when the ARI test was applied. When the resin area increases, the debonding resistance also increases, and when the enamel loss increases, the resin free metallic area of the bracket base decreases in the debonding. © 2017 Wiley Periodicals, Inc.

Dynamics of dipole- and valence bound anions in iodide-adenine binary complexes: A time-resolved photoelectron imaging and quantum mechanical investigation

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

Stephansen, Anne B.; King, Sarah B.; Li, Wei-Li

2015-09-14

Dipole bound (DB) and valence bound (VB) anions of binary iodide-adenine complexes have been studied using one-color and time-resolved photoelectron imaging at excitation energies near the vertical detachment energy. The experiments are complemented by quantum chemical calculations. One-color spectra show evidence for two adenine tautomers, the canonical, biologically relevant A9 tautomer and the A3 tautomer. In the UV-pump/IR-probe time-resolved experiments, transient adenine anions can be formed by electron transfer from the iodide. These experiments show signals from both DB and VB states of adenine anions formed on femto- and picosecond time scales, respectively. Analysis of the spectra and comparison withmore » calculations suggest that while both the A9 and A3 tautomers contribute to the DB signal, only the DB state of the A3 tautomer undergoes a transition to the VB anion. The VB anion of A9 is higher in energy than both the DB anion and the neutral, and the VB anion is therefore not accessible through the DB state. Experimental evidence of the metastable A9 VB anion is instead observed as a shape resonance in the one-color photoelectron spectra, as a result of UV absorption by A9 and subsequent electron transfer from iodide into the empty π-orbital. In contrast, the iodide-A3 complex constitutes an excellent example of how DB states can act as doorway state for VB anion formation when the VB state is energetically available.« less

Deformation of the self-adjusting file on simulated curved root canals: a time-dependent study.

PubMed

Akçay, Ilgın; Yiğit-Özer, Senem; Adigüzel, Özkan; Kaya, Sadulah

2011-11-01

This study examined the surface changes of self-adjusting file after operating in different degrees of canal curvatures with a fixed radius of curvature in different operation intervals. Artificial canals were manufactured in a 5-mm radius of curvature with 45° and 60° angles of curvature. Forty self-adjusting files were divided into 2 groups and submitted to functional fatigue to failure. Twenty files were tested using the 45° angle and the remaining 20 were tested using the 60° angle at 4 minutes for 7 periods in a total of 28 minutes. The average time frame for each 4-minute inspection period was considered as the moment of failure at 2, 6, 10, 14, 18, 22, and 26 minutes, respectively. Instruments were evaluated using scanning electron microscopy to characterize the material under study. The lattice detachment began at the second period for both groups and continued to increase along with the ongoing testing time. The detachment that occurred in 60° canal curvature was higher at the third and fourth periods when compared with the 45° group (P < .05). For both groups, during the third period, detachment of the arch of the lattice was only one sided; however, this deformation was severe between the fourth and sixth periods with a 2-sided detachment, which was easier to separate. The rough surface became smooth after usage. No full separation of the file was evident for both groups. In multirooted teeth with severely curved root canals, using more than one self-adjusting file might be recommended to prevent lattice detachment. Copyright © 2011 Mosby, Inc. All rights reserved.

Electron Affinity of trans-2-C4F8 from Electron Attachment-Detachment Kinetics

DTIC Science & Technology

2009-09-04

0.989, for DFT results. b Hartree units; G3(MP2) formalism and B3LYP/6-31+G(3df)// B3LYP/6-31+G(3df) + ZPE for DFT results. c Difference between the...units; G3(MP2) formalism and B3LYP/6-31+G(3df)// B3LYP/6-31+G(3df) + ZPE for DFT results. c Difference between the anion total energy at 0 K and that

Smooth Scaling of Valence Electronic Properties in Fullerenes: From One Carbon Atom, to C60, to Graphene

DTIC Science & Technology

2012-09-18

Smooth scaling of valence electronic properties in fullerenes: from one carbon atom , to C60, to graphene Greyson R. Lewis,1 William E. Bunting,1...pacitance scaling lines of the fullerenes. Lastly, it is found that points representing the carbon atom and the graphene limit lie on scaling lines for...icosahedral fullerenes, so their quantum capacitances and their detachment energies scale smoothly from one C atom , through C60, to graphene. I

Calculation of photoelectron spectra of molybdenum and tungsten complexes using Green's functions methods.

PubMed

Bayse, Craig A; Ortwine, Kristine N

2007-08-16

Green's functions calculations are presented for several complexes of molybdenum and tungsten, two metals that are similar structurally but display subtle, but significant, differences in electronic structure. Outer valence Green's functions IPs for M(CO)6, M(Me)6, MH6, [MCl4O](-), and [MO4](-) (M = Mo, W) are generally within +/-0.2 eV of available experimental photoelectron spectra. The calculations show that electrons in M-L bonding orbitals are ejected at lower energies for Mo while the detachment energy for electrons in d orbitals varies with metal and complex. For the metal carbonyls, the quasiparticle picture assumed in OVGF breaks down for the inner valence pi CO molecular orbitals due to the coupling of two-hole-one-particle charge transfer states to the one-hole states. Incorporation of the 2h1p states through a Tamm-Dancoff approximation calculation accurately represents the band due to detachment from these molecular orbitals. Though the ordering of IPs for Green's functions methods and DFT Koopmans' theorem IPs is similar for the highest IPs for most compounds considered, the breakdown of the quasiparticle picture for the metal carbonyls suggests that scaling of the latter values may result in a fortuitous or incorrect assignment of experimental VDEs.

Photodetachment process for beam neutralization

DOEpatents

Fink, Joel H. [Livermore, CA; Frank, Alan M. [Livermore, CA

1979-02-20

A process for neutralization of accelerated ions employing photo-induced charge detachment. The process involves directing a laser beam across the path of a negative ion beam such as to effect photodetachment of electrons from the beam ions. The frequency of the laser beam employed is selected to provide the maximum cross-section for the photodetachment process.

Parallel Energy Transport in Detached DIII-D Divertor Plasmas

NASA Astrophysics Data System (ADS)

Leonard, A. W.; Lore, J. D.; Canik, J. M.; McLean, A. G.; Makowski, M. A.

2017-10-01

A comparison of experiment and modeling of detached divertor plasmas is examined in the context of parallel energy transport. Experimental estimates of power carried by electron thermal conduction versus plasma convection are experimentally inferred from power balance measurements of radiated power and target plate heat flux combined with Thomson scattering measurements of the Te profile along the divertor leg. Experimental profiles of Te exhibit relatively low gradients with Te < 15 eV from the X-point to the target implying transport dominated by convection. In contrast, fluid modeling with SOLPS produces sharp Te gradients for Te > 3 eV, characteristic of transport dominated by electron conduction through the bulk of the divertor. This discrepancy with experimental transport dominated by convection and modeling by conduction has significant implications for the radiative capacity of divertor plasmas and may explain at least part of the difficulty for fluid modeling to obtain the experimentally observed radiative losses. Comparisons are also made for helium plasmas where the match between experiment and modeling is much better. Work supported by the US DOE under DE-FC02-04ER54698.

Photoelectron Spectroscopy of Free Multiply Charged Keggin Anions α-[PM12O40]3- (M = Mo, W) in the Gas Phase

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

Waters, Tom; Huang, Xin; Wang, Xue B.

2006-09-21

Two polyoxometalate Keggin-type anions, a-PM12O403- (M = Mo, W), were transferred to the gas phase by electrospray; their electronic structure and stability were probed by photoelectron spectroscopy. These triply charged anions were found to be highly stable in the gas phase with large adiabatic electron detachment energies of 1.7 and 2.1 eV for M = Mo and W, respectively. The magnitude of the repulsive Coulomb barrier was measured as ~3.4 eV for both anions, providing an experimental estimate for the intramolecular Coulomb repulsion present in these highly charged anions. Density functional theory calculations were carried out and compared with themore » experimental data, providing insight into the electronic structure and valence molecular orbitals of the two Keggin anions. The calculations indicated that the highest occupied molecular orbital and other frontier orbitals for PM12O403- are localized primarily on the u2-oxo bridging ligands of the polyoxometalate framework, consistent with the reactivity on the u2-oxo sites observed in solution. It was shown that the HOMO of PW12O403- is stabilized relative to that of PMo12O403- by ~0.35 eV. The experimental adiabatic electron detachment energies of PM12O403- (i.e., the electron affinities of PM12O402-) are combined with recent calculations on the proton affinity of PM12O403- to yield O-H bond dissociation energies in PM12O39(OH)2- as ~5.1 eV« less

Regular threshold-energy increase with charge for neutral-particle emission in collisions of electrons with oligonucleotide anions.

PubMed

Tanabe, T; Noda, K; Saito, M; Starikov, E B; Tateno, M

2004-07-23

Electron-DNA anion collisions were studied using an electrostatic storage ring with a merging electron-beam technique. The rate of neutral particles emitted in collisions started to increase from definite threshold energies, which increased regularly with ion charges in steps of about 10 eV. These threshold energies were almost independent of the length and sequence of DNA, but depended strongly on the ion charges. Neutral particles came from breaks of DNAs, rather than electron detachment. The step of the threshold energy increase approximately agreed with the plasmon excitation energy. It is deduced that plasmon excitation is closely related to the reaction mechanism. Copyright 2004 The American Physical Society

Electronic structure calculations on multiply charged anions containing M bond S bonds (M = Cr, Mo, W) and their heterobimetallic cluster complexes

NASA Astrophysics Data System (ADS)

Gili, Pedro; Tsipis, Athanassios C.

Molecular and electronic structures of multiply charged mononuclear [CrS4]2-/3-, [MoOxS4-x]2-/3- (x = 0-4) and [WS4]2-/3- anionic species, and their heterobimetallic dinuclear and trinuclear clusters formulated as [MoOS3(CuCl)]2-, [WOS3(CuCl)]2-, [MoS4{Cu(CN)}]2-, [(CN)Cu(?-CrS4)Cu(CN)]2-, [(CN)Cu(?-MoS4)Cu(CN)]2-, [ClCu(?-MoS4)CuCl]2-, [Cl2Fe(?-MoS4)CuCl2]2-, and [(CN)Cu(?-WS4)Cu(CN)]2- have been investigated using electronic structure calculation (HF, MP4SDQ and DFT) methods. For the discrete mononuclear anions HF/lanl2dz(M)?6-31+G*(S,O) method provided the best description of their molecular structures, while for the heterobimetallic dinuclear and trinuclear clusters the B3LYP/lanl2dz(M)?6-31+G* method gave equilibrium geometries closely resembling the experimental ones. Electronic and spectroscopic (IR, UV-Vis) properties of the thiometalates are discussed in relation to their structures, while the bonding mechanism was analyzed in the framework of the natural bond orbital (NBO) approach. The nature of the highest occupied molecular orbitals (HOMOs) of all thiometalates indicated their ability to act as ligands coordinated with metal centers and forming clusters of higher nuclearity. The lowest-lying vertical one-electron detachment processes from the ground state of the [CrS4]2/3-, [MoOxS4-x]2/3- (x = 0-4) and [WS4]2/3- anions have been calculated using the outer valence Green's function (OVGF) method. Interestingly, in the heterobimetallic dinuclear and trinuclear clusters intemetallic M?M? interactions exist corresponding to d10 ? d0 dative bonding. Finally, the complete energetic and geometric profile of the successive acid-catalyzed formation reactions:and the reverse hydrolysis reactions have been delineated and details of the mechanism have been furnished.

Investigation of ELF Signals Associated with Mine Warfare: A University of Idaho and Acoustic Research Detachment Collaboration, Phase 2

DTIC Science & Technology

2010-07-31

the expressions of each field components in terms of Fy and Fz. s dy dF>) dz P 1 dF. >~ edx E=-’dF> e dx CO/2£ dx dy dz OifJ...current can be ignored. The effective area is proportional to h2. Since the current decays vertically as 1/A2 and the effective area grows with fr , the...300 400 10" t 1010 :’TTTTTTTTTT-^^f 10 10 x 10 Hz I 100 Hz O 1kHz www ^ *-*** 100 200 300 400 Z(m) (b) Fig. 7. Results of the

KSC-2009-1877

NASA Image and Video Library

2009-02-25

CAPE CANAVERAL, Fla. – On Launch Pad 37 at Cape Canaveral Air Force Station in Florida, workers begin detaching the lifting mechanism that raised the GOES-O and Delta IV upper stage to vertical. GOES–O is one of a series of Geostationary Operational Environmental Satellites. The multi-mission GOES series N-P will be a vital contributor to weather, solar and space operations and science. NASA and the National Oceanic and Atmospheric Administration, or NOAA, are actively engaged in a cooperative program to expand the existing GOES system with the launch of the GOES N-P satellites. Launch of the GOES-O is targeted for no earlier than April 2009. Photo credit: NASA/Jim Grossmann

KSC-2009-1878

NASA Image and Video Library

2009-02-25

CAPE CANAVERAL, Fla. – On Launch Pad 37 at Cape Canaveral Air Force Station in Florida, workers begin detaching the lifting mechanism that raised the GOES-O and Delta IV upper stage to vertical. GOES–O is one of a series of Geostationary Operational Environmental Satellites. The multi-mission GOES series N-P will be a vital contributor to weather, solar and space operations and science. NASA and the National Oceanic and Atmospheric Administration, or NOAA, are actively engaged in a cooperative program to expand the existing GOES system with the launch of the GOES N-P satellites. Launch of the GOES-O is targeted for no earlier than April 2009. Photo credit: NASA/Jim Grossmann

The Al(I) molecule, Ph2COAl and its anion

NASA Astrophysics Data System (ADS)

Zhang, Xinxing; Eichhorn, Bryan; Schnöckel, Hansgeorg; Bowen, Kit

2016-08-01

We have formed the Al(I)-containing molecule, benzophenone-aluminum, i.e., Ph2COAl, and studied it by conducting density functional theory calculations on both its neutral and anionic forms and by measuring the photoelectron spectrum of its anion. Our calculations identified two nearly iso-energetic anion isomers, (Ph2COAl)-, the vertical detachment energies (VDE) of which are in excellent agreement with our photoelectron spectrum. Natural population analysis (NPA) of Ph2COAl found the Al moiety to be positively charged by +0.81 e, indicating a strongly ionic bond between Al and Ph2CO, i.e., Ph2CO-Al+.

Evaluation of the detachment energy of hydrated phosphate anion over a wide range of cluster size and revisiting solvent-berg model: a theoretical study

NASA Astrophysics Data System (ADS)

Pathak, Arup Kumar

2014-12-01

An explicit analytical expression has been obtained for vertical detachment energy (VDE) that can be used to calculate the same over a wide range (both stable and unstable regions) of cluster sizes including the bulk from the knowledge of VDE for a finite number of stable clusters (n = 16-23). The calculated VDE for the bulk is found to be very good in agreement (within 1%) with the available experimental result and the domain of instability lies between n = 0 and n = 15 for the hydrated clusters, PO3 -4 . nH2O. The minimum number (n0) of water molecules needed to stabilise the phosphate anion is 16. We are able to explain the origin of solvent-berg model and anomalous conductivity from the knowledge of first stable cluster. We have also provided a scheme to calculate the radius of the solvent-berg for phosphate anion. The calculated conductivity using Stokes-Einstein relation and the radius of solvent-berg is found to be very good in agreement (within 4%) with the available experimental results.

Vertical electronic transport in van de waals heterostructures

NASA Astrophysics Data System (ADS)

Qiao, Zhenhua; Zhenhua Qiao's Group Team

In this work, we will introduce the theoretical investigation of the vertical electronic transport in various heterostructrues by using both tight-binding method and first-principles calculations. Counterintuitively, we find that the maximum electronic transport is achieved at very limited scattering regions but not at large overlapped catering regions. Based on this finding, we design a special setup to measure the tunneling effect in rotated bilayer systems.

Numerical simulation of a radially injected barium cloud

NASA Technical Reports Server (NTRS)

Swift, D. W.; Wescott, E. M.

1981-01-01

Electrostatic two-dimensional numerical simulations of a radially symmetric barium injection experiment demonstrate that ions created by solar UV irradiation are electrostatically bound to the electrons which remain tied to the field lines on which they are created. Two possible instabilities are identified, but neither of them causes the barium plasma cloud to polarize in a way that would permit the plasma to keep up with the neutrals. In a second model, the velocity of the neutrals is allowed to be a function of the azimuthal angle. Here, a portion of the cloud does polarize in a way that allows a portion of the plasma to detach and move outward at the approximate speed of the neutrals. No rapid detachment is found when only the density of the neutrals is given an azimuthal asymmetry.

Fabrication of thermo-responsive PNIPAAm-g-ETFE for cell culture dishes by pre-irradiation grafting

NASA Astrophysics Data System (ADS)

Yamahara, Yumi; Nagasawa, Naotsugu; Taguchi, Mitsumasa; Oshima, Akihiro; Washio, Masakazu

2018-01-01

Thermo-responsive templates for the cell cultivation based on Poly(tetrafluoroethylene-co-ethylene) (ETFE) were fabricated by pre-irradiation grafting of N-isoproplyacrylamide (NIPAAm) monomer by electron beam (EB) irradiation under nitrogen gas atmosphere at room temperature, and their characteristic properties were studied. The detachment of cultured HeLa cells from fabricated thermo-responsive templates were attempted. Furthermore, the reaction mechanism is proposed using ESR spectroscopy and FT-IR spectroscopy. It is confirmed that the cultured HeLa cells were detached from fabricated thermo-responsive templates at 20 °C. Water contact angle analysis indicated that obtained templates had thermo-response around 30 °C. It is suggested that the grafted polymer chains would mainly react with peroxy radicals (-CF2-CF(OO･)-) on tetrafluoroethylene unit in ETFE.

Electric-field and strain-tunable electronic properties of MoS2/h-BN/graphene vertical heterostructures.

PubMed

Zan, Wenyan; Geng, Wei; Liu, Huanxiang; Yao, Xiaojun

2016-01-28

Vertical heterostructures of MoS2/h-BN/graphene have been successfully fabricated in recent experiments. Using first-principles analysis, we show that the structural and electronic properties of such vertical heterostructures are sensitive to applied vertical electric fields and strain. The applied electric field not only enhances the interlayer coupling but also linearly controls the charge transfer between graphene and MoS2 layers, leading to a tunable doping in graphene and controllable Schottky barrier height. Applied biaxial strain could weaken the interlayer coupling and results in a slight shift of graphene's Dirac point with respect to the Fermi level. It is of practical importance that the tunable electronic properties by strain and electric fields are immune to the presence of sulfur vacancies, the most common defect in MoS2.

Femtosecond laser cutting of multiple thin corneal stromal lamellae for endothelial bioengineering.

PubMed

Bernard, Aurélien; He, Zhiguo; Forest, Fabien; Gauthier, Anne-Sophie; Peocʼh, Michel; Dumollard, Jean-Marc; Acquart, Sophie; Montard, Romain; Delbosc, Bernard; Gain, Philippe; Thuret, Gilles

2015-02-01

To assess the feasibility of cutting multiple thin stromal lamellae in human donor corneas using a commercial femtosecond laser (FSL) to provide cell carriers for future endothelial graft bioengineering. Eight edematous organ-cultured corneas not suitable for grafting for endothelial reasons were mounted on a Ziemer anterior chamber and cut with a Z6 FSL with 6 successive parallel cuts, from depth to surface. Target thickness of each lamella ranged from 100 to 150 μm depending on initial corneal thickness. Thickness was measured using anterior segment optical coherence tomography before and after cutting on mounted corneas, and on each stromal lamella after detachment. Scanning electron microscopy observation was performed on 4 lamellae and histological cross sections on 1 cornea before detachment. A median of 5 (minimum 3, maximum 7) lamellae was obtained per cornea. All lamellae still attached were the most posterior ones, suggesting that FSL was less efficient because of light scattering by edematous stroma. Cut precision and postdetachment swelling were correlated with anterior-posterior position within the cornea. Median lamella thickness was 127 μm (56-222 μm) before detachment and 196 μm (80-304 μm) after detachment. Surface state was consistent with previously reported FSL lamellar cuts during Descemet stripping automated endothelial keratoplasty. Up to 7 thin lamellae can be cut in stored corneas with an FSL. This method, once optimized primarily by using deswelled, more transparent corneas, could prove effective for recycling unsuitable donor corneas in corneal bioengineering processes.

Near-infrared photoabsorption by C60 dianions in a storage ring.

PubMed

Kadhane, U; Andersen, J U; Bonderup, E; Concina, B; Hvelplund, P; Suhr Kirketerp, M-B; Liu, B; Nielsen, S Brøndsted; Panja, S; Rangama, J; Støchkel, K; Tomita, S; Zettergren, H; Hansen, K; Sundén, A E K; Canton, S E; Echt, O; Forster, J S

2009-07-07

We present a detailed study of the electronic structure and the stability of C(60) dianions in the gas phase. Monoanions were extracted from a plasma source and converted to dianions by electron transfer in a Na vapor cell. The dianions were then stored in an electrostatic ring, and their near-infrared absorption spectrum was measured by observation of laser induced electron detachment. From the time dependence of the detachment after photon absorption, we conclude that the reaction has contributions from both direct electron tunneling to the continuum and vibrationally assisted tunneling after internal conversion. This implies that the height of the Coulomb barrier confining the attached electrons is at least approximately 1.5 eV. For C(60)(2-) ions in solution electron spin resonance measurements have indicated a singlet ground state, and from the similarity of the absorption spectra we conclude that also the ground state of isolated C(60)(2-) ions is singlet. The observed spectrum corresponds to an electronic transition from a t(1u) lowest unoccupied molecular orbital (LUMO) of C(60) to the t(1g) LUMO+1 level. The electronic levels of the dianion are split due to Jahn-Teller coupling to quadrupole deformations of the molecule, and a main absorption band at 10,723 cm(-1) corresponds to a transition between the Jahn-Teller ground states. Also transitions from pseudorotational states with 200 cm(-1) and (probably) 420 cm(-1) excitation are observed. We argue that a very broad absorption band from about 11,500 cm(-1) to 13,500 cm(-1) consists of transitions to so-called cone states, which are Jahn-Teller states on a higher potential-energy surface, stabilized by a pseudorotational angular momentum barrier. A previously observed, high-lying absorption band for C(60)(-) may also be a transition to a cone state.

Photodetachment process for beam neutralization

DOEpatents

Fink, J.H.; Frank, A.M.

1979-02-20

A process for neutralization of accelerated ions employing photo-induced charge detachment is disclosed. The process involves directing a laser beam across the path of a negative ion beam such as to effect photodetachment of electrons from the beam ions. The frequency of the laser beam employed is selected to provide the maximum cross-section for the photodetachment process. 2 figs.

A Study of Vertical Transport through Graphene toward Control of Quantum Tunneling.

PubMed

Zhu, Xiaodan; Lei, Sidong; Tsai, Shin-Hung; Zhang, Xiang; Liu, Jun; Yin, Gen; Tang, Min; Torres, Carlos M; Navabi, Aryan; Jin, Zehua; Tsai, Shiao-Po; Qasem, Hussam; Wang, Yong; Vajtai, Robert; Lake, Roger K; Ajayan, Pulickel M; Wang, Kang L

2018-02-14

Vertical integration of van der Waals (vdW) materials with atomic precision is an intriguing possibility brought forward by these two-dimensional (2D) materials. Essential to the design and analysis of these structures is a fundamental understanding of the vertical transport of charge carriers into and across vdW materials, yet little has been done in this area. In this report, we explore the important roles of single layer graphene in the vertical tunneling process as a tunneling barrier. Although a semimetal in the lateral lattice plane, graphene together with the vdW gap act as a tunneling barrier that is nearly transparent to the vertically tunneling electrons due to its atomic thickness and the transverse momenta mismatch between the injected electrons and the graphene band structure. This is accentuated using electron tunneling spectroscopy (ETS) showing a lack of features corresponding to the Dirac cone band structure. Meanwhile, the graphene acts as a lateral conductor through which the potential and charge distribution across the tunneling barrier can be tuned. These unique properties make graphene an excellent 2D atomic grid, transparent to charge carriers, and yet can control the carrier flux via the electrical potential. A new model on the quantum capacitance's effect on vertical tunneling is developed to further elucidate the role of graphene in modulating the tunneling process. This work may serve as a general guideline for the design and analysis of vdW vertical tunneling devices and heterostructures, as well as the study of electron/spin injection through and into vdW materials.

SOLPS modeling of the effect on plasma detachment of closing the lower divertor in DIII-D

DOE PAGES

Sang, C. F.; Stangeby, P. C.; Guo, H. Y.; ...

2016-12-15

SOLPS modeling has been carried out to assess the effect of tightly closing the lower divertor in DIII-D, which at present is almost fully open, on the achievement of cold dissipative/detached divertor conditions. To isolate the impact of other factors on the divertor plasma solution and to make direct comparisons, most of the parameters including the meshes were kept as similar as possible. Only the neutral baffling was modified to compare a fully open divertor with a tightly closed one. The modeling shows that the tightly closed divertor greatly improves trapping of recycling neutrals, thereby increasing radiative and charge exchangemore » losses in the divertor and reducing the electron temperature T et and deposited power density q dep at the target plate. Furthermore, the closed structure enables the divertor plasma to enter into highly dissipative and detached divertor conditions at a significantly lower upstream density. The effects of divertor closure on the neutral density and pressure, and their correlation with the divertor plasma conditions are also demonstrated. The effect of molecular D 2- ion D + elastic collisions and neutral-neutral collisions on the divertor plasma solution are assessed.« less

Blastocyst production after intracytoplasmic sperm injection with semen from a stallion with testicular degeneration.

PubMed

Roels, K; Smits, K; Ververs, C; Govaere, J; D'Herde, K; Van Soom, A

2018-06-01

In horse breeding, intracytoplasmic sperm injection (ICSI) has gained interest to obtain offspring from subfertile individuals. This paper presents a case report of a stallion with severe testicular degeneration. Semen analysis showed very low motility and 83.5% of detached heads. Histology of a testicular biopsy showed severely decreased spermatogenesis, while transmission electron microscopy of the sperm cells revealed no significant abnormalities. A total of 39 oocytes were fertilized by ICSI with frozen-thawed spermatozoa of this stallion: 25 oocytes with intact spermatozoa and 24 with detached heads. When using intact sperm cells, 8 out of the 25 oocytes cleaved, and 1 developed to the blastocyst stage 9 days after ICSI. None of the oocytes injected with a detached sperm head cleaved. Studies on the paternal influence on ICSI outcome are limited in the horse and further research is needed to define which stallion factors may influence ICSI results. Here, we report the possibility to produce a blastocyst by ICSI of a stallion suffering from testicular degeneration with a poor spermiogram, as long as an intact sperm cell containing a centriole is selected. © 2018 Blackwell Verlag GmbH.

Instantly switchable adhesion of bridged fibrillar adhesive via gecko-inspired detachment mechanism and its application to a transportation system

NASA Astrophysics Data System (ADS)

Bae, Won-Gyu; Kim, Doogon; Suh, Kahp-Yang

2013-11-01

Inspired by the exceptional climbing ability of gecko lizards, artificial fibrillar adhesives have been extensively studied over the last decade both experimentally and theoretically. Therefore, a new leap towards practical uses beyond the academic horizon is timely and highly anticipated. To this end, we present a fibrillar adhesive in the form of bridged micropillars and its application to a transportation system with the detachment mechanism inspired by the climbing behaviour of gecko lizards. The adhesive shows strong normal attachment (~30 N cm-2) as well as easy and fast detachment within 0.5 s without involving complex dynamic mechanisms or specific stimulus-responsive materials. The fabrication of the bridged micropillars consists of replica moulding of polydimethylsiloxane (PDMS) micropillars, transfer of the PDMS precursor to the heads of the micropillars, and inverse placement on an inert Teflon-coated surface. Owing to the spontaneous interconnections of low viscosity PDMS precursor, bridged micropillars with a uniform capping nanomembrane (~800 nm thickness) are formed over a large area. Interestingly, macroscopic adhesion in the normal direction can be immediately switched between on and off states by changing the two detachment modes of pulling and peeling, respectively. To prove the potential of the fibrillar adhesive for practical use, an automated transportation system is demonstrated for lifting and releasing a mass of stacked glass slides over 1000 cycles of attachment and detachment.Inspired by the exceptional climbing ability of gecko lizards, artificial fibrillar adhesives have been extensively studied over the last decade both experimentally and theoretically. Therefore, a new leap towards practical uses beyond the academic horizon is timely and highly anticipated. To this end, we present a fibrillar adhesive in the form of bridged micropillars and its application to a transportation system with the detachment mechanism inspired by the climbing behaviour of gecko lizards. The adhesive shows strong normal attachment (~30 N cm-2) as well as easy and fast detachment within 0.5 s without involving complex dynamic mechanisms or specific stimulus-responsive materials. The fabrication of the bridged micropillars consists of replica moulding of polydimethylsiloxane (PDMS) micropillars, transfer of the PDMS precursor to the heads of the micropillars, and inverse placement on an inert Teflon-coated surface. Owing to the spontaneous interconnections of low viscosity PDMS precursor, bridged micropillars with a uniform capping nanomembrane (~800 nm thickness) are formed over a large area. Interestingly, macroscopic adhesion in the normal direction can be immediately switched between on and off states by changing the two detachment modes of pulling and peeling, respectively. To prove the potential of the fibrillar adhesive for practical use, an automated transportation system is demonstrated for lifting and releasing a mass of stacked glass slides over 1000 cycles of attachment and detachment. Electronic supplementary information (ESI) available: Photograph of a custom-built adhesion measurement system, video snapshots showing the switchable adhesion via gecko-inspired detachment mechanism, schematic of fabricating a master mould, and a SEM image showing the thickness of the nanomembrane. See DOI: 10.1039/c3nr02008h

Pulsed-field ionization zero electron kinetic energy spectrum of the ground electronic state of BeOBe+.

PubMed

Antonov, Ivan O; Barker, Beau J; Heaven, Michael C

2011-01-28

The ground electronic state of BeOBe(+) was probed using the pulsed-field ionization zero electron kinetic energy photoelectron technique. Spectra were rotationally resolved and transitions to the zero-point level, the symmetric stretch fundamental and first two bending vibrational levels were observed. The rotational state symmetry selection rules confirm that the ground electronic state of the cation is (2)Σ(g)(+). Detachment of an electron from the HOMO of neutral BeOBe results in little change in the vibrational or rotational constants, indicating that this orbital is nonbonding in nature. The ionization energy of BeOBe [65480(4) cm(-1)] was refined over previous measurements. Results from recent theoretical calculations for BeOBe(+) (multireference configuration interaction) were found to be in good agreement with the experimental data.

Significant relaxation of residual negative carrier in polar Alq3 film directly detected by high-sensitivity photoemission

NASA Astrophysics Data System (ADS)

Kinjo, Hiroumi; Lim, Hyunsoo; Sato, Tomoya; Noguchi, Yutaka; Nakayama, Yasuo; Ishii, Hisao

2016-02-01

Tris(8-hydroxyquinoline)aluminum (Alq3) has been widely applied as a good electron-injecting layer (EIL) in organic light-emitting diodes. High-sensitivity photoemission measurement revealed a clear photoemission by visible light, although its ionization energy is 5.7 eV. This unusual photoemission is ascribed to Alq3 anions captured by positive polarization charges. The observed electron detachment energy of the anion was about 1 eV larger than the electron affinity reported by inverse photoemission. This difference suggests that the injected electron in the Alq3 layer is energetically relaxed, leading to the reduction in injection barrier. This nature is one of the reasons why Alq3 worked well as the EIL.

Layer-by-layer assembly of two-dimensional materials into wafer-scale heterostructures

NASA Astrophysics Data System (ADS)

Kang, Kibum; Lee, Kan-Heng; Han, Yimo; Gao, Hui; Xie, Saien; Muller, David A.; Park, Jiwoong

2017-10-01

High-performance semiconductor films with vertical compositions that are designed to atomic-scale precision provide the foundation for modern integrated circuitry and novel materials discovery. One approach to realizing such films is sequential layer-by-layer assembly, whereby atomically thin two-dimensional building blocks are vertically stacked, and held together by van der Waals interactions. With this approach, graphene and transition-metal dichalcogenides--which represent one- and three-atom-thick two-dimensional building blocks, respectively--have been used to realize previously inaccessible heterostructures with interesting physical properties. However, no large-scale assembly method exists at present that maintains the intrinsic properties of these two-dimensional building blocks while producing pristine interlayer interfaces, thus limiting the layer-by-layer assembly method to small-scale proof-of-concept demonstrations. Here we report the generation of wafer-scale semiconductor films with a very high level of spatial uniformity and pristine interfaces. The vertical composition and properties of these films are designed at the atomic scale using layer-by-layer assembly of two-dimensional building blocks under vacuum. We fabricate several large-scale, high-quality heterostructure films and devices, including superlattice films with vertical compositions designed layer-by-layer, batch-fabricated tunnel device arrays with resistances that can be tuned over four orders of magnitude, band-engineered heterostructure tunnel diodes, and millimetre-scale ultrathin membranes and windows. The stacked films are detachable, suspendable and compatible with water or plastic surfaces, which will enable their integration with advanced optical and mechanical systems.

Layer-by-layer assembly of two-dimensional materials into wafer-scale heterostructures.

PubMed

Kang, Kibum; Lee, Kan-Heng; Han, Yimo; Gao, Hui; Xie, Saien; Muller, David A; Park, Jiwoong

2017-10-12

High-performance semiconductor films with vertical compositions that are designed to atomic-scale precision provide the foundation for modern integrated circuitry and novel materials discovery. One approach to realizing such films is sequential layer-by-layer assembly, whereby atomically thin two-dimensional building blocks are vertically stacked, and held together by van der Waals interactions. With this approach, graphene and transition-metal dichalcogenides-which represent one- and three-atom-thick two-dimensional building blocks, respectively-have been used to realize previously inaccessible heterostructures with interesting physical properties. However, no large-scale assembly method exists at present that maintains the intrinsic properties of these two-dimensional building blocks while producing pristine interlayer interfaces, thus limiting the layer-by-layer assembly method to small-scale proof-of-concept demonstrations. Here we report the generation of wafer-scale semiconductor films with a very high level of spatial uniformity and pristine interfaces. The vertical composition and properties of these films are designed at the atomic scale using layer-by-layer assembly of two-dimensional building blocks under vacuum. We fabricate several large-scale, high-quality heterostructure films and devices, including superlattice films with vertical compositions designed layer-by-layer, batch-fabricated tunnel device arrays with resistances that can be tuned over four orders of magnitude, band-engineered heterostructure tunnel diodes, and millimetre-scale ultrathin membranes and windows. The stacked films are detachable, suspendable and compatible with water or plastic surfaces, which will enable their integration with advanced optical and mechanical systems.

Quantum-chemical studies on the favored and rare tautomers of neutral and redox adenine.

PubMed

Raczyńska, Ewa D; Makowski, Mariusz; Zientara-Rytter, Katarzyna; Kolczyńska, Katarzyna; Stępniewski, Tomasz M; Hallmann, Małgorzata

2013-02-21

All possible twenty-three prototropic tautomers of neutral and redox adenine (nine amine and fourteen imine forms, including geometric isomerism of the exo ═NH group) were examined in vacuo {DFT(B3LYP)/6-311+G(d,p)}. The NH → NH conversions as well as those usually omitted, NH → CH and CH → CH, were considered. An interesting change of the tautomeric preference occurs when proceeding from neutral to reduced adenine. One-electron reduction favors the nonaromatic amine C8H-N10H tautomer. This tautomeric preference is similar to that (C2H) for reduced imidazole. Water molecules (PCM model) seem to not change this trend. They influence solely the relative energies. The DFT vertical detachment energy in the gas phase is positive for each tautomer, e.g., 0.03 eV for N9H-N10H and 1.84 eV for C8H-N10H. The DFT adiabatic electron affinity for the favored process, neutral N9H-N10H → reduced C8H-N10H (ground states), is equal to 0.18 eV at 0 K (ZPE included). One-electron oxidation does not change the tautomeric preference in the gas phase. The aromatic amine N9H-N10H tautomer is favored for the oxidized molecule similarly as for the neutral one. The DFT adiabatic ionization potential for the favored process, neutral N9H-N10H → oxidized N9H-N10H (ground states), is equal to 8.12 eV at 0 K (ZPE included). Water molecules (PCM model) seem to influence solely the composition of the tautomeric mixture and the relative energies. They change the energies of the oxidation and reduction processes by ca. 2 eV.

D3h [A-CE3-A]- (E = Al and Ga, A = Si, Ge, Sn, and Pb): A new class of hexatomic mono-anionic species with trigonal bipyramidal carbon

NASA Astrophysics Data System (ADS)

Wu, Yan-Bo; Li, Yan-Qin; Bai, Hui; Lu, Hai-Gang; Li, Si-Dian; Zhai, Hua-Jin; Wang, Zhi-Xiang

2014-03-01

The non-classical trigonal bipyramidal carbon (TBPC) arrangement generally exists as transition states (TSs) in nucleophilic bimolecular substitution (SN2) reactions. Nevertheless, chemists have been curious about whether such a carbon bonding could be stable in equilibrium structures for decades. As the TBPC arrangement was normally realized as cationic species theoretically and experimentally, only one anionic example ([At-C(CN)3-At]-) was computationally devised. Herein, we report the design of a new class of anionic TBPC species by using the strategy similar to that for stabilizing the non-classical planar hypercoordinate carbon. When electron deficient Al and Ga were used as the equatorial ligands, eight D3h [A-CE3-A]- (E = Al and Ga, A = Si, Ge, Sn, and Pb) TBPC structures were found to be the energy minima rather than TSs at both the B3LYP and MP2 levels. Remarkably, the energetic results at the CCSD(T) optimization level further identify [Ge-CAl3-Ge]- and [Sn-CGa3-Sn]- even to be the global minima and [Si-CAl3-Si]- and [Ge-CGa3-Ge]- to be the local minima, only slightly higher than their global minima. The electronic structure analyses reveal that the substantial ionic C-E bonding, the peripheral E-A covalent bonding, and the axial mc-2e (multi center-two electrons) bonding play roles in stabilizing these TBPC structures. The structural simplicity and the high thermodynamic stability suggest that some of these species may be generated and captured in the gas phase. Furthermore, as mono-anionic species, their first vertical detachment energies are differentiable from those of their nearest isomers, which would facilitate their characterization via experiments such as the negative ion photoelectron spectroscopy.

Fractal Interrelationships in Field and Seismic Data

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

Wilson, T.H.; Dominic, Jovita; Halverson, Joel

1997-10-01

Size scaling interrelationships are evaluated in this study using a fractal model. Fractal models of several geologic variables are examined and include fracture patterns, reflection travel times, structural relief, drainage, topographic relief and active fault patterns. The fractal properties of structural relief inferred from seismic data and structural cross sections provide a quantitative means to characterize and compare complex structural patterns. Studies were conducted using seismic data from the Granny Creek oil field in the Appalachian Plateau. Previous studies of the field reveal that subtle detached structures present on the limb of a larger structure are associated with enhanced productionmore » from the field. Vertical increases of fractal dimension across the zone of detachment provide a measure of the extent to which detachment has occurred. The increases of fractal dimension are greatest in the more productive areas of the field. A result with equally important ramifications is that fracture systems do not appear to be intrinsically fractal as is often suggested in the literature. While examples of nearly identical patterns can be found at different scales supporting the idea of self-similarity, these examples are often taken from different areas and from different lithologies. Examination of fracture systems at different scales in the Valley and Ridge Province suggest that their distribution become increasingly sparse with scale reduction, and therefore are dissimilar or non-fractal. Box counting data in all cases failed to yield a fractal regime. The results obtained from this analysis bring into question the general applicability of reservoir simulations employing fractal models of fracture distribution. The same conclusions were obtained from the analysis of 1D fracture patterns such as those that might appear in a horizontal well.« less

Photoelectron spectroscopy and electronic structure of ScO{sub n}{sup {minus}}(n = 1--4) and YO{sub n}{sup {minus}}(n = 1--5): Strong electron correlation effects in ScO{sup {minus}} and YO{sup {minus}}

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

Wu, H.; Wang, L.S.

A photoelectron spectroscopic study of ScO{sub n}{sup {minus}} (n = 1--4) and YO{sub n}{sup {minus}} (n = 1--5) was carried out at three photon energies: 532, 355, and 266 nm. Vibrationally resolved photoelectron spectra were obtained for ScO{sup {minus}} and YO{sup {minus}}. The electron affinities of both ScO and YO were measured to be identical (1.35 eV) within the experimental accuracy ({+-}0.02 eV). Three low-lying excited states were observed for the monoxides, {Alpha}{prime}{sup 2}{Delta}, {Alpha}{sup 2}{Pi}, and {Beta}{sup 2}{Sigma}{sup +}. The latter two excited states resulted from two-electron detachment, suggesting unusually strong electron correlation (configuration interaction) effects in the groundmore » state of the anions. The excitation energies of the low-lying states were also found to be similar for the two monoxides except that YO has a smaller vibrational frequency and larger spin-orbit splitting. The {Alpha}{prime}{sup 2}{Delta} states of both ScO and YO show very strong photon energy-dependent detachment cross sections. Four similar photoelectron features were observed for the dioxides with those of YO{sub 2}{sup {minus}} having lower binding energies. A second isomer due to an O{sub 2} complex was also observed for Sc and Y. Broad and featureless spectra were observed for the higher oxides. At least two isomers were present for the higher oxides, one with low and one with high binding energies.« less

Probing the intrinsic electronic structure of the bis(dithiolene) anions [M(mnt)2]2- and [M(mnt)2]1- (M = Ni, Pd, Pt; mnt = 1,2-S2C2(CN)2) in the gas phase by photoelectron spectroscopy.

PubMed

Waters, Tom; Woo, Hin-Koon; Wang, Xue-Bin; Wang, Lai-Sheng

2006-04-05

A detailed understanding of the electronic structure of transition metal bis(dithiolene) complexes is important because of their interesting redox, magnetic, optical, and conducting properties and their relevance to enzymes containing molybdenum and tungsten bis(dithiolene) centers. The electronic structures of the bis(dithiolene) anions [M(mnt)(2)](n-) (M = Ni, Pd, Pt; mnt = 1,2-S(2)C(2)(CN)(2); n = 0-2) were examined by a combination of photodetachment photoelectron spectroscopy (PES) and density functional theory calculations. The combined experimental and theoretical data provide insight into the molecular orbital energy levels of [M(mnt)(2)](2-) and the ground and excited states of [M(mnt)(2)](1-) and [M(mnt)(2)]. Detachment features from ligand-based orbitals of [M(mnt)(2)](2-) occur at similar energies for each species, independent of the metal center, while those arising from metal-based orbitals occur at higher energies for the heavier congeners. Electronic excitation energies inferred for [M(mnt)(2)](1-) from the PES experiments agree well with those obtained in optical absorption experiments in solution, with the PES experiments providing additional insight into the changes in energy of these transitions as a function of metal. The singly charged anions [M(mnt)(2)](1-) were also prepared and studied independently. Electron detachment from the ground states of these doublet anions accessed the lowest singlet and triplet states of neutral [M(mnt)(2)], thereby providing a direct experimental measure of their singlet-triplet splitting.

Time-resolved radiation chemistry: Dynamics of electron attachment to uracil following UV excitation of iodide-uracil complexes

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

King, Sarah B.; Yandell, Margaret A.; Stephansen, Anne B.

Electron attachment to uracil was investigated by applying time-resolved photoelectron imaging to iodide-uracil (I{sup –}U) complexes. In these studies, an ultraviolet pump pulse initiated charge transfer from the iodide to the uracil, and the resulting dynamics of the uracil temporary negative ion were probed. Five different excitation energies were used, 4.00 eV, 4.07 eV, 4.14 eV, 4.21 eV, and 4.66 eV. At the four lowest excitation energies, which lie near the vertical detachment energy of the I{sup –}U complex (4.11 eV), signatures of both the dipole bound (DB) as well as the valence bound (VB) anion of uracil were observed.more » In contrast, only the VB anion was observed at 4.66 eV, in agreement with previous experiments in this higher energy range. The early-time dynamics of both states were highly excitation energy dependent. The rise time of the DB anion signal was ∼250 fs at 4.00 eV and 4.07 eV, ∼120 fs at 4.14 eV and cross-correlation limited at 4.21 eV. The VB anion rise time also changed with excitation energy, ranging from 200 to 300 fs for excitation energies 4.00–4.21 eV, to a cross-correlation limited time at 4.66 eV. The results suggest that the DB state acts as a “doorway” state to the VB anion at 4.00–4.21 eV, while direct attachment to the VB anion occurs at 4.66 eV.« less

Electron attachment to the guanine-cytosine nucleic acid base pair and the effects of monohydration and proton transfer.

PubMed

Gupta, Ashutosh; Jaeger, Heather M; Compaan, Katherine R; Schaefer, Henry F

2012-05-17

The guanine-cytosine (GC) radical anion and its interaction with a single water molecule is studied using ab initio and density functional methods. Z-averaged second-order perturbation theory (ZAPT2) was applied to GC radical anion for the first time. Predicted spin densities show that the radical character is localized on cytosine. The Watson-Crick monohydrated GC anion is compared to neutral GC·H2O, as well as to the proton-transferred analogue on the basis of structural and energetic properties. In all three systems, local minima are identified that correspond to water positioned in the major and minor grooves of macromolecular DNA. On the anionic surface, two novel structures have water positioned above or below the GC plane. On the neutral and anionic surfaces, the global minimum can be described as water interacting with the minor groove. These structures are predicted to have hydration energies of 9.7 and 11.8 kcal mol(-1), respectively. Upon interbase proton-transfer (PT), the anionic global minimum has water positioned in the major groove, and the hydration energy increases to 13.4 kcal mol(-1). PT GC·H2O(•-) has distonic character; the radical character resides on cytosine, while the negative charge is localized on guanine. The effects of proton transfer are further investigated through the computed adiabatic electron affinities (AEA) of GC and monohydrated GC, and the vertical detachment energies (VDE) of the corresponding anions. Monohydration increases the AEAs and VDEs by only 0.1 eV, while proton-transfer increases the VDEs substantially (0.8 eV). The molecular charge distribution of monohydrated guanine-cytosine radical anion depends heavily on interbase proton transfer.

Transition-Metal-Catalyzed Selective Cage B-H Functionalization of o-Carboranes.

PubMed

Quan, Yangjian; Qiu, Zaozao; Xie, Zuowei

2018-02-26

Carboranes are a class of carbon-boron molecular clusters with unusual thermal and chemical stabilities. They have been proved as very useful building blocks in supramolecular design, optoelectronics, nanomaterials, boron neutron capture therapy agents and organometallic/coordination chemistry. Thus, the functionalization of o-carboranes has received growing interests. Over the past decades, most of the works in this area have been focused on cage carbon functionalization as the weakly acidic cage C-H proton can be readily deprotonated by strong bases. In sharp contrast, selective cage B-H activation/functionalization among chemically very similar ten B-H vertices is very challenging. Considering the differences in electron density of ten cage B-H bonds in o-carborane and the nature of transition metal complexes, we have tackled this selectivity issue by means of organometallic chemistry. Our strategy is as follows: using electron-rich transition metal catalysts for the functionalization of the most electron-deficient B(3,6)-H vertices (bonded to both cage CH vertices); using electron-deficient transition-metal catalysts for the functionalization of relatively electron-rich B(8,9,10,12)-H vertices (with no bonding to both cage CH vertices); and using the combination of directing groups and electrophilic transition metal catalysts for the functionalization of B(4,5,7,11)-H vertices (bonded to only one cage CH vertex). Successful applications of such a strategy result in the preparation of a large variety of cage B-functionalized carboranes in a regioselective and catalytic manner, which are inaccessible by other means. It is believed that as this field progresses, other cage B-functionalized carboranes are expected to be synthesized, and the results detailed in this concept article will further these efforts. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bottom-up substitution assembly of AuF4-n0,-+nPO3 (n = 1-4): a theoretical study of novel oxyfluoride hyperhalogen molecules and anions AuF4-n(PO3)n0,-

NASA Astrophysics Data System (ADS)

Yang, Yi-fan; Cui, Zhong-hua; Ding, Yi-hong

2014-06-01

Compounds with high electron affinity, i.e. superhalogens, have continued to attract chemists' attention, due to their potential importance in fundamental chemistry and materials science. It has now proven very effective to build up novel superhalogens with multi-positively charged centres, which are usually called 'hyperhalogens'. Herein, using AuF4- and PO3 as the model building blocks, we made the first attempt to design the Au,P-based hyperhalogen anions AuF4-n(PO3)n- (n = 1-4) at the B3LYP/6-311+G(d)&SDD and CCSD(T)/6-311+G(d)&SDD (single-point) levels (6-311+G(d) for O, F, P and SDD for Au). Notably, for all the considered Au,P systems, the ground state bears a dioxo-bonded structure with n ≤ 3, which is significantly more stable than the usually presumed mono-oxo-bonded one. Moreover, the clustering of the -PO3 moieties becomes energetically favoured for n ≥ 3. The ground states of AuP4O120,- are the first reported cage-like oxide hyperhalogens. Thus, the -PO3 moiety cannot be retained during the 'bottom-up' assembly. The vertical detachment energy (VDE) value of the most stable AuF4-n(PO3)n- (n = 1-4) ranges from 7.16 to 8.20 eV, higher than the VDE values of the corresponding building blocks AuF4- (7.08 eV) and PO3- (4.69 eV). The adiabatic detachment energy values of these four hyperhalogens exceed 6.00 eV. Possible generation routes for AuF4-n(PO3)n- (n = 1-4) were discussed. The presently designed oxyfluorides not only enriches the family of hyperhalogens, but also demonstrates the great importance of considering the structural transformation during the superhalogen → hyperhalogen design such as for the present Au-P based systems.

South Virgin-White Hills detachment fault system of SE Nevada and NW Arizona: Applying apatite fission track thermochronology to constrain the tectonic evolution of a major continental detachment fault

NASA Astrophysics Data System (ADS)

Fitzgerald, Paul G.; Duebendorfer, Ernest M.; Faulds, James E.; O'Sullivan, Paul

2009-04-01

The South Virgin-White Hills detachment (SVWHD) in the central Basin and Range province with an along-strike extent of ˜60 km is a major continental detachment fault system. Displacement on the SVWHD decreases north to south from ˜17 to <6 km. This is accompanied by a change in fault and footwall rock type from mylonite overprinted by cataclasite to chlorite cataclasite and then fault breccia reflecting decreasing fault displacement and footwall exhumation. Apatite fission track (AFT) thermochronology was applied both along-strike and across-strike to assess this displacement gradient. The overall thermal history reflects Laramide cooling (˜75 Ma) and then rapid cooling beginning in the late early Miocene. Age patterns reflect some complexity but extension along the SVWHD appears synchronous with rapid cooling initiated at ˜17 Ma due to tectonic exhumation. Slip rate is more rapid (˜8.6 km/Ma) in the north compared to ˜1 km/Ma in the south. The displacement gradient results from penecontemporaneous along-strike motion and formation of the SVWHD by linkage of originally separate fault segments that have differential displacements and hence differential slip rates. East-west transverse structures likely play a role in linkage of different fault segments. The preextension paleogeothermal gradient is well constrained in the Gold Butte block as 18-20°C/km. We present a new thermochronologic approach to constrain fault dip during slip, treating the vertical exhumation rate and the slip as vectors, with the angle between them used to constrain fault dip during slip through the closure temperature of a particular thermochronometer. AFT data from the western rim of the Colorado Plateau constrain the initiation of timing of cooling associated with the Laramide Orogeny at ˜75 Ma, and a reheating event in the late Eocene/early Oligocene associated with burial by sediments ("rim gravels") most likely shed from the Kingman High to the west of the plateau.

Electron microscopic evidence for the myosin head lever arm mechanism in hydrated myosin filaments using the gas environmental chamber

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

Minoda, Hiroki; CREST, Japan Science and Technology Agency, Kawaguchi, Saitama 332-0012; Okabe, Tatsuhiro

2011-02-25

Research highlights: {yields} We succeeded in recording structural changes of hydrated myosin cross-bridges. {yields} We succeeded in position-marking the cross-bridges with site-directed antibodies. {yields} We recorded cross-bridge movement at different regions in individual cross-bridge. {yields} The movement was smallest at the cross-bridge-subfragment two boundary. {yields} The results provide evidence for the cross-bridge lever arm mechanism. -- Abstract: Muscle contraction results from an attachment-detachment cycle between the myosin heads extending from myosin filaments and the sites on actin filaments. The myosin head first attaches to actin together with the products of ATP hydrolysis, performs a power stroke associated with release ofmore » hydrolysis products, and detaches from actin upon binding with new ATP. The detached myosin head then hydrolyses ATP, and performs a recovery stroke to restore its initial position. The strokes have been suggested to result from rotation of the lever arm domain around the converter domain, while the catalytic domain remains rigid. To ascertain the validity of the lever arm hypothesis in muscle, we recorded ATP-induced movement at different regions within individual myosin heads in hydrated myosin filaments, using the gas environmental chamber attached to the electron microscope. The myosin head were position-marked with gold particles using three different site-directed antibodies. The amplitude of ATP-induced movement at the actin binding site in the catalytic domain was similar to that at the boundary between the catalytic and converter domains, but was definitely larger than that at the regulatory light chain in the lever arm domain. These results are consistent with the myosin head lever arm mechanism in muscle contraction if some assumptions are made.« less

Low-voltage organic electronics based on a gate-tunable injection barrier in vertical graphene-organic semiconductor heterostructures.

PubMed

Hlaing, Htay; Kim, Chang-Hyun; Carta, Fabio; Nam, Chang-Yong; Barton, Rob A; Petrone, Nicholas; Hone, James; Kymissis, Ioannis

2015-01-14

The vertical integration of graphene with inorganic semiconductors, oxide semiconductors, and newly emerging layered materials has recently been demonstrated as a promising route toward novel electronic and optoelectronic devices. Here, we report organic thin film transistors based on vertical heterojunctions of graphene and organic semiconductors. In these thin heterostructure devices, current modulation is accomplished by tuning of the injection barriers at the semiconductor/graphene interface with the application of a gate voltage. N-channel devices fabricated with a thin layer of C60 show a room temperature on/off ratio >10(4) and current density of up to 44 mAcm(-2). Because of the ultrashort channel intrinsic to the vertical structure, the device is fully operational at a driving voltage of 200 mV. A complementary p-channel device is also investigated, and a logic inverter based on two complementary transistors is demonstrated. The vertical integration of graphene with organic semiconductors via simple, scalable, and low-temperature fabrication processes opens up new opportunities to realize flexible, transparent organic electronic, and optoelectronic devices.

Vertical sizes of 1-D and 2-D electrostatic solitons with nonextensive and trapped electrons in the upper ionosphere

NASA Astrophysics Data System (ADS)

Ali Shan, Shaukat; Saleem, Hamid

2018-05-01

The vertical sizes of one-dimensional (1-D) and two dimensional (2-D) electrostatic solitons are estimated in the oxygen-hydrogen (O - H) and pure oxygen plasmas of the upper ionosphere taking into account the effects of non-extensive and trapped electrons. The field-aligned flow of oxygen ions is also considered. It is found that both electron trapping and non-extensivity play a constructive role in the formation of 1-D and 2-D solitary structures. The vertical size of the solitons is not known through observations, but here it is pointed out that the vertical size of these structures should be of the order of a few meters at the altitude of 800 km in the 1-D case. On the other hand, in the 2-D case, the vertical size is much larger than the horizontal size and it turns out to be of the order of a few kilometers, while the width is about a few hundred meters in agreement with the observations.

Photoisomerization and photoionization of the photoactive yellow protein chromophore in solution.

PubMed

Larsen, Delmar S; Vengris, Mikas; van Stokkum, Ivo H M; van der Horst, Michael A; de Weerd, Frank L; Hellingwerf, Klaas J; van Grondelle, Rienk

2004-04-01

Dispersed pump-dump-probe spectroscopy has the ability to characterize and identify the underlying ultrafast dynamical processes in complicated chemical and biological systems. This technique builds on traditional pump-probe techniques by exploring both ground- and excited-state dynamics and characterizing the connectivity between constituent transient states. We have used the dispersed pump-dump-probe technique to investigate the ground-state dynamics and competing excited-state processes in the excitation-induced ultrafast dynamics of thiomethyl p-coumaric acid, a model chromophore for the photoreceptor photoactive yellow protein. Our results demonstrate the parallel formation of two relaxation pathways (with multiple transient states) that jointly lead to two different types of photochemistry: cis-trans isomerization and detachment of a hydrated electron. The relative transition rates and quantum yields of both pathways have been determined. We find that the relaxation of the photoexcited chromophores involves multiple, transient ground-state intermediates and the chromophore in solution does not generate persistent photoisomerized products, but instead undergoes photoionization resulting in the generation of detached electrons and radicals. These results are of great value in interpreting the more complex dynamical changes in the optical properties of the photoactive yellow protein.

Photoisomerization and Photoionization of the Photoactive Yellow Protein Chromophore in Solution

PubMed Central

Larsen, Delmar S.; Vengris, Mikas; van Stokkum, Ivo H. M.; van der Horst, Michael A.; de Weerd, Frank L.; Hellingwerf, Klaas J.; van Grondelle, Rienk

2004-01-01

Dispersed pump-dump-probe spectroscopy has the ability to characterize and identify the underlying ultrafast dynamical processes in complicated chemical and biological systems. This technique builds on traditional pump-probe techniques by exploring both ground- and excited-state dynamics and characterizing the connectivity between constituent transient states. We have used the dispersed pump-dump-probe technique to investigate the ground-state dynamics and competing excited-state processes in the excitation-induced ultrafast dynamics of thiomethyl p-coumaric acid, a model chromophore for the photoreceptor photoactive yellow protein. Our results demonstrate the parallel formation of two relaxation pathways (with multiple transient states) that jointly lead to two different types of photochemistry: cis-trans isomerization and detachment of a hydrated electron. The relative transition rates and quantum yields of both pathways have been determined. We find that the relaxation of the photoexcited chromophores involves multiple, transient ground-state intermediates and the chromophore in solution does not generate persistent photoisomerized products, but instead undergoes photoionization resulting in the generation of detached electrons and radicals. These results are of great value in interpreting the more complex dynamical changes in the optical properties of the photoactive yellow protein. PMID:15041690

A mechanism for large divertor plasma energy loss via lithium radiation in tokamaks

NASA Astrophysics Data System (ADS)

Rognlien, T. D.; Meier, E. T.; Soukhanovskii, V. A.

2012-10-01

Lithium has been used as a wall-conditioning element in a number of tokamaks over the years, including TFTR, FTU, and NSTX, where core plasma energy confinement and particle control are often found to improve following such conditioning. Here the possible role of Li in providing substantial energy loss for divertor plasmas via line radiation is reported. A multi-charge-state 2D UEDGE fluid model is used where the hydrogenic and Li ions and neutrals are each evolved as separate species and separate equations are solved for the electron and ion temperatures. It is shown that a sufficient level of Li neutrals evolving from the divertor surface via sputtering or evaporation can induce energy detachment of the divertor plasma, yielding a strongly radiating zone near the divertor where ionization and recombination from/to neutral Li can radiate most of the power flowing into the scrape-off layer while maintaining low core contamination. A local peaking of Li emissivity for electron temperatures near 1 eV appears to play an important role in the detachment of the mixed deuterium/Li plasma. Evidence of such behavior from NSTX discharges will be discussed.

Upgraded divertor Thomson scattering system on DIII-D

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

Glass, F., E-mail: glassf@fusion.gat.com; Carlstrom, T. N.; Du, D.

2016-11-15

A design to extend the unique divertor Thomson scattering system on DIII-D to allow measurements of electron temperature and density in high triangularity plasmas is presented. Access to this region is selectable on a shot-by-shot basis by redirecting the laser beam of the existing divertor Thomson system inboard — beneath the lower floor using a moveable, high-damage threshold, in-vacuum mirror — and then redirecting again vertically. The currently measured divertor region remains available with this mirror retracted. Scattered light is collected from viewchords near the divertor floor using in-vacuum, high temperature optical elements and relayed through the port window, beforemore » being coupled into optical fiber bundles. At higher elevations from the floor, measurements are made by dynamically re-focusing the existing divertor system collection optics. Nd:YAG laser timing, analysis of the scattered light spectrum via polychromators, data acquisition, and calibration are all handled by existing systems or methods of the current multi-pulse Thomson scattering system. Existing filtered polychromators with 7 spectral channels are employed to provide maximum measurement breadth (T{sub e} in the range of 0.5 eV–2 keV, n{sub e} in the range of 5 × 10{sup 18}–1 × 10{sup 21} m{sup 3}) for both low T{sub e} in detachment and high T{sub e} measurement up beyond the separatrix.« less

Molecular dynamics simulation, ab initio calculation, and size-selected anion photoelectron spectroscopy study of initial hydration processes of calcium chloride.

PubMed

He, Zhili; Feng, Gang; Yang, Bin; Yang, Lijiang; Liu, Cheng-Wen; Xu, Hong-Guang; Xu, Xi-Ling; Zheng, Wei-Jun; Gao, Yi Qin

2018-06-14

To understand the initial hydration processes of CaCl 2 , we performed molecular simulations employing the force field based on the theory of electronic continuum correction with rescaling. Integrated tempering sampling molecular dynamics were combined with ab initio calculations to overcome the sampling challenge in cluster structure search and refinement. The calculated vertical detachment energies of CaCl 2 (H 2 O) n - (n = 0-8) were compared with the values obtained from photoelectron spectra, and consistency was found between the experiment and computation. Separation of the Cl-Ca ion pair is investigated in CaCl 2 (H 2 O) n - anions, where the first Ca-Cl ionic bond required 4 water molecules, and both Ca-Cl bonds are broken when the number of water molecules is larger than 7. For neutral CaCl 2 (H 2 O) n clusters, breaking of the first Ca-Cl bond starts at n = 5, and 8 water molecules are not enough to separate the two ion pairs. Comparing with the observations on magnesium chloride, it shows that separating one ion pair in CaCl 2 (H 2 O) n requires fewer water molecules than those for MgCl 2 (H 2 O) n . Coincidentally, the solubility of calcium chloride is higher than that of magnesium chloride in bulk solutions.

Molecular dynamics simulation, ab initio calculation, and size-selected anion photoelectron spectroscopy study of initial hydration processes of calcium chloride

NASA Astrophysics Data System (ADS)

He, Zhili; Feng, Gang; Yang, Bin; Yang, Lijiang; Liu, Cheng-Wen; Xu, Hong-Guang; Xu, Xi-Ling; Zheng, Wei-Jun; Gao, Yi Qin

2018-06-01

To understand the initial hydration processes of CaCl2, we performed molecular simulations employing the force field based on the theory of electronic continuum correction with rescaling. Integrated tempering sampling molecular dynamics were combined with ab initio calculations to overcome the sampling challenge in cluster structure search and refinement. The calculated vertical detachment energies of CaCl2(H2O)n- (n = 0-8) were compared with the values obtained from photoelectron spectra, and consistency was found between the experiment and computation. Separation of the Cl—Ca ion pair is investigated in CaCl2(H2O)n- anions, where the first Ca—Cl ionic bond required 4 water molecules, and both Ca—Cl bonds are broken when the number of water molecules is larger than 7. For neutral CaCl2(H2O)n clusters, breaking of the first Ca—Cl bond starts at n = 5, and 8 water molecules are not enough to separate the two ion pairs. Comparing with the observations on magnesium chloride, it shows that separating one ion pair in CaCl2(H2O)n requires fewer water molecules than those for MgCl2(H2O)n. Coincidentally, the solubility of calcium chloride is higher than that of magnesium chloride in bulk solutions.

KSC-2009-1879

NASA Image and Video Library

2009-02-25

CAPE CANAVERAL, Fla. – On Launch Pad 37 at Cape Canaveral Air Force Station in Florida, the lifting mechanism that raised the GOES-O and Delta IV upper stage to vertical is being detached from the spacecraft-Delta stack. GOES–O is one of a series of Geostationary Operational Environmental Satellites. The multi-mission GOES series N-P will be a vital contributor to weather, solar and space operations and science. NASA and the National Oceanic and Atmospheric Administration, or NOAA, are actively engaged in a cooperative program to expand the existing GOES system with the launch of the GOES N-P satellites. Launch of the GOES-O is targeted for no earlier than April 2009. Photo credit: NASA/Jim Grossmann

Computational Analysis of Multi-Rotor Flows

NASA Technical Reports Server (NTRS)

Yoon, Seokkwan; Lee, Henry C.; Pulliam, Thomas H.

2016-01-01

Interactional aerodynamics of multi-rotor flows has been studied for a quadcopter representing a generic quad tilt-rotor aircraft in hover. The objective of the present study is to investigate the effects of the separation distances between rotors, and also fuselage and wings on the performance and efficiency of multirotor systems. Three-dimensional unsteady Navier-Stokes equations are solved using a spatially 5th order accurate scheme, dual-time stepping, and the Detached Eddy Simulation turbulence model. The results show that the separation distances as well as the wings have significant effects on the vertical forces of quadroror systems in hover. Understanding interactions in multi-rotor flows would help improve the design of next generation multi-rotor drones.

Evolution of Cell Size Homeostasis and Growth Rate Diversity during Initial Surface Colonization of Shewanella oneidensis.

PubMed

Lee, Calvin K; Kim, Alexander J; Santos, Giancarlo S; Lai, Peter Y; Lee, Stella Y; Qiao, David F; Anda, Jaime De; Young, Thomas D; Chen, Yujie; Rowe, Annette R; Nealson, Kenneth H; Weiss, Paul S; Wong, Gerard C L

2016-09-06

Cell size control and homeostasis are fundamental features of bacterial metabolism. Recent work suggests that cells add a constant size between birth and division ("adder" model). However, it is not known how cell size homeostasis is influenced by the existence of heterogeneous microenvironments, such as those during biofilm formation. Shewanella oneidensis MR-1 can use diverse energy sources on a range of surfaces via extracellular electron transport (EET), which can impact growth, metabolism, and size diversity. Here, we track bacterial surface communities at single-cell resolution to show that not only do bacterial motility appendages influence the transition from two- to three-dimensional biofilm growth and control postdivisional cell fates, they strongly impact cell size homeostasis. For every generation, we find that the average growth rate for cells that stay on the surface and continue to divide (nondetaching population) and that for cells that detach before their next division (detaching population) are roughly constant. However, the growth rate distribution is narrow for the nondetaching population, but broad for the detaching population in each generation. Interestingly, the appendage deletion mutants (ΔpilA, ΔmshA-D, Δflg) have significantly broader growth rate distributions than that of the wild type for both detaching and nondetaching populations, which suggests that Shewanella appendages are important for sensing and integrating environmental inputs that contribute to size homeostasis. Moreover, our results suggest multiplexing of appendages for sensing and motility functions contributes to cell size dysregulation. These results can potentially provide a framework for generating metabolic diversity in S. oneidensis populations to optimize EET in heterogeneous environments.

Experimental study of cake formation on heat treated and membrane coated needle felts in a pilot scale pulse jet bag filter using optical in-situ cake height measurement

PubMed Central

Saleem, Mahmood; Khan, Rafi Ullah; Tahir, M. Suleman; Krammer, Gernot

2011-01-01

Pulse-jet bag filters are frequently employed for particle removal from off gases. Separated solids form a layer on the permeable filter media called filter cake. The cake is responsible for increasing pressure drop. Therefore, the cake has to be detached at a predefined upper pressure drop limit or at predefined time intervals. Thus the process is intrinsically semi-continuous. The cake formation and cake detachment are interdependent and may influence the performance of the filter. Therefore, understanding formation and detachment of filter cake is important. In this regard, the filter media is the key component in the system. Needle felts are the most commonly used media in bag filters. Cake formation studies with heat treated and membrane coated needle felts in pilot scale pulse jet bag filter were carried out. The data is processed according to the procedures that were published already [Powder Technology, Volume 173, Issue 2, 19 April 2007, Pages 93–106]. Pressure drop evolution, cake height distribution evolution, cake patches area distribution and their characterization using fractal analysis on different needle felts are presented here. It is observed that concavity of pressure drop curve for membrane coated needle felt is principally caused by presence of inhomogeneous cake area load whereas it is inherent for heat treated media. Presence of residual cake enhances the concavity of pressure drop at the start of filtration cycle. Patchy cleaning is observed only when jet pulse pressure is too low and unable to provide the necessary force to detach the cake. The border line is very sharp. Based on experiments with limestone dust and three types of needle felts, for the jet pulse pressure above 4 bar and filtration velocity below 50 mm/s, cake is detached completely except a thin residual layer (100–200 μm). Uniformity and smoothness of residual cake depends on the surface characteristics of the filter media. Cake height distribution of residual cake and newly formed cake during filtration prevails. The patch size analysis and fractal analysis reveal that residual cake grow in size (latterly) following regeneration initially on the base with edges smearing out, however, the cake heights are not leveled off. Fractal dimension of cake patches boundary falls in the range of 1–1.4 and depends on vertical position as well as time of filtration. Cake height measurements with Polyimide (PI) needle felts were hampered on account of its photosensitive nature. PMID:24415801

Electron scattering at interfaces in nano-scale vertical interconnects: A combined experimental and ab initio study

NASA Astrophysics Data System (ADS)

Lanzillo, Nicholas A.; Restrepo, Oscar D.; Bhosale, Prasad S.; Cruz-Silva, Eduardo; Yang, Chih-Chao; Youp Kim, Byoung; Spooner, Terry; Standaert, Theodorus; Child, Craig; Bonilla, Griselda; Murali, Kota V. R. M.

2018-04-01

We present a combined theoretical and experimental study on the electron transport characteristics across several representative interface structures found in back-end-of-line interconnect stacks for advanced semiconductor manufacturing: Cu/Ta(N)/Co/Cu and Cu/Ta(N)/Ru/Cu. In particular, we evaluate the impact of replacing a thin TaN barrier with Ta while considering both Co and Ru as wetting layers. Both theory and experiment indicate a pronounced reduction in vertical resistance when replacing TaN with Ta, regardless of whether a Co or Ru wetting layer is used. This indicates that a significant portion of the total vertical resistance is determined by electron scattering at the Cu/Ta(N) interface. The electronic structure of these nano-sized interconnects is analyzed in terms of the atom-resolved projected density of states and k-resolved transmission spectra at the Fermi level. This work further develops a fundamental understanding of electron transport and material characteristics in nano-sized interconnects.

Vertical and Horizontal Integration of Laboratory Curricula and Course Projects across the Electronic Engineering Technology Program

ERIC Educational Resources Information Center

Zhan, Wei; Goulart, Ana; Morgan, Joseph A.; Porter, Jay R.

2011-01-01

This paper discusses the details of the curricular development effort with a focus on the vertical and horizontal integration of laboratory curricula and course projects within the Electronic Engineering Technology (EET) program at Texas A&M University. Both software and hardware aspects are addressed. A common set of software tools are…

Photoelectron spectroscopy of B4O4 (-): Dual 3c-4e π hyperbonds and rhombic 4c-4e o-bond in boron oxide clusters.

PubMed

Tian, Wen-Juan; Zhao, Li-Juan; Chen, Qiang; Ou, Ting; Xu, Hong-Guang; Zheng, Wei-Jun; Zhai, Hua-Jin; Li, Si-Dian

2015-04-07

Gas-phase anion photoelectron spectroscopy (PES) is combined with global structural searches and electronic structure calculations at the hybrid Becke 3-parameter exchange functional and Lee-Yang-Parr correlation functional (B3LYP) and single-point coupled-cluster with single, double, and perturbative triple excitations (CCSD(T)) levels to probe the structural and electronic properties and chemical bonding of the B4O4 (0/-) clusters. The measured PES spectra of B4O4 (-) exhibit a major band with the adiabatic and vertical detachment energies (ADE and VDE) of 2.64 ± 0.10 and 2.81 ± 0.10 eV, respectively, as well as a weak peak with the ADE and VDE of 1.42 ± 0.08 and 1.48 ± 0.08 eV. The former band proves to correspond to the Y-shaped global minimum of Cs B4O4 (-) ((2)A″), with the calculated ADE/VDE of 2.57/2.84 eV at the CCSD(T) level, whereas the weak band is associated with the second lowest-energy, rhombic isomer of D2h B4O4 (-) ((2)B2g) with the predicted ADE/VDE of 1.43/1.49 eV. Both anion structures are planar, featuring a B atom or a B2O2 core bonded with terminal BO and/or BO2 groups. The same Y-shaped and rhombic structures are also located for the B4O4 neutral cluster, albeit with a reversed energy order. Bonding analyses reveal dual three-center four-electron (3c-4e) π hyperbonds in the Y-shaped B4O4 (0/-) clusters and a four-center four-electron (4c-4e) π bond, that is, the so-called o-bond in the rhombic B4O4 (0/-) clusters. This work is the first experimental study on a molecular system with an o-bond.

Photoelectron spectrum of valence anions of uracil and first-principles calculations of excess electron binding energies.

PubMed

Bachorz, Rafał A; Klopper, Wim; Gutowski, Maciej; Li, Xiang; Bowen, Kit H

2008-08-07

The photoelectron spectrum (PES) of the uracil anion is reported and discussed from the perspective of quantum chemical calculations of the vertical detachment energies (VDEs) of the anions of various tautomers of uracil. The PES peak maximum is found at an electron binding energy of 2.4 eV, and the width of the main feature suggests that the parent anions are in a valence rather than a dipole-bound state. The canonical tautomer as well as four tautomers that result from proton transfer from an NH group to a C atom were investigated computationally. At the Hartree-Fock and second-order Moller-Plesset perturbation theory levels, the adiabatic electron affinity (AEA) and the VDE have been converged to the limit of a complete basis set to within +/-1 meV. Post-MP2 electron-correlation effects have been determined at the coupled-cluster level of theory including single, double, and noniterative triple excitations. The quantum chemical calculations suggest that the most stable valence anion of uracil is the anion of a tautomer that results from a proton transfer from N1H to C5. It is characterized by an AEA of 135 meV and a VDE of 1.38 eV. The peak maximum is as much as 1 eV larger, however, and the photoelectron intensity is only very weak at 1.38 eV. The PES does not lend support either to the valence anion of the canonical tautomer, which is the second most stable anion, and whose VDE is computed at about 0.60 eV. Agreement between the peak maximum and the computed VDE is only found for the third most stable tautomer, which shows an AEA of approximately -0.1 eV and a VDE of 2.58 eV. This tautomer results from a proton transfer from N3H to C5. The results illustrate that the characteristics of biomolecular anions are highly dependent on their tautomeric form. If indeed the third most stable anion is observed in the experiment, then it remains an open question why and how this species is formed under the given conditions.

Experiments to trap dust particles by a wire simulating an electron beam

NASA Astrophysics Data System (ADS)

Saeki, Hiroshi; Momose, Takashi; Ishimaru, Hajime

1991-11-01

Motion of trapped dust particles has been previously analyzed using high-energy bremsstrahlung data obtained during dust trapping in the TRISTAN accumulation ring. Because it is difficult to observe the actual motions of dust particles trapped in an electron beam due to the strong synchrotron light background, we carried out experiments to trap sample dust particles with a Cu wire simulating an electron beam. A negative potential was slowly applied to the wire using a high voltage dc power supply. Motions of dust particles trapped by the wire were recorded with a video camera system. In an experiment using a Cu wire (1.5 mm in diameter) with no magnetic field, the charged dust particle made vertical oscillation about the wire. In another experiment using the same wire but with a vertical magnetic field (0.135 T) simulating a bending magnetic field, both vertical and horizontal oscillating motions perpendicular to the wire were observed. Furthermore, it was found that the dust particle moved in the longitudinal direction of the wire in the bending magnetic field. Therefore, it is expected that charged dust particles trapped by the electric field of the electron beam oscillate vertically where there is no magnetic field in the TRISTAN accumulation ring. It is also expected that trapped dust particles where there is a bending magnetic field oscillate horizontally and vertically as the particle drifts in a longitudinal direction along the ring.

Plasma detachment in divertor tokamaks

NASA Astrophysics Data System (ADS)

Leonard, A. W.

2018-04-01

Observations of divertor plasma detachment in tokamaks are reviewed. Plasma detachment is characterized in terms of transport and dissipation of power, momentum and particle flux along the open field lines from the midplane to the divertor. Asymmetries in detachment onset and other characteristics between the inboard and outboard divertor plasmas is found to be primarily driven by plasma E× B drifts. The effect of divertor plate geometry and magnetic configuration on divertor detachment is summarized. Control of divertor detachment has progressed with a development of a number of diagnostics to characterize the detached state in real-time. Finally the compatibility of detached divertor operation with high performance core plasmas is examined.

Counterstreaming solar wind halo electron events on open field lines?

NASA Technical Reports Server (NTRS)

Gosling, J. T.; Mccomas, D. J.; Phillips, J. L.

1992-01-01

Counterstreaming solar wind halo electron events have been identified as a common 1 AU signature of coronal mass ejection events, and have generally been interpreted as indicative of closed magnetic field topologies, i.e., magnetic loops or flux ropes rooted at both ends in the Sun, or detached plasmoids. In this paper we examine the possibility that these events may instead occur preferentially on open field lines, and that counterstreaming results from reflection or injection behind interplanetary shocks or from mirroring from regions of compressed magnetic field farther out in the heliosphere. We conclude that neither of these suggested sources of counterstreaming electron beams is viable and that the best interpretation of observed counterstreaming electron events in the solar wind remains that of passage of closed field structures.

Numerical Investigation of Synthetic-jet based Flow Control on Vertical-axis Wind Turbine Blades

NASA Astrophysics Data System (ADS)

Menon, Ashwin; Tran, Steven; Sahni, Onkar

2013-11-01

Vertical-axis wind turbines encounter large unsteady aerodynamic loads in a sustained fashion due to the continuously varying angle of attack that is experienced by turbine blades during each revolution. Moreover, the detachment of the leading edge vortex at high angles of attack leads to sudden change in aerodynamic loads that result in structural vibrations and fatigue, and possibly failure. This numerical study focuses on using synthetic-jet based fluidic actuation to reduce the unsteady loading on VAWT blades. In the simulations, the jets are placed at the dominant separation location that is observed in the baseline case. We consider different tip-speed ratios, O(2-5), and we also study the effect of blowing ratio (to be in O(0.5-1.5)) and reduced frequency, i.e., ratio of jet frequency to flow frequency (to be in O(5-15)). For all cases, unsteady Reynolds-averaged Navier-Stokes simulations are carried out by using the Spallart-Allamaras turbulence model, where stabilized finite element method is employed for spatial discretization along with an implicit time-integration scheme.

A first-principles analysis of ballistic conductance, grain boundary scattering and vertical resistance in aluminum interconnects

NASA Astrophysics Data System (ADS)

Zhou, Tianji; Lanzillo, Nicholas A.; Bhosale, Prasad; Gall, Daniel; Quon, Roger

2018-05-01

We present an ab initio evaluation of electron scattering mechanisms in Al interconnects from a back-end-of-line (BEOL) perspective. We consider the ballistic conductance as a function of nanowire size, as well as the impact of surface oxidation on electron transport. We also consider several representative twin grain boundaries and calculate the specific resistivity and reflection coefficients for each case. Lastly, we calculate the vertical resistance across the Al/Ta(N)/Al and Cu/Ta(N)/Cu interfaces, which are representative of typical vertical interconnect structures with diffusion barriers. Despite a high ballistic conductance, the calculated specific resistivities at grain boundaries are 70-100% higher in Al than in Cu, and the vertical resistance across Ta(N) diffusion barriers are 60-100% larger for Al than for Cu. These results suggest that in addition to the well-known electromigration limitations in Al interconnects, electron scattering represents a major problem in achieving low interconnect line resistance at fine dimensions.

Calculation of Hammett Equation parameters for some N,N‧-bis (substituted-phenyl)-1,4-quinonediimines by density functional theory

NASA Astrophysics Data System (ADS)

Sein, Lawrence T.

2011-08-01

Hammett parameters σ' were determined from vertical ionization potentials, vertical electron affinities, adiabatic ionization potentials, adiabatic electron affinities, HOMO, and LUMO energies of a series of N, N' -bis (3',4'-substituted-phenyl)-1,4-quinonediimines computed at the B3LYP/6-311+G(2d,p) level on B3LYP/6-31G ∗ molecular geometries. These parameters were then least squares fit as a function of literature Hammett parameters. For N, N' -bis (4'-substituted-phenyl)-1,4-quinonediimines, the least squares fits demonstrated excellent linearity, with the square of Pearson's correlation coefficient ( r2) greater than 0.98 for all isomers. For N, N' -bis (3'-substituted-3'-aminophenyl)-1,4-quinonediimines, the least squares fits were less nearly linear, with r2 approximately 0.70 for all isomers when derived from calculated vertical ionization potentials, but those from calculated vertical electron affinities usually greater than 0.90.

STRUCTURE FOR SUB-ASSEMBLIES OF ELECTRONIC EQUIPMENT

DOEpatents

Bell, P.R.; Harris, C.C.

1959-03-31

Sub-assemblies for electronic systems, particularly a unit which is self- contained and which may be adapted for quick application to and detachment from a chassis or panel, are discussed. The disclosed structure serves the dual purpose of a cover or enclosure for a subassembly comprising a base plate and also acts as a clamp for retaining the base plate in position on a chassis. The clamping action is provided by flexible fingers projecting from the side walls of the cover and extending through grooves in the base plate to engage with the opposite side of the chassis.

Formation of Sub-Millimeter-Size Powerful X-Ray Sources in Low-Impedance Rod-Pinch Diodes

NASA Astrophysics Data System (ADS)

Sorokin, S. A.

2018-01-01

In the paper, experiments on the formation of a low-impedance diode and a focused electron beam as a result of detachment of radial wires, accelerated by the current of a high-current generator, from the rod anode have been described. In the experiments, along with studies of conditions for compact focusing of the electron beam and effective generation of hard x-rays, the shape of the tip of the anode rod is determined at which the x-ray source is point-sized when viewed in the radial direction.

Polarization asymmetry in two-electron photodetachment - A cogent test of the ionization threshold law

NASA Technical Reports Server (NTRS)

Temkin, A.; Bhatia, A. K.

1988-01-01

A very sensitive test of the electron-atom ionization threshold law is suggested: for spin-aligned heavy negative ions it consists of measuring the polarization asymmetry A(PA) coming from double detachment by left- versus right-circularly polarized light. The respective yields are worked out for the Te(-) (5p)5 2P(3/2) ion. The Coulomb-dipole theory predicts A(PA) to be the ratio of two oscillating functions in sharp contrast to any power law (specifically that of Wannier, 1953) for which the ratio is expected to be a smooth function of energy.

Human dental pulp stem cell adhesion and detachment in polycaprolactone electrospun scaffolds under direct perfusion

PubMed Central

Paim, A.; Braghirolli, D.I.; Cardozo, N.S.M.; Pranke, P.; Tessaro, I.C.

2018-01-01

Cell adhesion in three-dimensional scaffolds plays a key role in tissue development. However, stem cell behavior in electrospun scaffolds under perfusion is not fully understood. Thus, an investigation was made on the effect of flow rate and shear stress, adhesion time, and seeding density under direct perfusion in polycaprolactone electrospun scaffolds on human dental pulp stem cell detachment. Polycaprolactone scaffolds were electrospun using a solvent mixture of chloroform and methanol. The viable cell number was determined at each tested condition. Cell morphology was analyzed by confocal microscopy after various incubation times for static cell adhesion with a high seeding density. Scanning electron microscopy images were obtained before and after perfusion for the highest flow rate tested. The wall pore shear stress was calculated for all tested flow rates (0.005–3 mL/min). An inversely proportional relationship between adhesion time with cell detachment under perfusion was observed. Lower flow rates and lower seeding densities reduced the drag of cells by shear stress. However, there was an operational limit for the lowest flow rate that can be used without compromising cell viability, indicating that a flow rate of 0.05 mL/min might be more suitable for the tested cell culture in electrospun scaffolds under direct perfusion. PMID:29590258

Linking microcracks and mineral zoning of detachment-exhumed granites to their tectonomagmatic history: Evidence from the Salihli and Turgutlu plutons in western Turkey (Menderes Massif)

NASA Astrophysics Data System (ADS)

Catlos, Elizabeth J.; Baker, Courteney B.; Sorensen, Sorena S.; Jacob, Lauren; Çemen, Ibrahim

2011-05-01

The Menderes Massif (western Turkey) is a metamorphic core complex that displays linked syntectonic plutonism and detachment faulting. Fabrics in S-type peraluminous granites (Salihli and Turgutlu) in the detachment (Alaşehir) footwall change from isotropic to protomylonitic to mylonitic towards the structure. Samples from the isotropic and protomylonitic zones were imaged in transmitted light, cathodoluminescence (CL), backscattered (BSE), and secondary electrons (SE), and show that these rocks contain abundant microcracks, and that plagioclase grains have zoning consistent with magma mixing. The granites contain fluid inclusion planes (FIPs), myrmekite replacing plagioclase, and the removal of blue luminescence in K-feldspar along microcracks and grain boundaries. Calcite and hydrous minerals commonly fill microcracks. The samples record features that formed due to (1) magma crystallization and ductile deformation (FIPs, mineral zoning), (2) changes in P and/or T (impingement and stress-induced microcracks in protomylonitic rocks), and (3) differences in intrinsic mineral properties (radial, cleavage, blunted, and deflected microcracks). Overprinted microcracks indicate exhumation during pulses. The Middle Miocene ages of these granites reported elsewhere are similar to those from large-scale extensional structures in Greece's Cycladic Massif. The Menderes and Cycladic core complexes may have developed simultaneously due to the widespread intrusion of subduction-related granitoids.

Vertical electron transport in van der Waals heterostructures with graphene layers

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

Ryzhii, V., E-mail: v-ryzhii@riec.tohoku.ac.jp; Center for Photonics and Infrared Engineering, Bauman Moscow State Technical University and Institute of Ultra High Frequency Semiconductor Electronics of RAS, Moscow 111005; Otsuji, T.

We propose and analyze an analytical model for the self-consistent description of the vertical electron transport in van der Waals graphene-layer (GL) heterostructures with the GLs separated by the barriers layers. The top and bottom GLs serve as the structure emitter and collector. The vertical electron transport in such structures is associated with the propagation of the electrons thermionically emitted from GLs above the inter-GL barriers. The model under consideration describes the processes of the electron thermionic emission from and the electron capture to GLs. It accounts for the nonuniformity of the self-consistent electric field governed by the Poisson equationmore » which accounts for the variation of the electron population in GLs. The model takes also under consideration the cooling of electrons in the emitter layer due to the Peltier effect. We find the spatial distributions of the electric field and potential with the high-electric-field domain near the emitter GL in the GL heterostructures with different numbers of GLs. Using the obtained spatial distributions of the electric field, we calculate the current-voltage characteristics. We demonstrate that the Peltier cooling of the two-dimensional electron gas in the emitter GL can strongly affect the current-voltage characteristics resulting in their saturation. The obtained results can be important for the optimization of the hot-electron bolometric terahertz detectors and different devices based on GL heterostructures.« less

Effect of hydrogen on the integrity of aluminium–oxide interface at elevated temperatures

PubMed Central

Li, Meng; Xie, De-Gang; Ma, Evan; Li, Ju; Zhang, Xi-Xiang; Shan, Zhi-Wei

2017-01-01

Hydrogen can facilitate the detachment of protective oxide layer off metals and alloys. The degradation is usually exacerbated at elevated temperatures in many industrial applications; however, its origin remains poorly understood. Here by heating hydrogenated aluminium inside an environmental transmission electron microscope, we show that hydrogen exposure of just a few minutes can greatly degrade the high temperature integrity of metal–oxide interface. Moreover, there exists a critical temperature of ∼150 °C, above which the growth of cavities at the metal–oxide interface reverses to shrinkage, followed by the formation of a few giant cavities. Vacancy supersaturation, activation of a long-range diffusion pathway along the detached interface and the dissociation of hydrogen-vacancy complexes are critical factors affecting this behaviour. These results enrich the understanding of hydrogen-induced interfacial failure at elevated temperatures. PMID:28218260

Effects of G, a Growth Regulator from Eucalyptus grandis, on Photosynthesis

PubMed Central

Sharkey, Thomas D.; Stevenson, Gay F.; Paton, Dugald M.

1982-01-01

A growth regulator (G; 4-ethyl-1-hydroxy-4,8,8,10,10 pentamethyl-7,9-dioxo-2,3 dioxyabicyclo (4.4.0) decene-5) from Eucalyptus grandis (Maiden) reduced stomatal conductance and also photosynthetic capacity when fed through the transpiration stream of detached leaves. The concentration of G required for this effect was high (10−4 molar), but the amount of G taken up (dose) was below the level which has previously been found in E. grandis leaves. Similar effects were observed in detached leaves of Xanthium strumarium L. though almost 10 times more G was required. G reduced CO2-dependent O2 evolution from isolated cells of X. strumarium. In spinach (Spinacia oleracea L.) chloroplasts, electron transport through photosystem II was reduced by G. It is proposed that G affects stomatal conductance and photosynthesis by reducing photosystem II activity in both the guard cell chloroplasts and mesophyll cell chloroplasts. PMID:16662322

Secondary electron emission from textured surfaces

NASA Astrophysics Data System (ADS)

Huerta, C. E.; Patino, M. I.; Wirz, R. E.

2018-04-01

In this work, a Monte Carlo model is used to investigate electron induced secondary electron emission for varying effects of complex surfaces by using simple geometric constructs. Geometries used in the model include: vertical fibers for velvet-like surfaces, tapered pillars for carpet-like surfaces, and a cage-like configuration of interlaced horizontal and vertical fibers for nano-structured fuzz. The model accurately captures the secondary electron emission yield dependence on incidence angle. The model shows that unlike other structured surfaces previously studied, tungsten fuzz exhibits secondary electron emission yield that is independent of primary electron incidence angle, due to the prevalence of horizontally-oriented fibers in the fuzz geometry. This is confirmed with new data presented herein of the secondary electron emission yield of tungsten fuzz at incidence angles from 0-60°.

Rate and Localization of Graft Detachment in Descemet Membrane Endothelial Keratoplasty.

PubMed

Maier, Anna-Karina B; Gundlach, Enken; Pilger, Daniel; Rübsam, Anne; Klamann, Matthias K J; Gonnermann, Johannes; Bertelmann, Eckart; Joussen, Antonia M; Torun, Necip

2016-03-01

To investigate the rate and localization of graft detachment after Descemet membrane endothelial keratoplasty. Sixty-six consecutive cases operated between June and August 2014 at the Charité-Universitätsmedizin Berlin were examined prospectively 1 week postoperatively. A single masked observer analyzed the rate and localization of graft detachment using optical coherence tomography (OCT), and the rebubbling rate was measured. Localization of graft detachment was correlated to the incision approach. Preoperative data were correlated to the rate of graft detachment and rebubbling. Graft detachment occurred in more than 2 clock hours and with postoperative corneal edema in 33.3% and required rebubbling. In 33.3%, graft detachment occurred in more than 2 clock hours and with postoperative corneal edema and required rebubbling. The mean graft detachment rate was 8.3% per clock hour. A significantly higher graft detachment rate was noted in the inferior clock hours (21.1%, P < 0.0001, 16.7%, P = 0.003). Only higher age of the patient correlated to a higher rate of graft detachment (P = 0.022). No correlation was found between localization of graft detachment and the incision approach (P = 0.615). The graft detachment rate is high after Descemet membrane endothelial keratoplasty, but detachment is usually peripheral, partial and mainly inferior and involves only a few clock hours. Only higher age of the patient is strongly associated with a higher rate of graft detachment. The incision approach is not significantly correlated with the localization of graft detachment. Therefore, the postoperative supine position of the patient seems to be of major importance.Clinical Trial Registration-URL: http://www.clinicaltrials.gov. Unique identifier: NCT02020044.

Plasma detachment in divertor tokamaks

DOE PAGES

Leonard, A. W.

2018-02-07

In this study, observations of divertor plasma detachment in tokamaks are reviewed. Plasma detachment is characterized in terms of transport and dissipation of power, momentum and particle flux along the open field lines from the midplane to the divertor. Asymmetries in detachment onset and other characteristics between the inboard and outboard divertor plasmas is found to be primarily driven by plasmamore » $$\\vec{E}$$ x $$\\vec{B}$$ drifts. The effect of divertor plate geometry and magnetic configuration on divertor detachment is summarized. Control of divertor detachment has progressed with a development of a number of diagnostics to characterize the detached state in real-time. Finally the compatibility of detached divertor operation with high performance core plasmas is examined.« less

Plasma detachment in divertor tokamaks

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

Leonard, A. W.

In this study, observations of divertor plasma detachment in tokamaks are reviewed. Plasma detachment is characterized in terms of transport and dissipation of power, momentum and particle flux along the open field lines from the midplane to the divertor. Asymmetries in detachment onset and other characteristics between the inboard and outboard divertor plasmas is found to be primarily driven by plasmamore » $$\\vec{E}$$ x $$\\vec{B}$$ drifts. The effect of divertor plate geometry and magnetic configuration on divertor detachment is summarized. Control of divertor detachment has progressed with a development of a number of diagnostics to characterize the detached state in real-time. Finally the compatibility of detached divertor operation with high performance core plasmas is examined.« less

Detachment of solids and nitrifiers in integrated, fixed-film activated sludge systems.

PubMed

Maas, Carol L A; Parker, Wayne J; Legge, Raymond L

2008-12-01

Despite the importance of detachment to biofilm processes, detachment phenomena are not well understood. In this study, researchers investigated biofilm detachment from free-floating biofilm carriers that were established in an integrated, fixed-film activated sludge (IFAS) installation in Mississauga, Ontario. A method for assessing detachment from biofilm carrier systems was devised, evaluated, and refined during this study. In the absence of substrate, superficial air velocity significantly affected the 24-hour detachment rates of total suspended solids from the carriers. Short-term growth conditions did not appear to significantly affect the rate of detachment of solids and nitrifiers. The measured solids-detachment rates were found to be described by a second order function of biofilm attached growth total solids with a detachment coefficient of 0.006 +/- 0.0008 (g/m x d)(-1).

Folding of a detachment and fault - Modified detachment folding along a lateral ramp, southwestern Montana, USA

NASA Astrophysics Data System (ADS)

Schmidt, Christopher; Whisner, S. Christopher; Whisner, Jennifer B.

2014-12-01

The inversion of the Middle Proterozoic Belt sedimentary basin during Late Cretaceous thrusting in Montana produced a large eastwardly-convex salient, the southern boundary of which is a 200 km-long oblique to lateral ramp subtended by a detachment between the Belt rocks and Archean basement. A 10 km-long lateral ramp segment exposes the upper levels of the detachment where hanging wall Belt rocks have moved out over the Paleozoic and Mesozoic section. The hanging wall structure consists of a train of high amplitude, faulted, asymmetrical detachment folds. Initial west-east shortening produced layer parallel shortening fabrics and dominantly strike slip faulting followed by symmetrical detachment folding. 'Lock-up' of movement on the detachment surface produced regional simple shear and caused the detachment folds to become asymmetrical and faulted. Folding of the detachment surface after lock-up modified the easternmost detachment folds further into a southeast-verging, overturned fold pair with a ramp-related fault along the base of the stretched mutual limb.

Understanding Rubredoxin Redox Sites by Density Functional Theory Studies of Analogues

PubMed Central

Luo, Yan; Niu, Shuqiang; Ichiye, Toshiko

2012-01-01

Determining the redox energetics of redox site analogues of metalloproteins is essential in unraveling the various contributions to electron transfer properties of these proteins. Since studies of the [4Fe-4S] analogues show that the energies are dependent on the ligand dihedral angles, broken symmetry density functional theory (BS-DFT) with the B3LYP functional and double-ζ basis sets calculations of optimized geometries and electron detachment energies of [1Fe] rubredoxin analogues are compared to crystal structures and gas-phase photoelectron spectroscopy data, respectively, for [Fe(SCH3)4]0/1-/2-, [Fe(S2-o-xyl2)]0/1-/2-, and Na+[Fe(S2-o-xyl)2]1-/2- in different conformations. In particular, the study of Na+[Fe(S2-o-xyl)2]1-/2- is the only direct comparison of calculated and experimental gas phase detachment energies for the 1-/2- couple found in the rubredoxins. These results show that variations in the inner sphere energetics by up to ~0.4 eV can be caused by differences in the ligand dihedral angles in either or both redox states. Moreover, these results indicate that the protein stabilizes the conformation that favors reduction. In addition, the free energies and reorganization energies of oxidation and reduction as well as electrostatic potential charges are calculated, which can be used as estimates in continuum electrostatic calculations of electron transfer properties of [1Fe] proteins. PMID:22881577

Bilayer insulator tunnel barriers for graphene-based vertical hot-electron transistors

NASA Astrophysics Data System (ADS)

Vaziri, S.; Belete, M.; Dentoni Litta, E.; Smith, A. D.; Lupina, G.; Lemme, M. C.; Östling, M.

2015-07-01

Vertical graphene-based device concepts that rely on quantum mechanical tunneling are intensely being discussed in the literature for applications in electronics and optoelectronics. In this work, the carrier transport mechanisms in semiconductor-insulator-graphene (SIG) capacitors are investigated with respect to their suitability as electron emitters in vertical graphene base transistors (GBTs). Several dielectric materials as tunnel barriers are compared, including dielectric double layers. Using bilayer dielectrics, we experimentally demonstrate significant improvements in the electron injection current by promoting Fowler-Nordheim tunneling (FNT) and step tunneling (ST) while suppressing defect mediated carrier transport. High injected tunneling current densities approaching 103 A cm-2 (limited by series resistance), and excellent current-voltage nonlinearity and asymmetry are achieved using a 1 nm thick high quality dielectric, thulium silicate (TmSiO), as the first insulator layer, and titanium dioxide (TiO2) as a high electron affinity second layer insulator. We also confirm the feasibility and effectiveness of our approach in a full GBT structure which shows dramatic improvement in the collector on-state current density with respect to the previously reported GBTs. The device design and the fabrication scheme have been selected with future CMOS process compatibility in mind. This work proposes a bilayer tunnel barrier approach as a promising candidate to be used in high performance vertical graphene-based tunneling devices.

Evidence of Vertical and Horizontal Motions on Venus: Maxwell Montes

NASA Astrophysics Data System (ADS)

Ansan, V.; Vergely, P.

1995-01-01

Based on full-resolution Magellan radar images, the detailed structural analysis of central Ishtar Terra (Venus) provides new insight to the understanding of the Venusian tectonics. Ishtar Terra, centered on 65° N latitude and 0° E longitude includes a high plateau. Lakshmi Planum, surrounded by highlands, the most important being Maxwell Montes to the East. Structural analysis has been performed with classical remote-sensing methods. Folds and faults identified on radar images were reported on structural map. Their type and distribution allowed to define the style of the crustal deformation and the context in which these structures formed. This analysis shows that Lakshmi Planum formed under a crustal stretching associated with a volcanic activity. This area then became a relatively steady platform, throughout the formation of Maxwell Montes mountain belt. Maxwell Montes is characterized by a series of NNW-SSE trending thrust faults dipping to the East, formed during a WSW-ESE horizontal shortening. In its NW quarter, the mountain belt shows a disturbed deformation controlled by pre-existing grabens and old vertical crustal fault zone. The deformation of this area is characterized by a shortening of cover above a flat detachment zone, with a progressive accommodation to the southwest. All these tectonic structures show evidence of horizontal and vertical crustal movements on Venus, with subsidence, mountain belt raise, West regional overthrusting of this mountain belt, and regional shear zone.

Interaction of the stream from L 1 with the outer edge of the accretion disk in a cataclysmic variable

NASA Astrophysics Data System (ADS)

Kaigorodov, P. V.; Bisikalo, D. V.; Kurbatov, E. P.

2017-08-01

Vertical oscillations of the gas at the outer edge of the accretion disk in a semi-detached binary due to interaction with the stream of matter from the inner Lagrangian point L 1 are considered. Mixing of the matter from the stream from L 1 with matter of the disk halo results in the formation of a system of two diverging shocks and a contact discontinuity, or so-called "hot line". The passage of matter through the region of the hot line leads to an increase in its vertical velocity and a thickening of the disk at phases 0.7-0.8. Subsequently, the matter moving along the outer edge of the disk also experiences vertical oscillations, forming secondary maxima at phases 0.2-0.4. It is shown that, for systems with component mass ratios of 0.6, these oscillations will be amplified with each passage of the matter through the hotline zone, while the observations will be quenched in systems with component mass ratios 0.07 and 7. The most favorable conditions for the flow of matter from the stream through the edge of the disk arise for component mass ratios 0.62. A theoretical relation between the phases of disk thickenings and the component mass ratio of the system is derived.

Nonlinear interaction of an intense radio wave with ionospheric D/E layer plasma

NASA Astrophysics Data System (ADS)

Sodha, Mahendra Singh; Agarwal, Sujeet Kumar

2018-05-01

This paper considers the nonlinear interaction of an intense electromagnetic wave with the D/E layer plasma in the ionosphere. A simultaneous solution of the electromagnetic wave equation and the equations describing the kinetics of D/E layer plasma is obtained; the phenomenon of ohmic heating of electrons by the electric field of the wave causes enhanced collision frequency and ionization of neutral species. Electron temperature dependent recombination of electrons with ions, electron attachment to O 2 molecules, and detachment of electrons from O2 - ions has also been taken into account. The dependence of the plasma parameters on the square of the electric vector of the wave E0 2 has been evaluated for three ionospheric heights (viz., 90, 100, and 110 km) corresponding to the mid-latitude mid-day ionosphere and discussed; these results are used to investigate the horizontal propagation of an intense radio wave at these heights.

Extending Quantum Chemistry of Bound States to Electronic Resonances

NASA Astrophysics Data System (ADS)

Jagau, Thomas-C.; Bravaya, Ksenia B.; Krylov, Anna I.

2017-05-01

Electronic resonances are metastable states with finite lifetime embedded in the ionization or detachment continuum. They are ubiquitous in chemistry, physics, and biology. Resonances play a central role in processes as diverse as DNA radiolysis, plasmonic catalysis, and attosecond spectroscopy. This review describes novel equation-of-motion coupled-cluster (EOM-CC) methods designed to treat resonances and bound states on an equal footing. Built on complex-variable techniques such as complex scaling and complex absorbing potentials that allow resonances to be associated with a single eigenstate of the molecular Hamiltonian rather than several continuum eigenstates, these methods extend electronic-structure tools developed for bound states to electronic resonances. Selected examples emphasize the formal advantages as well as the numerical accuracy of EOM-CC in the treatment of electronic resonances. Connections to experimental observables such as spectra and cross sections, as well as practical aspects of implementing complex-valued approaches, are also discussed.

Negative Electron Transfer Dissociation Sequencing of Increasingly Sulfated Glycosaminoglycan Oligosaccharides on an Orbitrap Mass Spectrometer

NASA Astrophysics Data System (ADS)

Leach, Franklin E.; Riley, Nicholas M.; Westphall, Michael S.; Coon, Joshua J.; Amster, I. Jonathan

2017-09-01

The structural characterization of sulfated glycosaminoglycan (GAG) carbohydrates remains an important target for analytical chemists attributable to challenges introduced by the natural complexity of these mixtures and the defined need for molecular-level details to elucidate biological structure-function relationships. Tandem mass spectrometry has proven to be the most powerful technique for this purpose. Previously, electron detachment dissociation (EDD), in comparison to other methods of ion activation, has been shown to provide the largest number of useful cleavages for de novo sequencing of GAG oligosaccharides, but such experiments are restricted to Fourier transform ion cyclotron resonance mass spectrometers (FTICR-MS). Negative electron transfer dissociation (NETD) provides similar fragmentation results, and can be achieved on any mass spectrometry platform that is designed to accommodate ion-ion reactions. Here, we examine for the first time the effectiveness of NETD-Orbitrap mass spectrometry for the structural analysis of GAG oligosaccharides. Compounds ranging in size from tetrasaccharides to decasaccharides were dissociated by NETD, producing both glycosidic and cross-ring cleavages that enabled the location of sulfate modifications. The highly-sulfated, heparin-like synthetic GAG, ArixtraTM, was also successfully sequenced by NETD. In comparison to other efforts to sequence GAG chains without fully ionized sulfate constituents, the occurrence of sulfate loss peaks is minimized by judicious precursor ion selection. The results compare quite favorably to prior results with electron detachment dissociation (EDD). Significantly, the duty cycle of the NETD experiment is sufficiently short to make it an effective tool for on-line separations, presenting a straightforward path for selective, high-throughput analysis of GAG mixtures. [Figure not available: see fulltext.

Anisotropic electron temperature measurements without knowing the spectral transmissivity for a JT-60SA Thomson scattering diagnostic

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

Tojo, H.; Hatae, T.; Yatsuka, E.

2012-10-15

This paper focuses on a method for measuring the electron temperature (T{sub e}) without knowing the transmissivity using Thomson scattering diagnostic with a double-pass scattering system. Application of this method for measuring the anisotropic T{sub e}, i.e., the T{sub e} in the directions parallel (T{sub e Double-Vertical-Line Double-Vertical-Line }) and perpendicular (T{sub e Up-Tack }) to the magnetic field, is proposed. Simulations based on the designed parameters for a JT-60SA indicate the feasibility of the measurements except in certain T{sub e} ranges, e.g., T{sub e Double-Vertical-Line Double-Vertical-Line }{approx} 3.5T{sub e Up-Tack} at 120 Degree-Sign of the scattering angle.

Transconjunctival drainage of serous and hemorrhagic choroidal detachment.

PubMed

Rezende, Flávio A; Kickinger, Mônica C; Li, Gisèle; Prado, Renata F; Regis, Luiz Gustavo T

2012-02-01

To describe a novel surgical technique for drainage of bullous serous and hemorrhagic choroidal detachments. A prospective, consecutive case series of 6 eyes with serous and/or hemorrhagic choroidal detachments secondary to intraocular surgery was documented to evaluate the feasibility of using the 25-gauge and 20-gauge transconjunctival trocar/cannula systems to drain choroidal detachments. Two eyes had expulsive hemorrhagic choroidal detachments and 4 eyes had serous choroidal detachments after glaucoma surgeries. A 25-gauge infusion line was placed in the anterior chamber. A 20-gauge (in eyes with hemorrhagic choroidal detachments) or a 25-gauge (in eyes with serous detachments) trocar/cannula system was inserted into the suprachoroidal space 7.0 mm from limbus. After drainage, the cannulas were removed and no sutures were placed. Pars plana vitrectomy was performed only in eyes with concomitant pathology that demanded the additional procedure. The primary outcome measure was presence of choroidal detachment at 1 week, 2 weeks, and 1 month postoperatively. Secondary outcome measures were visual acuity at 6 months and intraocular pressure at 1 week and 1, 3, and 6 months postoperatively. Drainage of hemorrhagic choroidal detachments resulted in resolution of the detachments by 1 month postoperatively. In eyes with serous detachments, resolution was achieved by 1 week postdrainage. In both groups, intraocular pressure increased to at least 10 mmHg by postoperative Week 1. The visual acuity improved in all eyes. No complications related to the transconjunctival technique were noted. Transconjunctival drainage of serous and hemorrhagic choroidal detachments seems to be a feasible and simple surgical option with minimal scleral and conjunctival damage. Pars plana vitrectomy may not be necessary when draining choroidal detachments in this manner.

Hartree-Fock implementation using a Laguerre-based wave function for the ground state and correlation energies of two-electron atoms.

PubMed

King, Andrew W; Baskerville, Adam L; Cox, Hazel

2018-03-13

An implementation of the Hartree-Fock (HF) method using a Laguerre-based wave function is described and used to accurately study the ground state of two-electron atoms in the fixed nucleus approximation, and by comparison with fully correlated (FC) energies, used to determine accurate electron correlation energies. A variational parameter A is included in the wave function and is shown to rapidly increase the convergence of the energy. The one-electron integrals are solved by series solution and an analytical form is found for the two-electron integrals. This methodology is used to produce accurate wave functions, energies and expectation values for the helium isoelectronic sequence, including at low nuclear charge just prior to electron detachment. Additionally, the critical nuclear charge for binding two electrons within the HF approach is calculated and determined to be Z HF C =1.031 177 528.This article is part of the theme issue 'Modern theoretical chemistry'. © 2018 The Author(s).

Carbon dioxide is tightly bound in the [Co(Pyridine)(CO2)]- anionic complex

NASA Astrophysics Data System (ADS)

Graham, Jacob D.; Buytendyk, Allyson M.; Zhang, Xinxing; Kim, Seong K.; Bowen, Kit H.

2015-11-01

The [Co(Pyridine)(CO2)]- anionic complex was studied through the combination of photoelectron spectroscopy and density functional theory calculations. This complex was envisioned as a primitive model system for studying CO2 binding to negatively charged sites in metal organic frameworks. The vertical detachment energy (VDE) measured via the photoelectron spectrum is 2.7 eV. Our calculations imply a structure for [Co(Pyridine)(CO2)]- in which a central cobalt atom is bound to pyridine and CO2 moieties on either sides. This structure was validated by acceptable agreement between the calculated and measured VDE values. Based on our calculations, we found CO2 to be bound within the anionic complex by 1.4 eV.

Carbon dioxide is tightly bound in the [Co(Pyridine)(CO2)](-) anionic complex.

PubMed

Graham, Jacob D; Buytendyk, Allyson M; Zhang, Xinxing; Kim, Seong K; Bowen, Kit H

2015-11-14

The [Co(Pyridine)(CO2)](-) anionic complex was studied through the combination of photoelectron spectroscopy and density functional theory calculations. This complex was envisioned as a primitive model system for studying CO2 binding to negatively charged sites in metal organic frameworks. The vertical detachment energy (VDE) measured via the photoelectron spectrum is 2.7 eV. Our calculations imply a structure for [Co(Pyridine)(CO2)](-) in which a central cobalt atom is bound to pyridine and CO2 moieties on either sides. This structure was validated by acceptable agreement between the calculated and measured VDE values. Based on our calculations, we found CO2 to be bound within the anionic complex by 1.4 eV.

Photoelectron spectroscopic study of the hydrated nucleoside anions: Uridine(-)(H(2)O)(n=0-2), cytidine(-)(H(2)O)(n=0-2), and thymidine(-)(H(2)O)(n=0,1).

PubMed

Li, Xiang; Wang, Haopeng; Bowen, Kit H

2010-10-14

The hydrated nucleoside anions, uridine(-)(H(2)O)(n=0-2), cytidine(-)(H(2)O)(n=0-2), and thymidine(-)(H(2)O)(n=0,1), have been prepared in beams and studied by anion photoelectron spectroscopy in order to investigate the effects of a microhydrated environment on parent nucleoside anions. Vertical detachment energies (VDEs) were measured for all eight anions, and from these, estimates were made for five sequential anion hydration energies. Excellent agreement was found between our measured VDE value for thymidine(-)(H(2)O)(1) and its calculated value in the companion article by S. Kim and H. F. Schaefer III.

Photoelectron spectroscopic study of the hydrated nucleoside anions: Uridine-(H2O)n=0-2, cytidine-(H2O)n=0-2, and thymidine-(H2O)n=0,1

NASA Astrophysics Data System (ADS)

Li, Xiang; Wang, Haopeng; Bowen, Kit H.

2010-10-01

The hydrated nucleoside anions, uridine-(H2O)n=0-2, cytidine-(H2O)n=0-2, and thymidine-(H2O)n=0,1, have been prepared in beams and studied by anion photoelectron spectroscopy in order to investigate the effects of a microhydrated environment on parent nucleoside anions. Vertical detachment energies (VDEs) were measured for all eight anions, and from these, estimates were made for five sequential anion hydration energies. Excellent agreement was found between our measured VDE value for thymidine-(H2O)1 and its calculated value in the companion article by S. Kim and H. F. Schaefer III.

Electron Detachment Dissociation of Underivatized Chloride-Adducted Oligosaccharides

NASA Astrophysics Data System (ADS)

Kornacki, James R.; Adamson, Julie T.; Håkansson, Kristina

2012-11-01

Chloride anion attachment has previously been shown to aid determination of saccharide anomeric configuration and generation of linkage information in negative ion post-source decay MALDI tandem mass spectrometry. Here, we employ electron detachment dissociation (EDD) and collision activated dissociation (CAD) for the structural characterization of underivatized oligosaccharides bearing a chloride ion adduct. Both neutral and sialylated oligosaccharides are examined, including maltoheptaose, an asialo biantennary glycan (NA2), disialylacto- N-tetraose (DSLNT), and two LS tetrasaccharides (LSTa and LSTb). Gas-phase chloride-adducted species are generated by negative ion mode electrospray ionization. EDD and CAD spectra of chloride-adducted oligosaccharides are compared to the corresponding spectra for doubly deprotonated species not containing a chloride anion to assess the role of chloride adduction in the stimulation of alternative fragmentation pathways and altered charge locations allowing detection of additional product ions. In all cases, EDD of singly chloridated and singly deprotonated species resulted in an increase in observed cross-ring cleavages, which are essential to providing saccharide linkage information. Glycosidic cleavages also increased in EDD of chloride-adducted oligosaccharides to reveal complementary structural information compared to traditional (non-chloride-assisted) EDD and CAD. Results indicate that chloride adduction is of interest in alternative anion activation methods such as EDD for oligosaccharide structural characterization.

Sinusoidal obstruction syndrome (SOS): A light and electron microscopy study in human liver.

PubMed

Vreuls, C P H; Driessen, A; Olde Damink, S W M; Koek, G H; Duimel, H; van den Broek, M A J; Dejong, C H C; Braet, F; Wisse, E

2016-05-01

Oxaliplatin is an important chemotherapeutic agent, used in the treatment of hepatic colorectal metastases, and known to induce the sinusoidal obstruction syndrome (SOS). Pathophysiological knowledge concerning SOS is based on a rat model. Therefore, the aim was to perform a comprehensive study of the features of human SOS, using both light microscopy (LM) and electron microscopy (EM). Included were all patients of whom wedge liver biopsies were collected during a partial hepatectomy for colorectal liver metastases, in a 4-year period. The wedge biopsy were perfusion fixated and processed for LM and EM. The SOS lesions were selected by LM and details were studied using EM. Material was available of 30 patients, of whom 28 patients received neo-adjuvant oxaliplatin. Eighteen (64%) of the 28 patients showed SOS lesions, based on microscopy. The lesions consisted of sinusoidal endothelial cell detachment from the space of Disse on EM. In the enlarged space of Disse a variable amount of erythrocytes were located. Sinusoidal endothelial cell detachment was present in human SOS, accompanied by enlargement of the space of Disse and erythrocytes in this area. These findings, originally described in a rat model, were now for the first time confirmed in human livers under clinically relevant settings. Copyright © 2016 Elsevier Ltd. All rights reserved.

Cellular volume regulation and substrate stiffness modulate the detachment dynamics of adherent cells

NASA Astrophysics Data System (ADS)

Yang, Yuehua; Jiang, Hongyuan

2018-03-01

Quantitative characterizations of cell detachment are vital for understanding the fundamental mechanisms of cell adhesion. Experiments have found that cell detachment shows strong rate dependence, which is mostly attributed to the binding-unbinding kinetics of receptor-ligand bond. However, our recent study showed that the cellular volume regulation can significantly regulate the dynamics of adherent cell and cell detachment. How this cellular volume regulation contributes to the rate dependence of cell detachment remains elusive. Here, we systematically study the role of cellular volume regulation in the rate dependence of cell detachment by investigating the cell detachments of nonspecific adhesion and specific adhesion. We find that the cellular volume regulation and the bond kinetics dominate the rate dependence of cell detachment at different time scales. We further test the validity of the traditional Johnson-Kendall-Roberts (JKR) contact model and the detachment model developed by Wyart and Gennes et al (W-G model). When the cell volume is changeable, the JKR model is not appropriate for both the detachments of convex cells and concave cells. The W-G model is valid for the detachment of convex cells but is no longer applicable for the detachment of concave cells. Finally, we show that the rupture force of adherent cells is also highly sensitive to substrate stiffness, since an increase in substrate stiffness will lead to more associated bonds. These findings can provide insight into the critical role of cell volume in cell detachment and might have profound implications for other adhesion-related physiological processes.

Three dimensional fluid-kinetic model of a magnetically guided plasma jet

NASA Astrophysics Data System (ADS)

Ramos, Jesús J.; Merino, Mario; Ahedo, Eduardo

2018-06-01

A fluid-kinetic model of the collisionless plasma flow in a convergent-divergent magnetic nozzle is presented. The model combines the leading-order Vlasov equation and the fluid continuity and perpendicular momentum equation for magnetized electrons, and the fluid equations for cold ions, which must be solved iteratively to determine the self-consistent plasma response in a three-dimensional magnetic field. The kinetic electron solution identifies three electron populations and provides the plasma density and pressure tensor. The far downstream asymptotic behavior shows the anisotropic cooling of the electron populations. The fluid equations determine the electric potential and the fluid velocities. In the small ion-sound gyroradius case, the solution is constructed one magnetic line at a time. In the large ion-sound gyroradius case, ion detachment from magnetic lines makes the problem fully three-dimensional.

Beam based measurement of beam position monitor electrode gains

NASA Astrophysics Data System (ADS)

Rubin, D. L.; Billing, M.; Meller, R.; Palmer, M.; Rendina, M.; Rider, N.; Sagan, D.; Shanks, J.; Strohman, C.

2010-09-01

Low emittance tuning at the Cornell Electron Storage Ring (CESR) test accelerator depends on precision measurement of vertical dispersion and transverse coupling. The CESR beam position monitors (BPMs) consist of four button electrodes, instrumented with electronics that allow acquisition of turn-by-turn data. The response to the beam will vary among the four electrodes due to differences in electronic gain and/or misalignment. This variation in the response of the BPM electrodes will couple real horizontal offset to apparent vertical position, and introduce spurious measurements of coupling and vertical dispersion. To alleviate this systematic effect, a beam based technique to measure the relative response of the four electrodes has been developed. With typical CESR parameters, simulations show that turn-by-turn BPM data can be used to determine electrode gains to within ˜0.1%.

Highly efficient gate-tunable photocurrent generation in vertical heterostructures of layered materials

PubMed Central

Yu, Woo Jong; Liu, Yuan; Zhou, Hailong; Yin, Anxiang; Li, Zheng; Huang, Yu

2014-01-01

Layered materials of graphene and MoS2, for example, have recently emerged as an exciting material system for future electronics and optoelectronics. Vertical integration of layered materials can enable the design of novel electronic and photonic devices. Here, we report highly efficient photocurrent generation from vertical heterostructures of layered materials. We show that vertically stacked graphene–MoS2–graphene and graphene–MoS2–metal junctions can be created with a broad junction area for efficient photon harvesting. The weak electrostatic screening effect of graphene allows the integration of single or dual gates under and/or above the vertical heterostructure to tune the band slope and photocurrent generation. We demonstrate that the amplitude and polarity of the photocurrent in the gated vertical heterostructures can be readily modulated by the electric field of an external gate to achieve a maximum external quantum efficiency of 55% and internal quantum efficiency up to 85%. Our study establishes a method to control photocarrier generation, separation and transport processes using an external electric field. PMID:24162001

Observation of electron cloud instabilities and emittance dilution at the Cornell electron-positron Storage ring Test Accelerator

DOE PAGES

Holtzapple, R. L.; Billing, M. G.; Campbell, R. C.; ...

2016-04-11

Electron cloud related emittance dilution and instabilities of bunch trains limit the performance of high intensity circular colliders. One of the key goals of the Cornell electron-positron storage ring Test Accelerator (CesrTA) research program is to improve our understanding of how the electron cloud alters the dynamics of bunches within the train. Single bunch beam diagnostics have been developed to measure the beam spectra, vertical beam size, two important dynamical effects of beams interacting with the electron cloud, for bunch trains on a turn-by-turn basis. Experiments have been performed at CesrTA to probe the interaction of the electron cloud withmore » stored positron bunch trains. The purpose of these experiments was to characterize the dependence of beam-electron cloud interactions on the machine parameters such as bunch spacing, vertical chromaticity, and bunch current. The beam dynamics of the stored beam, in the presence of the electron cloud, was quantified using: 1) a gated beam position monitor (BPM) and spectrum analyzer to measure the bunch-by-bunch frequency spectrum of the bunch trains, 2) an x-ray beam size monitor to record the bunch-by-bunch, turn-by-turn vertical size of each bunch within the trains. In this study we report on the observations from these experiments and analyze the effects of the electron cloud on the stability of bunches in a train under many different operational conditions.« less

Observation of Electron Cloud Instabilities and Emittance Dilution at the Cornell Electron-Positron Storage Ring Test Accelerator

NASA Astrophysics Data System (ADS)

Holtzapple, R. L.; Billing, M. G.; Campbell, R. C.; Dugan, G. F.; Flanagan, J.; McArdle, K. E.; Miller, M. I.; Palmer, M. A.; Ramirez, G. A.; Sonnad, K. G.; Totten, M. M.; Tucker, S. L.; Williams, H. A.

2016-04-01

Electron cloud related emittance dilution and instabilities of bunch trains limit the performance of high intensity circular colliders. One of the key goals of the Cornell electron-positron storage ring Test Accelerator (CesrTA) research program is to improve our understanding of how the electron cloud alters the dynamics of bunches within the train. Single bunch beam diagnotics have been developed to measure the beam spectra, vertical beam size, two important dynamical effects of beams interacting with the electron cloud, for bunch trains on a turn-by-turn basis. Experiments have been performed at CesrTA to probe the interaction of the electron cloud with stored positron bunch trains. The purpose of these experiments was to characterize the dependence of beam-electron cloud interactions on the machine parameters such as bunch spacing, vertical chromaticity, and bunch current. The beam dynamics of the stored beam, in the presence of the electron cloud, was quantified using: 1) a gated beam position monitor (BPM) and spectrum analyzer to measure the bunch-by-bunch frequency spectrum of the bunch trains; 2) an x-ray beam size monitor to record the bunch-by-bunch, turn-by-turn vertical size of each bunch within the trains. In this paper we report on the observations from these experiments and analyze the effects of the electron cloud on the stability of bunches in a train under many different operational conditions.

Psychological Detachment Mediating the Daily Relationship between Workload and Marital Satisfaction

PubMed Central

Germeys, Lynn; De Gieter, Sara

2017-01-01

Scholars already demonstrated that psychologically detaching from work after workhours can diminish or avoid the negative effects of job demands on employees' well-being. In this study, we examined a curvilinear relationship between workload and psychological detachment. Moreover, we investigated the moderating influence of an employee's work-home segmentation preference on the relation between detachment and marital satisfaction. In addition, we applied and extended the stressor-detachment model by examining detachment as a mediator of the relation between workload and marital satisfaction. A total of 136 employees participated in our daily diary survey study during 10 consecutive working days. The results of the Bayesian 2-level path analyses revealed a negative linear and curvilinear relationship between workload and psychological detachment on a daily basis. Daily detachment positively related to marital satisfaction, with one's preference to segment work from home reinforcing this relationship. Moreover, psychological detachment fully mediated the daily relationship between workload and marital satisfaction. Implications for practice and suggestions for future research are discussed. PMID:28101076

Characterization and Reliability of Vertical N-Type Gallium Nitride Schottky Contacts

DTIC Science & Technology

2016-09-01

barrier diode SEM scanning electron microscopy SiC silicon carbide SMU source measure unit xvi THIS PAGE INTENTIONALLY LEFT BLANK xvii...arguably the Schottky barrier diode (SBD). The SBD is a fundamental component in the majority of power electronic devices; specifically, those used in...Ishizuka, and Ueno demonstrated the long-term reliability of vertical metal-GaN Schottky barrier diodes through their analysis of the degradation

Psychological Detachment in the Relationship between Job Stressors and Strain

PubMed Central

Safstrom, My; Hartig, Terry

2013-01-01

We investigated the mediating versus moderating role of psychological detachment in the relationship between job stressors and psychological strain. Our sample consisted of 173 university students invested in challenging programs of advanced professional studies, who could find it difficult to detach from work. Hierarchical regression analyses of cross-sectional survey data affirmed the role of psychological detachment as a mediator in the relationship between job demands and perceived stress. Detachment also mediated the relationship between job demands and satisfaction with life, although the association disappeared when controlling for negative affectivity. Detachment did not mediate relationships between job demands and cognitive failures. Psychological detachment did not moderate any of the investigated relationships. The study contributes to a view of psychological detachment as less subject to individual differences than to the imposition of stressors in the given context. PMID:25379246

Direct Observation of Ultralow Vertical Emittance using a Vertical Undulator

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

Wootton, Kent

2015-09-17

In recent work, the first quantitative measurements of electron beam vertical emittance using a vertical undulator were presented, with particular emphasis given to ultralow vertical emittances [K. P. Wootton, et al., Phys. Rev. ST Accel. Beams, 17, 112802 (2014)]. Using this apparatus, a geometric vertical emittance of 0.9 ± 0.3 pm rad has been observed. A critical analysis is given of measurement approaches that were attempted, with particular emphasis on systematic and statistical uncertainties. The method used is explained, compared to other techniques and the applicability of these results to other scenarios discussed.

Are core self-evaluations a suitable moderator in stressor-detachment relationships? A study among managers' perceived job demands, detachment and strain reactions.

PubMed

Hentrich, Stephan; Zimber, Andreas; Sosnowsky-Waschek, Nadia; Gregersen, Sabine; Petermann, Franz

2018-01-01

The relationships among job demands, personality factors, recovery and psychological health receive increasing attention but are not well understoodOBJECTIVE:Therefore, the present study tests moderating effects among a sample of managers as proposed by the stressor-detachment model. We aimed to determine whether core self-evaluations (CSE) had an influence on the correlations between detachment and strain reactions (depressive symptoms, irritation, exhaustion) and between job demands and detachment. Further, we tested whether detachment attenuates the positive relation between job demands and strain reactions. A convenience sample of managers in three German settings (N = 282) participated in the cross-sectional study. Results based on hierarchical regression analysis showed that high CSE significantly weakened the negative relationship between detachment and depressive symptoms in this sample. However, CSE did not moderate the negative relationship between job demands and detachment. Moreover, results revealed that detachment moderated the positive relation between job demands and exhaustion. The authors tested whether CSE was able to moderate the relationship between job demands, psychological detachment and different stress reactions. Although we found a significant interaction effect, CSE may be too distal to moderate all respective associations.

Psychological detachment from work during non-work time: linear or curvilinear relations with mental health and work engagement?

PubMed

Shimazu, Akihito; Matsudaira, Ko; Jonge, Jan DE; Tosaka, Naoya; Watanabe, Kazuhiro; Takahashi, Masaya

2016-06-10

This study examined whether a higher level of psychological detachment during non-work time is associated with better employee mental health (Hypothesis 1), and examined whether psychological detachment has a curvilinear relation (inverted U-shaped pattern) with work engagement (Hypothesis 2). A large cross-sectional Internet survey was conducted among registered monitors of an Internet survey company in Japan. The questionnaire included scales for psychological detachment, employee mental health, and work engagement as well as for job characteristics and demographic variables as potential confounders. The hypothesized model was tested with moderated structural equation modeling techniques among 2,234 respondents working in the tertiary industries with regular employment. Results showed that psychological detachment had curvilinear relations with mental health as well as with work engagement. Mental health improved when psychological detachment increased from a low to higher levels but did not benefit any further from extremely high levels of psychological detachment. Work engagement showed the highest level at an intermediate level of detachment (inverted U-shaped pattern). Although high psychological detachment may enhance employee mental health, moderate levels of psychological detachment are most beneficial for his or her work engagement.

Psychological detachment from work during non-work time: linear or curvilinear relations with mental health and work engagement?

PubMed Central

SHIMAZU, Akihito; MATSUDAIRA, Ko; DE JONGE, Jan; TOSAKA, Naoya; WATANABE, Kazuhiro; TAKAHASHI, Masaya

2016-01-01

This study examined whether a higher level of psychological detachment during non-work time is associated with better employee mental health (Hypothesis 1), and examined whether psychological detachment has a curvilinear relation (inverted U-shaped pattern) with work engagement (Hypothesis 2). A large cross-sectional Internet survey was conducted among registered monitors of an Internet survey company in Japan. The questionnaire included scales for psychological detachment, employee mental health, and work engagement as well as for job characteristics and demographic variables as potential confounders. The hypothesized model was tested with moderated structural equation modeling techniques among 2,234 respondents working in the tertiary industries with regular employment. Results showed that psychological detachment had curvilinear relations with mental health as well as with work engagement. Mental health improved when psychological detachment increased from a low to higher levels but did not benefit any further from extremely high levels of psychological detachment. Work engagement showed the highest level at an intermediate level of detachment (inverted U-shaped pattern). Although high psychological detachment may enhance employee mental health, moderate levels of psychological detachment are most beneficial for his or her work engagement. PMID:26829972

Critical screening in the one- and two-electron Yukawa atoms

NASA Astrophysics Data System (ADS)

Montgomery, H. E.; Sen, K. D.; Katriel, Jacob

2018-02-01

The one- and two-electron Yukawa atoms, also referred to as the Debye-Hückel or screened Coulomb atoms, have been topics of considerable interest both for intrinsic reasons and because of their relevance to terrestrial and astrophysical plasmas. At sufficiently high screening the one-electron Yukawa atom ceases to be bound. Some calculations appeared to suggest that as the screening increases in the ground state of the two-electron Yukawa atom (in which both the one-particle attraction and the interparticle repulsion are screened) the two electrons are detached simultaneously, at the same screening constant at which the one-electron atom becomes unbound. Our results rule this scenario out, offering an alternative that is not less interesting. In particular, it is found that for Z <1 a mild amount of screening actually increases the binding energy of the second electron. At the nuclear charge Zc≈0.911028 ... , at which the bare Coulomb two-electron atom becomes unbound, and even over a range of lower nuclear charges, an appropriate amount of screening gives rise to a bound two-electron system.

Ultra-thin flexible GaAs photovoltaics in vertical forms printed on metal surfaces without interlayer adhesives

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

Kim, Juho; Song, Kwangsun; Kim, Namyun

2016-06-20

Wearable flexible electronics often require sustainable power sources that are also mechanically flexible to survive the extreme bending that accompanies their general use. In general, thinner microelectronic devices are under less strain when bent. This paper describes strategies to realize ultra-thin GaAs photovoltaics through the interlayer adhesiveless transfer-printing of vertical-type devices onto metal surfaces. The vertical-type GaAs photovoltaic devices recycle reflected photons by means of bottom electrodes. Systematic studies with four different types of solar microcells indicate that the vertical-type solar microcells, at only a quarter of the thickness of similarly designed lateral-type cells, generate a level of electric powermore » similar to that of thicker cells. The experimental results along with the theoretical analysis conducted here show that the ultra-thin vertical-type solar microcells are durable under extreme bending and thus suitable for use in the manufacturing of wearable flexible electronics.« less

Gas separation and bubble behavior at a woven screen

NASA Astrophysics Data System (ADS)

Conrath, Michael; Dreyer, Michael E.

Gas-liquid two phase flows are widespread and in many applications the separation of both phases is necessary. Chemical reactors, water treatment devices or gas-free delivery of liquids like propellant are only some of them. We study the performance of a woven metal screen in respect to its phase separation behavior under static and dynamic conditions. Beside hydraulic screen resistance and static bubble point, our study also comprises the bubble detachment from the screen upon gas breakthrough. Since a woven screen is essentially an array of identical pores, analogies to bubble detachment from a needle can be established. While the bubble point poses an upper limit for pressurized gas at a wetted screen to preclude gas breakthrough, the necessary pressure for growing bubbles to detach from the screen pores a lower limit when breakthrough is already in progress. Based on that inside, the dynamic bubble point effects were constituted that relate to a trapped bubble at such a screen in liquid flow. A trapped is caused to break through the screen by the flow-induced pressure drop across it. Our model includes axially symmetric bubble shapes, degree of coverage of the screen and bubble pressurization due to hydraulic losses in the rest of the circuit. We have built an experiment that consists of a Dutch Twilled woven screen made of stainless steel in a vertical acrylic glass tube. The liquid is silicon oil SF0.65. The screen is suspended perpendicular to the liquid flow which is forced through it at variable flow rate. Controlled injection of air from a needle allows us to examine the ability of the screen to separate gas and liquid along the former mentioned effects. We present experimental data on static bubble point and detachment pressure for breakthrough at different gas supply rates that suggest a useful criterion for reliable static bubble point measurements. Results for the dynamic bubble point are presented that include i) screen pressure drop for different trapped bubble volumes, liquid flow rates and flow-induced compression, ii) typical breakthrough of a trapped bubble at rising liquid flow rate and iii) steady gas supply in steady liquid flow. It shows that our model can explain the experimental observations. One of the interesting findings for the dynamic bubble point is that hydraulic losses in the rest of the circuit will shift the breakthrough of gas to higher liquid flow rates.

Copper vertical micro dendrite fin arrays and their superior boiling heat transfer capability

NASA Astrophysics Data System (ADS)

Wang, Ya-Qiao; Lyu, Shu-Shen; Luo, Jia-Li; Luo, Zhi-Yong; Fu, Yuan-Xiang; Heng, Yi; Zhang, Jian-Hui; Mo, Dong-Chuan

2017-11-01

Micro pin fin arrays have been widely used in electronic cooling, micro reactors, catalyst support, and wettability modification and so on, and a facile way to produce better micro pin fin arrays is demanded. Herein, a simple electrochemical method has been developed to fabricate copper vertical micro dendrite fin arrays (Cu-VMDFA) with controllable shapes, number density and height. High copper sulphate concentration is one key point to make the dendrite stand vertically. Besides, the applied current should rise at an appropriate rate to ensure the copper dendrite can grow vertically on its own. The Cu-VMDFA can significantly enhance the heat transfer coefficient by approximately twice compared to the plain copper surface. The Cu-VMDFA may be widely used in boiling heat transfer areas such as nuclear power plants, electronic cooling, heat exchangers, and so on.

Photoelectron spectroscopy of the bis(dithiolene) anions [M(mnt)2]n- (M = Fe - Zn; n = 1, 2): changes in electronic structure with variation of metal center and with oxidation.

PubMed

Waters, Tom; Wang, Xue-Bin; Woo, Hin-Koon; Wang, Lai-Sheng

2006-07-24

A detailed understanding of the electronic structures of transition metal bis(dithiolene) centers is important in the context of their interesting redox, magnetic, and optical properties. The electronic structures of the series [M(mnt)2]n- (M = Fe - Zn; mnt = 1,2-S2C2(CN)2; n = 1, 2) were examined by a combination of photodetachment photoelectron spectroscopy and density functional theory calculations, providing insights into changes in electronic structure with variation of the metal center and with oxidation. Significant changes were observed for the dianions [M(mnt)2]2- due to stabilization of the metal 3d levels from Fe to Zn and the transition from square-planar to tetrahedral coordination about the metal center (Fe-Ni, D(2h) --> Cu D2 --> Zn, D(2d). Changes with oxidation from [M(mnt)2]2- to [M(mnt)2]1- were largely dependent on the nature of the redox-active orbital in the couple [M(mnt)2](2-/1-). In particular, the first detachment feature for [Fe(mnt)2]2- originated from a metal-based orbital (Fe(II) --> Fe(III)) while that for [Fe(mnt)2]1- originated from a ligand-based orbital, a consequence of stabilization of Fe 3d levels in the latter. In contrast, the first detachment feature for both of [Ni(mnt)2]2- and [Ni(mnt)2]1- originated from the same ligand-based orbital in both cases, a result of occupied Ni 3d levels being stabilized relative those of Fe 3d and occurring below the highest energy occupied ligand-based orbital for both of [Ni(mnt)2]2- and [Ni(mnt)2]1- . The combined data illustrate the subtle interplay between metal- and ligand-based redox chemistry in these species and demonstrate changes in their electronic structures with variation of metal center, oxidation, and coordination geometry.

Happy, healthy, and productive: the role of detachment from work during nonwork time.

PubMed

Fritz, Charlotte; Yankelevich, Maya; Zarubin, Anna; Barger, Patricia

2010-09-01

Mentally distancing oneself from work during nonwork time can help restore resources lost because of work demands. In this study, we examined possible outcomes of such psychological detachment from work, specifically well-being and job performance. Although employees may need to mentally detach from work to restore their well-being, high levels of detachment may require a longer time to get back into "working mode," which may be negatively associated with job performance. Our results indicate that higher levels of self-reported detachment were associated with higher levels of significant other-reported life satisfaction as well as lower levels of emotional exhaustion. In addition, we found curvilinear relationships between psychological detachment and coworker reported job performance (task performance and proactive behavior). Thus, although high psychological detachment may enhance employee well-being, it seems that medium levels of detachment are most beneficial for job performance. Copyright 2010 APA, all rights reserved

Theoretical Study on the Photoelectron Spectra of Ln(COT)2-: Lanthanide Dependence of the Metal-Ligand Interaction.

PubMed

Nakajo, Erika; Masuda, Tomohide; Yabushita, Satoshi

2016-12-08

We have performed a theoretical analysis of the recently reported photoelectron (PE) spectra of the series of sandwich complex anions Ln(COT) 2 - (Ln = La-Lu, COT = 1,3,5,7-cyclooctatetraene), focusing on the Ln dependence of the vertical detachment energies. For most Ln, the π molecular orbitals, largely localized on the COT ligands, have the energy order of e 1g < e 1u < e 2g < e 2u as in the actinide analogues, reflecting the substantial orbital interaction with the Ln 5d and 5p orbitals. Thus, it would be expected that the lanthanide contraction would increase the orbital interaction so that the overlaps between the COT π and Ln atomic orbitals tend to increase across the series. However, the PE spectra and theoretical calculations were not consistent with this expectation, and the details have been clarified in this study. Furthermore, the energy level splitting patterns of the anion and neutral complexes have been studied by multireference ab initio methods, and the X peak splittings observed in the PE spectra only for the middle-range Ln complexes were found to be due to the specific interaction between the Ln 4f and ligand π orbitals of the neutral complexes in e 2u symmetry. Because the magnitude of this 4f-ligand interaction depends critically on the final state 4f electron configuration and the spin state, a significant Ln dependence in the PE spectra is explained.

Assessment of Quantum Mechanical Methods for Copper and Iron Complexes by Photoelectron Spectroscopy.

PubMed

Niu, Shuqiang; Huang, Dao-Ling; Dau, Phuong D; Liu, Hong-Tao; Wang, Lai-Sheng; Ichiye, Toshiko

2014-03-11

Broken-symmetry density functional theory (BS-DFT) calculations are assessed for redox energetics [Cu(SCH 3 ) 2 ] 1-/0 , [Cu(NCS) 2 ] 1-/0 , [FeCl 4 ] 1-/0 , and [Fe(SCH 3 ) 4 ] 1-/0 against vertical detachment energies (VDE) from valence photoelectron spectroscopy (PES), as a prelude to studies of metalloprotein analogs. The M06 and B3LYP hybrid functionals give VDE that agree with the PES VDE for the Fe complexes, but both underestimate it by ∼400 meV for the Cu complexes; other hybrid functionals give VDEs that are an increasing function of the amount of Hartree-Fock (HF) exchange and so cannot show good agreement for both Cu and Fe complexes. Range-separated (RS) functionals appear to give a better distribution of HF exchange since the negative HOMO energy is approximately equal to the VDEs but also give VDEs dependent on the amount of HF exchange, sometimes leading to ground states with incorrect electron configurations; the LRC- ω PBEh functional reduced to 10% HF exchange at short-range give somewhat better values for both, although still ∼150 meV too low for the Cu complexes and ∼50 meV too high for the Fe complexes. Overall, the results indicate that while HF exchange compensates for self-interaction error in DFT calculations of both Cu and Fe complexes, too much may lead to more sensitivity to nondynamical correlation in the spin-polarized Fe complexes.

Assessment of Quantum Mechanical Methods for Copper and Iron Complexes by Photoelectron Spectroscopy

PubMed Central

2015-01-01

Broken-symmetry density functional theory (BS-DFT) calculations are assessed for redox energetics [Cu(SCH3)2]1–/0, [Cu(NCS)2]1–/0, [FeCl4]1–/0, and [Fe(SCH3)4]1–/0 against vertical detachment energies (VDE) from valence photoelectron spectroscopy (PES), as a prelude to studies of metalloprotein analogs. The M06 and B3LYP hybrid functionals give VDE that agree with the PES VDE for the Fe complexes, but both underestimate it by ∼400 meV for the Cu complexes; other hybrid functionals give VDEs that are an increasing function of the amount of Hartree–Fock (HF) exchange and so cannot show good agreement for both Cu and Fe complexes. Range-separated (RS) functionals appear to give a better distribution of HF exchange since the negative HOMO energy is approximately equal to the VDEs but also give VDEs dependent on the amount of HF exchange, sometimes leading to ground states with incorrect electron configurations; the LRC-ωPBEh functional reduced to 10% HF exchange at short-range give somewhat better values for both, although still ∼150 meV too low for the Cu complexes and ∼50 meV too high for the Fe complexes. Overall, the results indicate that while HF exchange compensates for self-interaction error in DFT calculations of both Cu and Fe complexes, too much may lead to more sensitivity to nondynamical correlation in the spin-polarized Fe complexes. PMID:24803858

Detachment of particulate iron sulfide during shale-water interaction

NASA Astrophysics Data System (ADS)

Emmanuel, S.; Kreisserman, Y.

2017-12-01

Hydraulic fracturing, a commonly used technique to extract oil and gas from shales, is controversial in part because of the threat it poses to water resources. The technique involves the injection into the subsurface of large amounts of fluid, which can become contaminated by fluid-rock interaction. The dissolution of pyrite is thought to be a primary pathway for the contamination of fracturing fluids with toxic elements, such as arsenic and lead. In this study, we use direct observations with atomic force microscopy to show that the dissolution of carbonate minerals in Eagle Ford shale leads to the physical detachment of embedded pyrite grains. To simulate the way fluid interacts with a fractured shale surface, we also reacted rock samples in a flow-through cell, and used environmental scanning electron microscopy to compare the surfaces before and after interaction with water. Crucially, our results show that the flux of particulate iron sulfide into the fluid may be orders of magnitude higher than the flux of pyrite from chemical dissolution. This result suggests that mechanical detachment of pyrite grains could be the dominant mode by which arsenic and other inorganic elements are mobilized in the subsurface. Thus, during hydraulic fracturing operations and in groundwater systems containing pyrite, the transport of many toxic species may be controlled by the transport of colloidal iron sulfide particles.

Multipurpose Vacuum Induction Processing System

NASA Astrophysics Data System (ADS)

Govindaraju, M.; Kulkarni, Deepak; Balasubramanian, K.

2012-11-01

Multipurpose vacuum processing systems are cost effective; occupy less space, multiple functional under one roof and user friendly. A multipurpose vacuum induction system was designed, fabricated and installed in a record time of 6 months time at NFTDC Hyderabad. It was designed to function as a) vacuum induction melting/refining of oxygen free electronic copper/pure metals, b) vacuum induction melting furnace for ferrous materials c) vacuum induction melting for non ferrous materials d) large vacuum heat treatment chamber by resistance heating (by detachable coil and hot zone) e) bottom discharge vacuum induction melting system for non ferrous materials f) Induction heat treatment system and g) directional solidification /investment casting. It contains provision for future capacity addition. The attachments require to manufacture multiple shaped castings and continuous rod casting can be added whenever need arises. Present capacity is decided on the requirement for 10years of development path; presently it has 1.2 ton liquid copper handling capacity. It is equipped with provision for capacity addition up to 2 ton liquid copper handling capacity in future. Provision is made to carry out the capacity addition in easy steps quickly. For easy operational maintenance and troubleshooting, design was made in easily detachable sections. High vacuum system is also is detachable, independent and easily movable which is first of its kind in the country. Detailed design parameters, advantages and development history are presented in this paper.

Detachment of secondary dendrite arm in a directionally solidified Sn-Ni peritectic alloy under deceleration growth condition

PubMed Central

Peng, Peng; Li, Xinzhong; Li, Jiangong; Su, Yanqing; Guo, Jingjie; Fu, Hengzhi

2016-01-01

In order to better understand the detachment mechanism of secondary dendrite arm during peritectic solidification, the detachment of secondary dendrite arm from the primary dendrite arms in directionally solidified Sn-36at.%Ni peritectic alloys is investigated at different deceleration rates. Extensive detachment of secondary dendrite arms from primary stem is observed below peritectic reaction temperature TP. And an analytical model is established to characterize the detachment process in terms of the secondary dendrite arm spacing λ2, the root radius of detached arms and the specific surface area (SV) of dendrites. It is found that the detachment mechanism is caused by not only curvature difference between the tips and roots of secondary branches, but also that between the thicker secondary branches and the thinner ones. Besides, this detachment process is significantly accelerated by the temperature gradient zone melting (TGZM) effect during peritectic solidification. It is demonstrated that the reaction constant (f) which is used to characterize the kinetics of peritectic reaction is crucial for the determination of the detachment process. The value of f not only changes with growth rate but also with solidification time at a given deceleration rate. In conclusion, these findings help the better understanding of the detachment mechanism. PMID:27270334

Fabrication of graphene/titanium carbide nanorod arrays for chemical sensor application.

PubMed

Fu, Chong; Li, Mingji; Li, Hongji; Li, Cuiping; Qu, Changqing; Yang, Baohe

2017-03-01

Vertically stacked graphene nanosheet/titanium carbide nanorod array/titanium (graphene/TiC nanorod array) wires were fabricated using a direct current arc plasma jet chemical vapor deposition (DC arc plasma jet CVD) method. The graphene/TiC nanorod arrays were characterized by scanning electron microscopy, transmission electron microscopy, Raman spectroscopy, X-ray photoelectron spectroscopy, and X-ray diffraction spectroscopy. The TiO 2 nanotube array was reduced to the TiC nanorod array, and using those TiC nanorods as nucleation sites, the vertical graphene layer was formed on the TiC nanorod surface. The multi-target response mechanisms of the graphene/TiC nanorod array were investigated for ascorbic acid (AA), dopamine (DA), uric acid (UA), and hydrochlorothiazide (HCTZ). The vertically stacked graphene sheets facilitated the electron transfer and reactant transport with a unique porous surface, high surface area, and high electron transport network of CVD graphene sheets. The TiC nanorod array facilitated the electron transfer and firmly held the graphene layer. Thus, the graphene/TiC nanorod arrays could simultaneously respond to trace biomarkers and antihypertensive drugs. Copyright © 2016 Elsevier B.V. All rights reserved.

Highly excited electronic image states of metallic nanorings

PubMed Central

Fey, Christian; Jabusch, Henrik; Knörzer, Johannes; Schmelcher, Peter

2017-01-01

We study electronic image states around a metallic nanoring and show that the interplay between the attractive polarization force and a repulsive centrifugal force gives rise to Rydberg-like image states trapped several nanometers away from the surface. The nanoring is modeled as a perfectly conducting isolated torus whose classical electrostatic image potential is derived analytically. The image states are computed via a two-dimensional finite-difference scheme as solutions of the effective Schrödinger equation describing the outer electron subject to this image potential. These findings demonstrate not only the existence of detached image states around nanorings but allow us also to provide general criteria on the ring geometry, i.e., the aspect ratio of the torus, that need to be fulfilled in order to support such states. PMID:28527466

Integration of photoactive and electroactive components with vertical cavity surface emitting lasers

DOEpatents

Bryan, R.P.; Esherick, P.; Jewell, J.L.; Lear, K.L.; Olbright, G.R.

1997-04-29

A monolithically integrated optoelectronic device is provided which integrates a vertical cavity surface emitting laser and either a photosensitive or an electrosensitive device either as input or output to the vertical cavity surface emitting laser either in parallel or series connection. Both vertical and side-by-side arrangements are disclosed, and optical and electronic feedback means are provided. Arrays of these devices can be configured to enable optical computing and neural network applications. 9 figs.

Integration of photoactive and electroactive components with vertical cavity surface emitting lasers

DOEpatents

Bryan, Robert P.; Esherick, Peter; Jewell, Jack L.; Lear, Kevin L.; Olbright, Gregory R.

1997-01-01

A monolithically integrated optoelectronic device is provided which integrates a vertical cavity surface emitting laser and either a photosensitive or an electrosensitive device either as input or output to the vertical cavity surface emitting laser either in parallel or series connection. Both vertical and side-by-side arrangements are disclosed, and optical and electronic feedback means are provided. Arrays of these devices can be configured to enable optical computing and neural network applications.

Divertor detachment

NASA Astrophysics Data System (ADS)

Krasheninnikov, Sergei

2015-11-01

The heat exhaust is one of the main conceptual issues of magnetic fusion reactor. In a standard operational regime the large heat flux onto divertor target reaches unacceptable level in any foreseeable reactor design. However, about two decades ago so-called ``detached divertor'' regimes were found. They are characterized by reduced power and plasma flux on divertor targets and look as a promising solution for heat exhaust in future reactors. In particular, it is envisioned that ITER will operate in a partly detached divertor regime. However, even though divertor detachment was studied extensively for two decades, still there are some issues requiring a new look. Among them is the compatibility of detached divertor regime with a good core confinement. For example, ELMy H-mode exhibits a very good core confinement, but large ELMs can ``burn through'' detached divertor and release large amounts of energy on the targets. In addition, detached divertor regimes can be subject to thermal instabilities resulting in the MARFE formation, which, potentially, can cause disruption of the discharge. Finally, often inner and outer divertors detach at different plasma conditions, which can lead to core confinement degradation. Here we discuss basic physics of divertor detachment including different mechanisms of power and momentum loss (ionization, impurity and hydrogen radiation loss, ion-neutral collisions, recombination, and their synergistic effects) and evaluate the roles of different plasma processes in the reduction of the plasma flux; detachment stability; and an impact of ELMs on detachment. We also evaluate an impact of different magnetic and divertor geometries on detachment onset, stability, in- out- asymmetry, and tolerance to the ELMs. Supported by the U.S. Department of Energy Office of Science, Office of Fusion Energy Sciences under Award Number DE-DE-FG02-04ER54739 at UCSD.

Evaluation of hyaloid-retinal relationship during triamcinolone-assisted vitrectomy for primary rhegmatogenous retinal detachment.

PubMed

Sundar, Dheepak; Takkar, Brijesh; Venkatesh, Pradeep; Chawla, Rohan; Temkar, Shreyas; Azad, Shorya Vardhan; Vohra, Rajpal

2018-03-01

To determine hyaloid-retinal relationship in primary rhegmatogenous retinal detachment during vitreous surgery. This is a prospective, interventional study of patients (n = 72) undergoing triamcinolone-assisted 25G vitreous surgery for primary rhegmatogenous retinal detachment. Hyaloid-retinal relationship was noted intraoperatively to identify regions and patterns of firm attachment and was classified into subgroups. Analysis was done to determine association between hyaloid-retinal relationship patterns and preoperative findings: posterior vitreous detachment, proliferative vitreoretinopathy, type of retinal tear, the presence of peripheral degenerations, and postoperative outcomes. Three patterns of hyaloid-retinal relationship were identified: type1 (complete absence of posterior vitreous detachment (21%)), type 2 (incomplete posterior vitreous detachment (47%)) and type 3 (complete posterior vitreous detachment (32%)). Posterior vitreous detachment in some form was present in 84% of the cases with retinal tears as the causative break but none of the cases with retinal holes (p < 0.001). None of the cases with vitreoretinal degeneration had complete posterior vitreous detachment (p = 0.001). 69% of proliferative vitreoretinopathy-C cases had type 1 hyaloid-retinal relationship as compared to 11% cases with no proliferative vitreoretinopathy (p < 0.001). Proliferative vitreoretinopathy-related anatomical failure was seen in 7.5%, and 80% of these eyes with recurrent RD had type 1 hyaloid-retinal relationship (p<0.001). Nearly half the patients diagnosed as complete posterior vitreous detachment preoperatively were found to have incomplete posterior vitreous detachment intraoperatively. Majority of the cases with rhegmatogenous retinal detachment have some form of strong vitreoretinal adhesion. Hyaloid-retinal relationship varies with types of retinal breaks, retinal degeneration, and proliferative vitreoretinopathy. Intraoperative hyaloid-retinal relationship is frequently different from that assessed before surgery and the proposed classification may improve surgical decision making and prognostication.

Theoretical investigation of the electronic structure and quantum transport in the graphene-C(111) diamond surface system.

PubMed

Selli, Daniele; Baburin, Igor; Leoni, Stefano; Zhu, Zhen; Tománek, David; Seifert, Gotthard

2013-10-30

We investigate the interaction of a graphene monolayer with the C(111) diamond surface using ab initio density functional theory. To accommodate the lattice mismatch between graphene and diamond, the overlayer deforms into a wavy structure that binds strongly to the diamond substrate. The detached ridges of the wavy graphene overlayer behave electronically as free-standing polyacetylene chains with delocalized π electrons, separated by regions containing only sp(3) carbon atoms covalently bonded to the (111) diamond surface. We performed quantum transport calculations for different geometries of the system to study how the buckling of the graphene layer and the associated bonding to the diamond substrate affect the transport properties. The system displays high carrier mobility along the ridges and a wide transport gap in the direction normal to the ridges. These intriguing, strongly anisotropic transport properties qualify the hybrid graphene-diamond system as a viable candidate for electronic nanodevices.

The threshold laws for electron-atom and positron-atom impact ionization

NASA Technical Reports Server (NTRS)

Temkin, A.

1983-01-01

The Coulomb-dipole theory is employed to derive a threshold law for the lowest energy needed for the separation of three particles from one another. The study focuses on an electron impinging on a neutral atom, and the dipole is formed between an inner electron and the nucleus. The analytical dependence of the transition matrix element on energy is reduced to lowest order to obtain the threshold law, with the inner electron providing a shield for the nucleus. Experimental results using the LAMPF accelerator to produce a high energy beam of H- ions, which are then exposed to an optical laser beam to detach the negative H- ion, are discussed. The threshold level is found to be confined to the region defined by the upper bound of the inverse square of the Coulomb-dipole region. Difficulties in exact experimental confirmation of the threshold are considered.

Detached-Eddy Simulations of Attached and Detached Boundary Layers

NASA Astrophysics Data System (ADS)

Caruelle, B.; Ducros, F.

2003-12-01

This article presents Detached-Eddy Simulations (DESs) of attached and detached turbulent boundary layers. This hybrid Reynolds Averaged Navier-Stokes (RANS) / Large Eddy Simulation (LES) model goes continuously from RANS to LES according to the mesh definition. We propose a parametric study of the model over two "academic" configurations, in order to get information on the influence of the mesh to correctly treat complex flow with attached and detached boundary layers.

6. Detail, vertical guides adjacent to east portal of Tunnel ...

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

6. Detail, vertical guides adjacent to east portal of Tunnel 28, view to southwest, 135mm lens with electronic flash fill. - Central Pacific Transcontinental Railroad, Tunnel No. 28, Milepost 134.75, Applegate, Placer County, CA

Ultra-fast microwave-assisted hydrothermal synthesis of long vertically aligned ZnO nanowires for dye-sensitized solar cell application.

PubMed

Mahpeykar, S M; Koohsorkhi, J; Ghafoori-Fard, H

2012-04-27

Long vertically aligned ZnO nanowire arrays were synthesized using an ultra-fast microwave-assisted hydrothermal process. Using this method, we were able to grow ZnO nanowire arrays at an average growth rate as high as 200 nm min(-1) for maximum microwave power level. This method does not suffer from the growth stoppage problem at long growth times that, according to our investigations, a normal microwave-assisted hydrothermal method suffers from. Longitudinal growth of the nanowire arrays was investigated as a function of microwave power level and growth time using cross-sectional FESEM images of the grown arrays. Effect of seed layer on the alignment of nanowires was also studied. X-ray diffraction analysis confirmed c-axis orientation and single-phase wurtzite structure of the nanowires. J-V curves of the fabricated ZnO nanowire-based mercurochrome-sensitized solar cells indicated that the short-circuit current density is increased with increasing the length of the nanowire array. According to the UV-vis spectra of the dyes detached from the cells, these increments were mainly attributed to the enlarged internal surface area and therefore dye loading enhancement in the lengthened nanowire arrays.

Vertically stacked multi-heterostructures of layered materials for logic transistors and complementary inverters

PubMed Central

Yu, Woo Jong; Li, Zheng; Zhou, Hailong; Chen, Yu; Wang, Yang; Huang, Yu; Duan, Xiangfeng

2014-01-01

The layered materials such as graphene have attracted considerable interest for future electronics. Here we report the vertical integration of multi-heterostructures of layered materials to enable high current density vertical field-effect transistors (VFETs). An n-channel VFET is created by sandwiching few-layer molybdenum disulfide (MoS2) as the semiconducting channel between a monolayer graphene and a metal thin film. The VFETs exhibit a room temperature on-off ratio >103, while at same time deliver a high current density up to 5,000 A/cm2, sufficient for high performance logic applications. This study offers a general strategy for the vertical integration of various layered materials to obtain both p- and n-channel transistors for complementary logic functions. A complementary inverter with larger than unit voltage gain is demonstrated by vertically stacking the layered materials of graphene, Bi2Sr2Co2O8 (p-channel), graphene, MoS2 (n-channel), and metal thin film in sequence. The ability to simultaneously achieve high on-off ratio, high current density, and logic integration in the vertically stacked multi-heterostructures can open up a new dimension for future electronics to enable three-dimensional integration. PMID:23241535

Modeling of Detached Solidification

NASA Technical Reports Server (NTRS)

Regel, Liya L.; Wilcox, William R.; Popov, Dmitri

1997-01-01

Our long term goal is to develop techniques to achieve detached solidification reliably and reproducibly, in order to produce crystals with fewer defects. To achieve this goal it is necessary to understand thoroughly the physics of detached solidification. It was the primary objective of the current project to make progress toward this complete understanding. 'Me products of this grant are attached. These include 4 papers and a preliminary survey of the observations of detached solidification in space. We have successfully modeled steady state detached solidification, examined the stability of detachment, and determined the influence of buoyancy-driven convection under different conditions. Directional solidification in microgravity has often led to ingots that grew with little or no contact with the ampoule wall. When this occurred, crystallographic perfection was usually greatly improved -- often by several orders of magnitude. Indeed, under the Soviet microgravity program the major objective was to achieve detached solidification with its resulting improvement in perfection and properties. Unfortunately, until recently the true mechanisms underlying detached solidification were unknown. As a consequence, flight experiments yielded erratic results. Within the past three years, we have developed a new theoretical model that explains many of the flight results. This model gives rise to predictions of the conditions required to yield detached solidification.

Triphasic 2D Materials by Vertically Stacking Laterally Heterostructured 2H-/1T'-MoS 2 on Graphene for Enhanced Photoresponse

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

Cui, Weili; Xu, Shanshan S.; Yan, Bo

Recently the applications of two-dimensional (2D) materials have been broadened by engineering their mechanical, electronic, and optical properties through either lateral or vertical hybridization. Along with this line, we report the successful design and fabrication of a novel triphasic 2D material by vertically stacking lateral 2H-/1T'-molybdenum disulfide (MoS 2) heterostructures on graphene with the assistance of supercritical carbon dioxide. This triphasic structure is experimentally shown to significantly enhance the photocurrent densities for hydrogen evolution reactions. First-principles theoretical analyses reveal that the improved photoresponse should be ascribed to the beneficial band alignments of the triphasic heterostructure. More specifically, electrons can efficientlymore » hop to the 1T'-MoS 2 phase via the highly conductive graphene layer as a result of their strong vertical interfacial electronic coupling. Subsequently, the electrons acquired on the 1T'-MoS 2 phase are exploited to fill the photoholes on the photo-excited 2H-MoS 2 phase through the lateral heterojunction structure, thereby suppressing the recombination process of the photo-induced charge carriers on the 2H-MoS 2 phase. This novel triphasic concept promises to open a new avenue to widen the molecular design of 2D hybrid materials for photonics-based energy conversion applications.« less

Triphasic 2D Materials by Vertically Stacking Laterally Heterostructured 2H-/1T'-MoS 2 on Graphene for Enhanced Photoresponse

DOE PAGES

Cui, Weili; Xu, Shanshan S.; Yan, Bo; ...

2017-05-11

Recently the applications of two-dimensional (2D) materials have been broadened by engineering their mechanical, electronic, and optical properties through either lateral or vertical hybridization. Along with this line, we report the successful design and fabrication of a novel triphasic 2D material by vertically stacking lateral 2H-/1T'-molybdenum disulfide (MoS 2) heterostructures on graphene with the assistance of supercritical carbon dioxide. This triphasic structure is experimentally shown to significantly enhance the photocurrent densities for hydrogen evolution reactions. First-principles theoretical analyses reveal that the improved photoresponse should be ascribed to the beneficial band alignments of the triphasic heterostructure. More specifically, electrons can efficientlymore » hop to the 1T'-MoS 2 phase via the highly conductive graphene layer as a result of their strong vertical interfacial electronic coupling. Subsequently, the electrons acquired on the 1T'-MoS 2 phase are exploited to fill the photoholes on the photo-excited 2H-MoS 2 phase through the lateral heterojunction structure, thereby suppressing the recombination process of the photo-induced charge carriers on the 2H-MoS 2 phase. This novel triphasic concept promises to open a new avenue to widen the molecular design of 2D hybrid materials for photonics-based energy conversion applications.« less

Characteristics of Organic-Metal Interaction: A Perspective from Bonding Distance to Orbital Delocalization

NASA Astrophysics Data System (ADS)

Kera, Satoshi; Hosokai, Takuya; Duhm, Steffen

2018-06-01

Understanding the mechanisms of energy-level alignment and charge transfer at the interface is one of the key issues in realizing organic electronics. However, the relation between the interface structure and the electronic structure is still not resolved in sufficient detail. An important character of materials used in organic electronics is the electronic localization of organic molecules at interfaces. To elucidate the impact of the molecular orbital distribution on the electronic structure, detailed structural information is required, particularly the vertical bonding distance at the interface, which is a signature of the interaction strength. We describe the recent progress in experimental studies on the impact of the molecule-metal interaction on the electronic structure of organic-metal interfaces by using various photoelectron spectroscopies, and review the results, focusing on the X-ray standing wave technique, to demonstrate the evaluation of the vertical bonding distance.

Photo-detachment of negative ions in Ar-CO2 dc discharge employing Langmuir probe

NASA Astrophysics Data System (ADS)

Rodríguez, Jannet; Yousif, Farook Bashir; Fuentes, Beatriz E.; Vázquez, Federico; Rivera, Marco; López-Patiño, J.; Figueroa, Aldo; Martínez, Horacio

2018-05-01

The electronegativity of the A r - C O 2 gas mixture was investigated, and the total relative negative oxygen ion density O2- + O- in the bulk of a dc discharge has been determined employing Langmuir probe assisted laser photo-detachment. The relative electron density and absolute temperature were obtained for the mixture at discharge powers between 200 and 3000 mW and pressures between 0.2 and 0.6 mbar, employing the collisional radiative model for several Ar gas mixtures. The absolute metastable number density for 1s3 and 1s5 levels was measured, and both showed an increasing trend as a function of pressure and power. The absolute number density of the 1s5 level was found to be higher than that of the 1s3 level. Electronegativity was found to decrease as a function of power and as a function of the increasing Ar percentage in the gas mixture.

Evidence of significant covalent bonding in Au(CN)(2)(-).

PubMed

Wang, Xue-Bin; Wang, Yi-Lei; Yang, Jie; Xing, Xiao-Peng; Li, Jun; Wang, Lai-Sheng

2009-11-18

The Au(CN)(2)(-) ion is the most stable Au compound known for centuries, yet a detailed understanding of its chemical bonding is still lacking. Here we report direct experimental evidence of significant covalent bonding character in the Au-C bonds in Au(CN)(2)(-) using photoelectron spectroscopy and comparisons with its lighter congeners, Ag(CN)(2)(-) and Cu(CN)(2)(-). Vibrational progressions in the Au-C stretching mode were observed for all detachment transitions for Au(CN)(2)(-), in contrast to the atomic-like transitions for Cu(CN)(2)(-), revealing the Au-C covalent bonding character. In addition, rich electronic structural information was obtained for Au(CN)(2)(-) by employing 118 nm detachment photons. Density functional theory and high-level ab initio calculations were carried out to understand the photoelectron spectra and obtain insight into the nature of the chemical bonding in the M(CN)(2)(-) complexes. Significant covalent character in the Au-C bonding due to the strong relativistic effects was revealed in Au(CN)(2)(-), consistent with its high stability.

Lis1 acts as a "clutch" between the ATPase and microtubule-binding domains of the dynein motor.

PubMed

Huang, Julie; Roberts, Anthony J; Leschziner, Andres E; Reck-Peterson, Samara L

2012-08-31

The lissencephaly protein Lis1 has been reported to regulate the mechanical behavior of cytoplasmic dynein, the primary minus-end-directed microtubule motor. However, the regulatory mechanism remains poorly understood. Here, we address this issue using purified proteins from Saccharomyces cerevisiae and a combination of techniques, including single-molecule imaging and single-particle electron microscopy. We show that rather than binding to the main ATPase site within dynein's AAA+ ring or its microtubule-binding stalk directly, Lis1 engages the interface between these elements. Lis1 causes individual dynein motors to remain attached to microtubules for extended periods, even during cycles of ATP hydrolysis that would canonically induce detachment. Thus, Lis1 operates like a "clutch" that prevents dynein's ATPase domain from transmitting a detachment signal to its track-binding domain. We discuss how these findings provide a conserved mechanism for dynein functions in living cells that require prolonged microtubule attachments. Copyright © 2012 Elsevier Inc. All rights reserved.

Lis1 Acts as a “Clutch” between the ATPase and Microtubule-Binding Domains of the Dynein Motor

PubMed Central

Huang, Julie; Roberts, Anthony J.; Leschziner, Andres E.; Reck-Peterson, Samara L.

2012-01-01

Summary The lissencephaly protein Lis1 has been reported to regulate the mechanical behavior of cytoplasmic dynein, the primary minus-end-directed microtubule motor. However, the regulatory mechanism remains poorly understood. Here, we address this issue using purified proteins from Saccharomyces cerevisiae and a combination of techniques, including single-molecule imaging and single-particle electron microscopy. We show that rather than binding to the main ATPase site within dynein's AAA+ ring or its microtubule-binding stalk directly, Lis1 engages the interface between these elements. Lis1 causes individual dynein motors to remain attached to microtubules for extended periods, even during cycles of ATP hydrolysis that would canonically induce detachment. Thus, Lis1 operates like a “clutch” that prevents dynein's ATPase domain from transmitting a detachment signal to its track-binding domain. We discuss how these findings provide a conserved mechanism for dynein functions in living cells that require prolonged microtubule attachments. PMID:22939623

Dynamics of the formation of an aureole in the bursting of soap films

NASA Astrophysics Data System (ADS)

Liang, N. Y.; Chan, C. K.; Choi, H. J.

1996-10-01

The thickness profiles of the aureole created in the bursting of vertical soap films are studied by a fast line scan charge-coupled device camera. Detail dynamics of the aureole are reported. Phenomena of the wavelike motions of the bursting rim and detachments of the aureole from the bursting film are also observed. We find that the stability of the aureole increases with the surfactant concentrations and is sensitive to the types of surfactant being used. The concentration dependence suggests that the interaction of micelles might be important in the bursting process. Furthermore, the surfactant monolayer in the aureole is found to be highly compressed and behaves like a rigid film. Existing theories of the aureole formation cannot account for all the observed phenomena.

Method for enhancing selectivity and recovery in the fractional flotation of particles in a flotation column

DOEpatents

Klunder, Edgar B [Bethel Park, PA

2011-08-09

The method relates to particle separation from a feed stream. The feed stream is injected directly into the froth zone of a vertical flotation column in the presence of a counter-current reflux stream. A froth breaker generates a reflux stream and a concentrate stream, and the reflux stream is injected into the froth zone to mix with the interstitial liquid between bubbles in the froth zone. Counter-current flow between the plurality of bubbles and the interstitial liquid facilitates the attachment of higher hydrophobicity particles to bubble surfaces as lower hydrophobicity particles detach. The height of the feed stream injection and the reflux ratio may be varied in order to optimize the concentrate or tailing stream recoveries desired based on existing operating conditions.

High yield growth of patterned vertically aligned carbon nanotubes using inkjet-printed catalyst.

PubMed

Beard, James D; Stringer, Jonathan; Ghita, Oana R; Smith, Patrick J

2013-10-09

This study reports on the fabrication of vertically aligned carbon nanotubes localized at specific sites on a growth substrate by deposition of a nanoparticle suspension using inkjet printing. Carbon nanotubes were grown with high yield as vertically aligned forests to a length of approximately 400 μm. The use of inkjet printing for catalyst fabrication considerably improves the production rate of vertically aligned patterned nanotube forests compared with conventional patterning techniques, for example, electron beam lithography or photolithography.

Design, fabrication, and performance analysis of GaN vertical electron transistors with a buried p/n junction

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

Yeluri, Ramya, E-mail: ramyay@ece.ucsb.edu; Lu, Jing; Keller, Stacia

2015-05-04

The Current Aperture Vertical Electron Transistor (CAVET) combines the high conductivity of the two dimensional electron gas channel at the AlGaN/GaN heterojunction with better field distribution offered by a vertical design. In this work, CAVETs with buried, conductive p-GaN layers as the current blocking layer are reported. The p-GaN layer was regrown by metalorganic chemical vapor deposition and the subsequent channel regrowth was done by ammonia molecular beam epitaxy to maintain the p-GaN conductivity. Transistors with high ON current (10.9 kA/cm{sup 2}) and low ON-resistance (0.4 mΩ cm{sup 2}) are demonstrated. Non-planar selective area regrowth is identified as the limiting factormore » to transistor breakdown, using planar and non-planar n/p/n structures. Planar n/p/n structures recorded an estimated electric field of 3.1 MV/cm, while non-planar structures showed a much lower breakdown voltage. Lowering the p-GaN regrowth temperature improved breakdown in the non-planar n/p/n structure. Combining high breakdown voltage with high current will enable GaN vertical transistors with high power densities.« less

Correction of Electron Density Profiles in the Low Ionosphere Based on the Data of Vertical Sounding with the IRI Model

NASA Astrophysics Data System (ADS)

Denisenko, P. F.; Maltseva, O. A.; Sotsky, V. V.

2018-03-01

The method of correcting the daytime vertical profiles of electron plasma frequency in the low ionosphere from International Refererence Ionosphere (IRI) model in accordance with the measured data of the virtual heights and absorption of signal radiowaves (method A1) reflected from the bottom of E-region at vertical sounding (VS) is presented. The method is based on the replacement of the IRI model profile by an approximation of analytical dependence with parameters determined according to VS data and partially by the IRI model. The method is tested by the results of four joint ground-based and rocket experiments carried out in the 1970s at midlatitudes of the European part of Russia upon the launches of high-altitude geophysical rockets of the Vertical series. It is shown that the consideration of both virtual reflection heigths and absorption makes it possible to obtain electron density distributions that show the best agreement with the rocket measurements made at most height ranges in the D- and E-regions. In additional, the obtained distributions account more adequately than the IRI model for the contributions of D- and E-regions to absorption of signals reflected above these regions.

Pathogenesis of rhegmatogenous retinal detachment: predisposing anatomy and cell biology.

PubMed

Mitry, Danny; Fleck, Brian W; Wright, Alan F; Campbell, Harry; Charteris, David G

2010-01-01

The pathogenesis of rhegmatogenous retinal detachment is complex, and our knowledge of the exact mechanism of vitreoretinal attachment and detachment remains incomplete. We performed a Medline, Ovid, and EMBASE search using search words rhegmatogenous, retinal detachment, vitreous, and retinal adhesion. All appropriate articles were reviewed, and the evidence was compiled. Cortical vitreous contains fibrillar collagens type II, V/XI, and IX. The inner limiting membrane of the retina contains collagens type I, IV, VI, and XVIII as well as numerous other glycoproteins and potential adhesion molecules. The distribution and age-related changes in the structure of these molecules play an important role in the formation of a retinal break, which may compromise and disrupt the normal mechanisms of neurosensory retinal adhesion. Rhegmatogenous retinal detachment development is intimately related to changes in the fibrillar structure of the aging vitreous culminating in posterior vitreous detachment with regions of persistent and tangential vitreoretinal traction predisposing to retinal tear formation. A complex interplay of factors such as weakening of vitreoretinal adhesion, posterior migration of the vitreous base, and molecular changes at the vitreoretinal interface are important in predisposing to focal areas of vitreoretinal traction precipitating rhegmatogenous retinal detachment. Once formed, the passage of liquefied vitreous through a retinal break may overwhelm normal neurosensory-retinal pigment epithelium adhesion perpetuating and extending detachment and causing visual loss. To understand the molecular events underlying rhegmatogenous retinal detachment so that new therapies can be developed, it is important to appreciate the structural organization of the vitreous, the biology underlying vitreous liquefaction and posterior vitreous detachment, and the mechanisms of vitreoretinal attachment and detachment.

Paediatric retinal detachment: aetiology, characteristics and outcomes.

PubMed

McElnea, Elizabeth; Stephenson, Kirk; Gilmore, Sarah; O'Keefe, Michael; Keegan, David

2018-01-01

To provide contemporary data on the aetiology, clinical features and outcomes of paediatric retinal detachment. A retrospective review of all those under 16y who underwent surgical repair for retinal detachment at a single centre between the years 2008 and 2015 inclusive was performed. In each case the cause of retinal detachment, the type of detachment, the presence or absence of macular involvement, the number and form of reparative surgeries undertaken, and the surgical outcome achieved was recorded. Twenty-eight eyes of 24 patients, 15 (62.5%) of whom were male and 9 (37.5%) of whom were female, their mean age being 11.6y and range 2-16y developed retinal detachment over the eight year period studied. Trauma featured in the development of retinal detachment in 14 (50.0%) cases. Retinal detachment was associated with other ocular and/or systemic conditions in 11 (39.3%) cases. A mean of 3.0 procedures with a range of 1-9 procedures per patient were undertaken in the management of retinal detachment. Complex vitrectomy combined with scleral buckling or complex vitrectomy alone were those most frequently performed. Mean postoperative visual acuity was 1.2 logMAR with range 0.0-3.0 logMAR. In 22 of 26 (84.6%) cases which underwent surgical repair the retina was attached at last follow-up. Aggressive management of paediatric retinal detachment including re-operation increases the likelihood of anatomical success. In cases where the retinal detachment can be repaired by an external approach alone there is a more favourable visual outcome.

32 CFR 700.723 - Administration and discipline: Separate and detached command.

Code of Federal Regulations, 2010 CFR

2010-07-01

... detached command. 700.723 Section 700.723 National Defense Department of Defense (Continued) DEPARTMENT OF... Administration and discipline: Separate and detached command. Any flag or general officer in command, any officer... are separate or detached commands. Such officer shall state in writing that it is a separate or...

32 CFR 700.723 - Administration and discipline: Separate and detached command.

Code of Federal Regulations, 2014 CFR

2014-07-01

... detached command. 700.723 Section 700.723 National Defense Department of Defense (Continued) DEPARTMENT OF... Administration and discipline: Separate and detached command. Any flag or general officer in command, any officer... are separate or detached commands. Such officer shall state in writing that it is a separate or...

32 CFR 700.723 - Administration and discipline: Separate and detached command.

Code of Federal Regulations, 2011 CFR

2011-07-01

... detached command. 700.723 Section 700.723 National Defense Department of Defense (Continued) DEPARTMENT OF... Administration and discipline: Separate and detached command. Any flag or general officer in command, any officer... are separate or detached commands. Such officer shall state in writing that it is a separate or...

32 CFR 700.723 - Administration and discipline: Separate and detached command.

Code of Federal Regulations, 2013 CFR

2013-07-01

... detached command. 700.723 Section 700.723 National Defense Department of Defense (Continued) DEPARTMENT OF... Administration and discipline: Separate and detached command. Any flag or general officer in command, any officer... are separate or detached commands. Such officer shall state in writing that it is a separate or...

32 CFR 700.723 - Administration and discipline: Separate and detached command.

Code of Federal Regulations, 2012 CFR

2012-07-01

... detached command. 700.723 Section 700.723 National Defense Department of Defense (Continued) DEPARTMENT OF... Administration and discipline: Separate and detached command. Any flag or general officer in command, any officer... are separate or detached commands. Such officer shall state in writing that it is a separate or...

In vivo performance of two different hydroxyapatite coatings on titanium prepared by discharging in electrolytes.

PubMed

Yamamoto, Hiroki; Shibata, Yo; Tachikawa, Tetsuhiko; Miyazaki, Takashi

2006-07-01

This study reports a discharging method for bone-like carbonated HA (cHA)-coating (Ca/P 1.71) and stoichiometric HA (sHA)-coating (Ca/P 1.67) with micrometer order thicknesses on titanium plates, using modified body fluid and acidic calcium phosphate solutions, respectively. In vivo histological performance of the HA coatings prepared by discharging in electrolytes was evaluated. Bone-contact indexes of HA coatings were measured microscopically. Additionally, bone-coating interface was analyzed by scanning electron microscopy and the use of an electron probe microanalyzer. Results demonstrated that there was no significant difference in contact index between HA coatings. However, the cHA coating was practically replaced by immature bone, and the titanium metal substrate was directly connected to the bone structure whereas the sHA coating layer remained and was partially detached from the titanium metal substrate. Since detached coating particles are pathogens, and can cause peri-implantitis, the cHA coating was more favorable than the sHA coating even if contact index was equivalent to that of the sHA coating. It is thought that coating thickness and chemical composition of coatings are important for biological stability of implants. In conclusion, since bone-like thin cHA coating showed high osteoconductivity and bone replacement, bone-like HA is superior to sHA coating for use in dental implants.

Management of inadvertent needle penetration resulting in subretinal triamcinolone acetonide and retinal detachment.

PubMed

Tran, Kimberly D; Crane, Ashley M; Flynn, Harry W

2018-06-01

To report management of inadvertent needle penetration during subtenons triamcinolone acetonide administration resulting in retinal detachment. A 71-year-old female with history of diabetes, hypothyroidism, and mild myopia underwent subtenons triamcinolone acetonide (TA) injection in the right eye for nodular scleritis. There was unexpected patient movement concurrent with the injection resulting in needle penetration, subretinal and intravitreal injection of TA, superotemporal retinal break, and macula-involving retinal detachment. The patient underwent partial subretinal TA removal, successful retinal detachment repair, and recovered 20/25 visual acuity. In spite of prominent subretinal TA and retinal detachment, successful repair of retinal detachment and recovery of good visual acuity is possible.

A history of detachable coils: 1987-2012.

PubMed

Hui, Ferdinand K; Fiorella, David; Masaryk, Thomas J; Rasmussen, Peter A; Dion, Jacques E

2014-03-01

The development of detachable coils is one of the most pivotal developments in neurointervention, providing a tool that could be used to treat a wide variety of hemorrhagic stroke. From the original Guglielmi detachable coil, a number of different coil designs and delivery designs have evolved. This article reviews the history of commercially available detachable coils. A timeline of detachable coils was constructed and coil design philosophies were reviewed. A complete list of commercially available coils is presented in a timeline format. Detachable coil technology continues to evolve. Advances in construction and design have yielded products which may benefit patients in terms of safety, radiation dose reduction and cost of treatment. Continued evolution is expected, irrespective of competing disruptive technologies.

The Relationship between Job Demands and Employees' Counterproductive Work Behaviors: The Mediating Effect of Psychological Detachment and Job Anxiety.

PubMed

Chen, Yang; Li, Shuang; Xia, Qing; He, Chao

2017-01-01

This study aims to explore the relation between job demands and counterproductive work behaviors (CWBs). A cross-sectional sample of 439 coal miners completed a self-report questionnaire that assessed their job demands, psychological detachment, job anxiety, and CWBs in a Chinese context. The conceptual model, based on the stressor-detachment model, was examined using structural equation modeling. The results suggest that psychological detachment mediates not only the relation between job demands and job anxiety but also that between job demands and CWBs. Furthermore, the relation between job demands and CWBs is sequentially mediated by psychological detachment and job anxiety. Our findings validate the effectiveness of the stressor-detachment model. Moreover, we demonstrate that the underlying mechanism of the relation between job demands and CWBs can be explained by psychological detachment and job anxiety.

The Relationship between Job Demands and Employees’ Counterproductive Work Behaviors: The Mediating Effect of Psychological Detachment and Job Anxiety

PubMed Central

Chen, Yang; Li, Shuang; Xia, Qing; He, Chao

2017-01-01

This study aims to explore the relation between job demands and counterproductive work behaviors (CWBs). A cross-sectional sample of 439 coal miners completed a self-report questionnaire that assessed their job demands, psychological detachment, job anxiety, and CWBs in a Chinese context. The conceptual model, based on the stressor-detachment model, was examined using structural equation modeling. The results suggest that psychological detachment mediates not only the relation between job demands and job anxiety but also that between job demands and CWBs. Furthermore, the relation between job demands and CWBs is sequentially mediated by psychological detachment and job anxiety. Our findings validate the effectiveness of the stressor-detachment model. Moreover, we demonstrate that the underlying mechanism of the relation between job demands and CWBs can be explained by psychological detachment and job anxiety. PMID:29163274

Photoelectron spectroscopy of B{sub 4}O{sub 4}{sup −}: Dual 3c-4e π hyperbonds and rhombic 4c-4e o-bond in boron oxide clusters

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

Tian, Wen-Juan; Chen, Qiang; Ou, Ting

2015-04-07

Gas-phase anion photoelectron spectroscopy (PES) is combined with global structural searches and electronic structure calculations at the hybrid Becke 3-parameter exchange functional and Lee-Yang-Parr correlation functional (B3LYP) and single-point coupled-cluster with single, double, and perturbative triple excitations (CCSD(T)) levels to probe the structural and electronic properties and chemical bonding of the B{sub 4}O{sub 4}{sup 0/−} clusters. The measured PES spectra of B{sub 4}O{sub 4}{sup −} exhibit a major band with the adiabatic and vertical detachment energies (ADE and VDE) of 2.64 ± 0.10 and 2.81 ± 0.10 eV, respectively, as well as a weak peak with the ADE and VDEmore » of 1.42 ± 0.08 and 1.48 ± 0.08 eV. The former band proves to correspond to the Y-shaped global minimum of C{sub s} B{sub 4}O{sub 4}{sup −} ({sup 2}A″), with the calculated ADE/VDE of 2.57/2.84 eV at the CCSD(T) level, whereas the weak band is associated with the second lowest-energy, rhombic isomer of D{sub 2h} B{sub 4}O{sub 4}{sup −} ({sup 2}B{sub 2g}) with the predicted ADE/VDE of 1.43/1.49 eV. Both anion structures are planar, featuring a B atom or a B{sub 2}O{sub 2} core bonded with terminal BO and/or BO{sub 2} groups. The same Y-shaped and rhombic structures are also located for the B{sub 4}O{sub 4} neutral cluster, albeit with a reversed energy order. Bonding analyses reveal dual three-center four-electron (3c-4e) π hyperbonds in the Y-shaped B{sub 4}O{sub 4}{sup 0/−} clusters and a four-center four-electron (4c-4e) π bond, that is, the so-called o-bond in the rhombic B{sub 4}O{sub 4}{sup 0/−} clusters. This work is the first experimental study on a molecular system with an o-bond.« less

Importance of anisotropy in detachment rates for force production and cargo transport by a team of motor proteins.

PubMed

Takshak, Anjneya; Kunwar, Ambarish

2016-05-01

Many cellular processes are driven by collective forces generated by a team consisting of multiple molecular motor proteins. One aspect that has received less attention is the detachment rate of molecular motors under mechanical force/load. While detachment rate of kinesin motors measured under backward force increases rapidly for forces beyond stall-force; this scenario is just reversed for non-yeast dynein motors where detachment rate from microtubule decreases, exhibiting a catch-bond type behavior. It has been shown recently that yeast dynein responds anisotropically to applied load, i.e. detachment rates are different under forward and backward pulling. Here, we use computational modeling to show that these anisotropic detachment rates might help yeast dynein motors to improve their collective force generation in the absence of catch-bond behavior. We further show that the travel distance of cargos would be longer if detachment rates are anisotropic. Our results suggest that anisotropic detachment rates could be an alternative strategy for motors to improve the transport properties and force production by the team. © 2016 The Protein Society.

Vertical GaN Devices for Power Electronics in Extreme Environments

DTIC Science & Technology

2016-03-31

electronics applications. In this paper vertical p-n diodes and transistors fabricated on pseudo bulk low defect density (104 to 106 cm-2) GaN substrates are...holes in p-GaN has deleterious effect on p-n junction behavior (Fig. 2), p-GaN contacts, and channel control in junction field-effect transistors at...and transistors ) utilizing p-n junctions are suitable for most practical applications including automotive (210K < T < 423K) but may have limitations

Star-like superalkali cations featuring planar pentacoordinate carbon

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

Guo, Jin-Chang; Tian, Wen-Juan; Zhao, Xue-Feng

Superalkali cations, known to possess low vertical electron affinities (VEAs), high vertical detachment energies, and large highest occupied molecular orbital (HOMO)-lowest unoccupied molecular orbital (LUMO) energy gaps, are intriguing chemical species. Thermodynamically, such species need to be the global minima in order to serve as the promising targets for experimental realization. In this work, we propose the strategies of polyhalogenation and polyalkalination for designing the superalkali cations. By applying these strategies, the local-minimum planar pentacoordinate carbon (ppC) cluster CBe{sub 5} can be modified to form a series of star-like superalkali ppC or quasi-ppC CBe{sub 5}X{sub 5}{sup +} (X = F,more » Cl, Br, Li, Na, K) cations containing a CBe{sub 5} moiety. Polyhalogenation and polyalkalination on the CBe{sub 5} unit may help eliminate the high reactivity of bare CBe{sub 5} molecule by covering the reactive Be atoms with noble halogen anions and alkali cations. Computational exploration of the potential energy surfaces reveals that the star-like ppC or quasi-ppC CBe{sub 5}X{sub 5}{sup +} (X = F, Cl, Br, Li, Na, K) clusters are the true global minima of the systems. The predicted VEAs for CBe{sub 5}X{sub 5}{sup +} range from 3.01 to 3.71 eV for X = F, Cl, Br and 2.12–2.51 eV for X = Li, Na, K, being below the lower bound of the atomic ionization potential of 3.89 eV in the periodic table. Large HOMO-LUMO energy gaps are also revealed for the species: 10.76–11.07 eV for X = F, Cl, Br and 4.99–6.91 eV for X = Li, Na, K. These designer clusters represent the first series of superalkali cations with a ppC center. Bonding analyses show five Be–X–Be three-center two-electron (3c-2e) σ bonds for the peripheral bonding, whereas the central C atom is associated with one 6c-2e π bond and three 6c-2e σ bonds, rendering (π and σ) double aromaticity. Born-Oppenheimer molecular dynamics simulations indicate that the CBe{sub 5} motif is robust in the clusters. As planar hypercoordination carbon species are often thermodynamically unstable and highly reactive, the superalkali cation characters of these ppC species should be highlighted, which may be suitable for experimental realization.« less

Atomistic investigation on the detachment of oil molecules from defective alumina surface

NASA Astrophysics Data System (ADS)

Xie, W. K.; Sun, Y. Z.; Liu, H. T.

2017-12-01

The mechanism of oil detachment from defective alumina surface in aqueous solution was investigated via atomistic molecular dynamics (MD) simulations. Special attention was focused on the effect of surface defect on the oil detachment. Our simulation results suggest that compared with perfect Al2O3 surface, defective substrate surface provides much more sites for the adsorption of oil molecules, thus it has higher oil adsorption energy. However, higher oil-solid adsorption energy does not mean that oil contaminants are much more difficult to be detached. It is found that surface defect could induce the spontaneous imbibition of water molecules, effectively promoting the detachment of oil molecules. Thus, compared with perfect alumina surface, the detachment of oil molecules from defective alumina surface tends to be much easier. Moreover, surface defect could lead to the oil residues inside surface defect. In water solution, the entire detachment process of oil molecules on defective surface consists of following stages, including the early detachment of oil molecules inside surface defect induced by capillary-driven spontaneous imbibition of water molecules, the following conformational change of oil molecules on topmost surface and the final migration of detached oil molecules from solid surface. These findings may help to sufficiently enrich the removal mechanism of oil molecules adhered onto defective solid surface.

Large current modulation and spin-dependent tunneling of vertical graphene/MoS2 heterostructures.

PubMed

Myoung, Nojoon; Seo, Kyungchul; Lee, Seung Joo; Ihm, G

2013-08-27

Vertical graphene heterostructures have been introduced as an alternative architecture for electronic devices by using quantum tunneling. Here, we present that the current on/off ratio of vertical graphene field-effect transistors is enhanced by using an armchair graphene nanoribbon as an electrode. Moreover, we report spin-dependent tunneling current of the graphene/MoS2 heterostructures. When an atomically thin MoS2 layer sandwiched between graphene electrodes becomes magnetic, Dirac fermions with different spins feel different heights of the tunnel barrier, leading to spin-dependent tunneling. Our finding will develop the present graphene heterostructures for electronic devices by improving the device performance and by adding the possibility of spintronics based on graphene.

The effect of vertical drift on the equatorial F-region stability

NASA Technical Reports Server (NTRS)

Hanson, W. B.; Cragin, B. L.; Dennis, A.

1986-01-01

Time-dependent ionospheric model calculations for day-time and night-time solutions are presented. The behavior of the growth rate and ion-electron recombination rate for the Rayleigh-Taylor instability on the F-region bottomside is examined as a function of the vertical eastward electric field-magnetic field strength drift velocity. It is observed that on the bottomside F-layer the growth rate exceeds the ion-electron recombination rate even without vertical drift; however, an eastward electric field-magnetic field strength drift can produce an increase in the growth rate by an order of magnitude. The calculated data are compared with previous research and good correlation is detected. The formation of bubbles from a seeding mechanism is investigated.

Final Act of an Oceanic Detachment Fault Revealed by Submersible Dives at 13°48'N on the Mid-Atlantic Ridge

NASA Astrophysics Data System (ADS)

Parnell-Turner, R. E.; Mittelstaedt, E. L.; Kurz, M. D.; Klein, F.

2017-12-01

A large proportion of crustal accretion on the slow-spreading Mid-Atlantic Ridge occurs under the influence of slip on low-angle detachment faults. The final stages of activity on an individual detachment system remain poorly understood, since it is difficult to place age constraints on exposed fault surfaces or lava flows. We use data from a combination of manned (Alvin) and autonomous (Sentry) submersible dives on a detachment near 13°48'N, to infer the history of slip and volcanism on a detachment fault which has recently become extinct. The corrugated surface, near the toe of the detachment, is cross-cut by a volcanic ridge, where pillow lavas have been photographed and sampled. Sub-bottom (CHIRP) profiles acquired by Sentry provide estimates of sediment thickness, which we use as a proxy for seafloor age, thus providing a relative dating tool for the exposed detachment footwall and erupted lavas. Sediments covering the footwall are 2 m thinner than those on lavas which cut across the detachment, implying that slip continued for 150 ka after eruption (assuming a constant sedimentation rate of 7 ± 2 mm/yr). Alternatively, sediment on the footwall may have been mass-wasted, and volcanism could have been contemporaneous with detachment inactivity. These results demonstrate that detachment faults may be highly sensitive to local changes in magma supply, and that direct seafloor observations are crucial to understanding slow-spreading ridge mechanics.

The mechanism for keratinocyte detaching from pH-responsive chitosan.

PubMed

Chen, Yi-Hsin; Chang, Shao-Hsuan; Wang, I-Jong; Young, Tai-Horng

2014-11-01

In this study, we compared the detachment ratio of HaCaT and Hs68 cells from pH-responsive chitosan surface by raising medium pH from 7.20 to 7.65 for 60 min. The detachment ratio of elongated Hs68 cells was over 75%, but that of round-shaped HaCaT cells was less than 50%, even extending the incubation time to 6 h or enhancing the cytoskeletal contractile force with the Rho activator CN01. However, the addition of 2 mm of EDTA into the medium at pH 7.65 could effectively detach HaCaT cells (detachment ratio > 90%), indicating that the calcium ion played an important role in the detachment process. Therefore, the family of Ca(+2)-dependent integrin receptors was examined by RT-PCR, real-time PCR and immunocytochemistry. It was found the expression of integrin β4 (ITGb4) was HaCaT cell-specific and the mRNA level of ITGb4 in undetached HaCaT cells was significantly higher than that in detached ones. By modulating ITGb4 activity with specific functional blocking antibody ASC-8, the detachment ratio of HaCaT cells could be increased to be greater than 85%. Conversely, the addition of the ligand of ITGb4 laminin into the culture system decreased the medium pH-induced detachment ratio for HaCaT cells, but not for Hs68 cells. Further addition of ASC-8 could rescue the effect of laminin on preventing the detachment of HaCaT cells from pH-sensitive chitosan surface. Therefore, this study demonstrated the interaction of ITGb4 and laminin played an important role in controlling the detachment of HaCaT cells on pH-responsive chitosan. Copyright © 2014 Elsevier Ltd. All rights reserved.

Effect of Asparagus racemosus extract on transdermal delivery of carvedilol: a mechanistic study.

PubMed

Sapra, Bharti; Jain, Subheet; Tiwary, Ashok K

2009-01-01

This study was designed for investigating the effect of Asparagus racemosus (AR) extract and chitosan (CTN) in facilitating the permeation of carvedilol (CDL) across rat epidermis. Transdermal flux of carvedilol through heat-separated rat epidermis was investigated in vitro using vertical Keshary-Chien diffusion cells. Biophysical and microscopic manifestations of epidermis treated with AR extract, CTN, and AR extract-CTN mixture were investigated by using differential scanning calorimetry, transepidermal water loss, scanning electron microscopy (SEM), and transmission electron microscopy (TEM). Biochemical estimations of cholesterol, sphingosine, and triglycerides were carried out for treated excised as well as viable rat epidermis. The antihypertensive activity of the patches in comparison with that of oral carvedilol was studied in deoxycorticosterone acetate-induced hypertensive rats. The permeation of carvedilol across excised rat epidermis was significantly higher (p < 0.05) when AR extract, CTN, or AR extract-CTN mixture was used as donor vehicle as compared to propylene glycol/ethanol (7:3) mixture. Epidermis obtained after 12 h treatment of viable rat skin with AR extract-CTN mixture showed significantly higher (p < 0.05) permeability to CDL as compared to that after treatment with AR extract or CTN alone. Further, the application of patches containing AR extract-CTN mixture resulted in sustained release of CDL which was able to control the hypertension in deoxycorticosterone acetate-induced hypertensive rats through 36 h. Estimation of micro constituents in rat epidermis revealed maximum extraction of cholesterol, sphingosine, and triglycerides after treatment with AR extract-CTN mixture. This was manifested in altered lipid and protein-specific thermotropic transitions. Further, increase in intercellular space, disordered lipid structure, and corneocyte detachment as observed in SEM and TEM suggested great potential of AR extract for use as percutaneous permeation enhancer. The developed transdermal patches of CDL containing AR extract-CTN mixture exhibited better performance as compared to oral administration in controlling hypertension in rats.

Why are SiX5(-) and GeX5(-) (X = F, Cl) stable but not CF5(-) and CCl5(-)?

PubMed

Marchaj, Marzena; Freza, Sylwia; Skurski, Piotr

2012-03-01

The possible existence of the CF(5)(-), CCl(5)(-), SiF(5)(-), SiCl(5)(-), GeF(5)(-), and GeCl(5)(-) anions has been investigated using ab initio methods. The species containing Si and Ge as central atoms were found to adopt the D(3h)-symmetry trigonal bipyramidal equilibrium structures whose thermodynamic stabilities were confirmed by examining the most probable fragmentation channels. The ab initio re-examination of the electronic stabilities of the SiF(5)(-), SiCl(5)(-), GeF(5)(-), and GeCl(5)(-) anions [using the OVGF(full) method with the 6-311+G(3df) basis set] led to the very large vertical electron detachment (VDE) energies of 9.316 eV (SiF(5)(-)) and 9.742 eV (GeF(5)(-)), whereas smaller VDEs of 6.196 and 6.452 eV were predicted for the SiCl(5)(-) and GeCl(5)(-) species, respectively. By contrast, the high-symmetry and structurally compact anionic CF(5)(-) and CCl(5)(-) systems cannot exist due to the strongly repulsive potential predicted for the X(-) (F(-) or Cl(-)) approaching the CX(4) (CF(4) or CCl(4)). The formation of weakly bound CX(4)···X(-) (CF(4)···F(-) and CCl(4)···Cl(-)) anionic complexes (consisting of pseudotetrahedral neutral CX(4) with the weakly tethered X(-)) might be expected at low temperatures (approaching 0 K), whereas neither CX(5)(-) (CF(5)(-), CCl(5)(-)) systems nor CX(4)···X(-) (CF(4)···F(-) and CCl(4)···Cl(-)) complexes can exist in the elevated temperatures (above 0K) due to their susceptibility to the fragmentation (leading to the X(-) loss). © 2012 American Chemical Society

Analysis of Bacterial Detachment from Substratum Surfaces by the Passage of Air-Liquid Interfaces

PubMed Central

Gómez-Suárez, Cristina; Busscher, Henk J.; van der Mei, Henny C.

2001-01-01

A theoretical analysis of the detachment of bacteria adhering to substratum surfaces upon the passage of an air-liquid interface is given, together with experimental results for bacterial detachment in the absence and presence of a conditioning film on different substratum surfaces. Bacteria (Streptococcus sobrinus HG1025, Streptococcus oralis J22, Actinomyces naeslundii T14V-J1, Bacteroides fragilis 793E, and Pseudomonas aeruginosa 974K) were first allowed to adhere to hydrophilic glass and hydrophobic dimethyldichlorosilane (DDS)-coated glass in a parallel-plate flow chamber until a density of 4 × 106 cells cm−2 was reached. For S. sobrinus HG1025, S. oralis J22, and A. naeslundii T14V-J1, the conditioning film consisted of adsorbed salivary components, while for B. fragilis 793E and P. aeruginosa 974K, the film consisted of adsorbed human plasma components. Subsequently, air bubbles were passed through the flow chamber and the bacterial detachment percentages were measured. For some experimental conditions, like with P. aeruginosa 974K adhering to DDS-coated glass and an air bubble moving at high velocity (i.e., 13.6 mm s−1), no bacteria detached upon passage of an air-liquid interface, while for others, detachment percentages between 80 and 90% were observed. The detachment percentage increased when the velocity of the passing air bubble decreased, regardless of the bacterial strain and substratum surface hydrophobicity involved. However, the variation in percentages of detachment by a passing air bubble depended greatly upon the strain and substratum surface involved. At low air bubble velocities the hydrophobicity of the substratum had no influence on the detachment, but at high air bubble velocities all bacterial strains were more efficiently detached from hydrophilic glass substrata. Furthermore, the presence of a conditioning film could either inhibit or stimulate detachment. The shape of the bacterial cell played a major role in detachment at high air bubble velocities, and spherical strains (i.e., streptococci) detached more efficiently than rod-shaped organisms. The present results demonstrate that methodologies to study bacterial adhesion which include contact with a moving air-liquid interface (i.e., rinsing and dipping) yield detachment of an unpredictable number of adhering microorganisms. Hence, results of studies based on such methodologies should be referred as “bacterial retention” rather than “bacterial adhesion”. PMID:11375160

Analysis of bacterial detachment from substratum surfaces by the passage of air-liquid interfaces.

PubMed

Gómez-Suárez, C; Busscher, H J; van der Mei, H C

2001-06-01

A theoretical analysis of the detachment of bacteria adhering to substratum surfaces upon the passage of an air-liquid interface is given, together with experimental results for bacterial detachment in the absence and presence of a conditioning film on different substratum surfaces. Bacteria (Streptococcus sobrinus HG1025, Streptococcus oralis J22, Actinomyces naeslundii T14V-J1, Bacteroides fragilis 793E, and Pseudomonas aeruginosa 974K) were first allowed to adhere to hydrophilic glass and hydrophobic dimethyldichlorosilane (DDS)-coated glass in a parallel-plate flow chamber until a density of 4 x 10(6) cells cm(-2) was reached. For S. sobrinus HG1025, S. oralis J22, and A. naeslundii T14V-J1, the conditioning film consisted of adsorbed salivary components, while for B. fragilis 793E and P. aeruginosa 974K, the film consisted of adsorbed human plasma components. Subsequently, air bubbles were passed through the flow chamber and the bacterial detachment percentages were measured. For some experimental conditions, like with P. aeruginosa 974K adhering to DDS-coated glass and an air bubble moving at high velocity (i.e., 13.6 mm s(-1)), no bacteria detached upon passage of an air-liquid interface, while for others, detachment percentages between 80 and 90% were observed. The detachment percentage increased when the velocity of the passing air bubble decreased, regardless of the bacterial strain and substratum surface hydrophobicity involved. However, the variation in percentages of detachment by a passing air bubble depended greatly upon the strain and substratum surface involved. At low air bubble velocities the hydrophobicity of the substratum had no influence on the detachment, but at high air bubble velocities all bacterial strains were more efficiently detached from hydrophilic glass substrata. Furthermore, the presence of a conditioning film could either inhibit or stimulate detachment. The shape of the bacterial cell played a major role in detachment at high air bubble velocities, and spherical strains (i.e., streptococci) detached more efficiently than rod-shaped organisms. The present results demonstrate that methodologies to study bacterial adhesion which include contact with a moving air-liquid interface (i.e., rinsing and dipping) yield detachment of an unpredictable number of adhering microorganisms. Hence, results of studies based on such methodologies should be referred as "bacterial retention" rather than "bacterial adhesion".

Fast moving plasma structures in the distant magnetotail

NASA Technical Reports Server (NTRS)

Scholer, M.; Klecker, B.; Hovestadt, D.; Gloeckler, G.; Ipavich, F. M.; Smith, E. J.

1984-01-01

The paper reports for the first time the detailed time behavior of the intensities and the angular distributions of energetic protons and electrons in the distant magnetotail of the earth at 220 earth radii and 110 earth radii. The data have been obtained by the Max-Planck-Institut/University of Maryland sensor system on ISEE 3 during the spacecraft's first deep tail passage. Three energetic particle bursts are studied in detail. It is suggested that the satellite encounters detached plasma structures evidenced by the isotropic electrons. These structures, probably plasmoids, move with high velocities (about 800 km/s) down the tail. The energetic electrons and protons stream ahead of these fast tailward moving plasma structures, which leads to the various time dispersion effects. This allows, in principle, a determination of the source distance from the satellite.

Analytical method for determining rill detachment rate of purple soil as compared with that of loess soil

USDA-ARS?s Scientific Manuscript database

Rill detachment is an important process in rill erosion. The rill detachment rate is the fundamental basis for determination of the parameters of a rill erosion model. In this paper, an analytical method was proposed to estimate the rill detachment rate. The method is based on the exact analytical s...

Repair of Traumatic Rhegmatogenous Retinal Detachment Combined with Congenital Falciform Retinal Detachment.

PubMed

Mano, Fukutaro; Chang, Kuo-Chung; Mano, Tomiya

2018-01-01

To report a case of surgical repair of traumatic rhegmatogenous retinal detachment combined with congenital falciform retinal detachment (FRD). A retrospective case report. A 36-year-old man with traumatic rhegmatogenous retinal detachment complicating a previously known FRD was successfully treated despite residual FRD following pars plana lensectomy, vitrectomy, and encircling scleral buckling. His best corrected visual acuity improved from hand motion at 50 cm to 20/1,000. We concluded that the root of the FRD is susceptible to trauma because of the contraction of fibrovascular tissue. The early intervention of modern vitrectomy to traumatic rhegmatogenous retinal detachment complicating a previously known FRD is an important consideration for enhanced quality of care and optimal patient outcomes.

Repair of Traumatic Rhegmatogenous Retinal Detachment Combined with Congenital Falciform Retinal Detachment

PubMed Central

Mano, Fukutaro; Chang, Kuo-Chung; Mano, Tomiya

2018-01-01

Purpose To report a case of surgical repair of traumatic rhegmatogenous retinal detachment combined with congenital falciform retinal detachment (FRD). Methods A retrospective case report. Results A 36-year-old man with traumatic rhegmatogenous retinal detachment complicating a previously known FRD was successfully treated despite residual FRD following pars plana lensectomy, vitrectomy, and encircling scleral buckling. His best corrected visual acuity improved from hand motion at 50 cm to 20/1,000. Conclusion We concluded that the root of the FRD is susceptible to trauma because of the contraction of fibrovascular tissue. The early intervention of modern vitrectomy to traumatic rhegmatogenous retinal detachment complicating a previously known FRD is an important consideration for enhanced quality of care and optimal patient outcomes. PMID:29643782

Ocular toxoplasmosis and retinal detachment: five case reports.

PubMed

Kianersi, F; Naderi Beni, A; Ghanbari, H; Fazel, F

2012-10-01

Ocular toxoplasmosis is a potentially blinding cause of posterior uveitis. Retinal detachment is rare complication of ocular toxoplasmosis. To report the clinical course and prognosis of retinal breaks and detachments occurring in patients with ocular toxoplasmosis. This study was a retrospective, non-comparative case series of five patients with ocular toxoplasmosis who had consulted us with retinal detachment. All of the participants had retinal detachment after severe and treatment resistant toxoplasmic retinochoroiditis, leaving one of them with decreased visual acuity to light perception in spite of treatment and final visual acuity was 20/100 or better in four patients. The functional prognosis for the patients with retinal detachment was poor. Careful retinal examination in ocular toxoplasmosis is warranted, especially in patients with severe intraocular inflammation.

Magnetically Controlled Upper Ionosphere of Mars

NASA Astrophysics Data System (ADS)

Majeed, T.; Al Aryani, O.; Al Mutawa, S.; Bougher, S. W.; Haider, S. A.

2017-12-01

The electron density (Ne) profiles measured by the Mars Express spacecraft over regions of strong crustal magnetic fields have shown anomalous characteristics of the topside plasma distribution with variable scale heights. One of such Ne profiles is located at 82oS and 180oE whose topside ionosphere is extended up to an altitude of 700 km. The crustal magnetic field at this southern site is nearly vertical and open to the access of solar wind plasma through magnetic reconnection with the interplanetary magnetic field. This can lead to the acceleration of electrons and ions during the daytime ionosphere. The downward accelerated electrons with energies >200 eV can penetrate deep into the Martian upper ionosphere along vertical magnetic field lines and cause heating, excitation and ionization of the background atmosphere. The upward acceleration of ions resulting from energy input by precipitating electrons can lead to enhance ion escape rate and modify scale heights of the topside ionosphere. We have developed a 1-D chemical diffusive model from 100 km to 400 km to interpret the Martian ionospheric structure at 82oS latitude. The primary source of ionization in the model is due to solar EUV radiation. An extra ionization source due to precipitating electrons of 0.25 keV, peaking near an altitude of 145 km is added in the model to reasonably reproduce the measured ionospheric structure below an altitude of 180 km. The behavior of the topside ionosphere can be interpreted by the vertical plasma transport caused by precipitating electrons. The vertical transport of plasma in our model is simulated by vertical ion velocities, whose values can be interpreted as drift velocities along magnetic field lines. We find that the variation of the topside Ne scale heights is sensitive to the magnitudes of upward and downward drifts with an imposed outward flux boundary condition at the top of the model. The model requires an upward flux of more than 107 ions cm-2 s-1 for both O2+ and O+, and drift speeds of 200 m/s to interpret the measured topside ionospheric structure for altitudes >180 km. The magnitudes of outward ion fluxes and drift velocities are compared with those simulated by existing models. The model results will be presented in comparison with the measured electron density profile. This work is supported by MBRSC, Dubai, UAE.

Robust forests of vertically aligned carbon nanotubes chemically assembled on carbon substrates.

PubMed

Garrett, David J; Flavel, Benjamin S; Shapter, Joseph G; Baronian, Keith H R; Downard, Alison J

2010-02-02

Forests of vertically aligned carbon nanotubes (VACNTs) have been chemically assembled on carbon surfaces. The structures show excellent stability over a wide potential range and are resistant to degradation from sonication in acid, base, and organic solvent. Acid-treated single-walled carbon nanotubes (SWCNTs) were assembled on amine-terminated tether layers covalently attached to pyrolyzed photoresist films. Tether layers were electrografted to the carbon substrate by reduction of the p-aminobenzenediazonium cation and oxidation of ethylenediamine. The amine-modified surfaces were incubated with cut SWCNTs in the presence of N,N'-dicyclohexylcarbodiimide (DCC), giving forests of vertically aligned carbon nanotubes (VACNTs). The SWCNT assemblies were characterized by scanning electron microscopy, atomic force microscopy, and electrochemistry. Under conditions where the tether layers slow electron transfer between solution-based redox probes and the underlying electrode, the assembly of VACNTs on the tether layer dramatically increases the electron-transfer rate at the surface. The grafting procedure, and hence the preparation of VACNTs, is applicable to a wide range of materials including metals and semiconductors.

Measurement of a density profile of a hot-electron plasma in RT-1 with three-chord interferometry

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

Saitoh, H.; Yano, Y.; Yoshida, Z.

2015-02-15

The electron density profile of a plasma in a magnetospheric dipole field configuration was measured with a multi-chord interferometry including a relativistic correction. In order to improve the accuracy of density reconstruction, a 75 GHz interferometer was installed at a vertical chord of the Ring Trap 1 (RT-1) device in addition to previously installed ones at tangential and another vertical chords. The density profile was calculated by using the data of three-chord interferometry including relativistic effects for a plasma consisting of hot and cold electrons generated by electron cyclotron resonance heating (ECH). The results clearly showed the effects of density peakingmore » and magnetic mirror trapping in a strongly inhomogeneous dipole magnetic field.« less

Mixing Time Effects on the Dispersion Performance of Adhesive Mixtures for Inhalation

PubMed Central

Grasmeijer, Floris; Hagedoorn, Paul; Frijlink, Henderik W.; de Boer, H. Anne

2013-01-01

This paper deals with the effects of mixing time on the homogeneity and dispersion performance of adhesive mixtures for inhalation. Interactions between these effects and the carrier size fraction, the type of drug and the inhalation flow rate were studied. Furthermore, it was examined whether or not changes in the dispersion performance as a result of prolonged mixing can be explained with a balance of three processes that occur during mixing, knowing drug redistribution over the lactose carrier; (de-) agglomeration of the drug (and fine lactose) particles; and compression of the drug particles onto the carrier surface. For this purpose, mixtures containing salmeterol xinafoate or fluticasone propionate were mixed for different periods of time with a fine or coarse crystalline lactose carrier in a Turbula mixer. Drug detachment experiments were performed using a classifier based inhaler at different flow rates. Scanning electron microscopy and laser diffraction techniques were used to measure drug distribution and agglomeration, whereas changes in the apparent solubility were measured as a means to monitor the degree of mechanical stress imparted on the drug particles. No clear trend between mixing time and content uniformity was observed. Quantitative and qualitative interactions between the effect of mixing time on drug detachment and the type of drug, the carrier size fraction and the flow rate were measured, which could be explained with the three processes mentioned. Generally, prolonged mixing caused drug detachment to decrease, with the strongest decline occurring in the first 120 minutes of mixing. For the most cohesive drug (salmeterol) and the coarse carrier, agglomerate formation seemed to dominate the overall effect of mixing time at a low inhalation flow rate, causing drug detachment to increase with prolonged mixing. The optimal mixing time will thus depend on the formulation purpose and the choice for other, interacting variables. PMID:23844256

A numerical analysis of forces exerted by laminar flow on spreading cells in a parallel plate flow chamber assay.

PubMed

Olivier, L A; Truskey, G A

1993-10-01

Exposure of spreading anchorage-dependent cells to laminar flow is a common technique to measure the strength of cell adhesion. Since cells protrude into the flow stream, the force exerted by the fluid on the cells is a function of cell shape. To assess the relationship between cell shape and the hydrodynamic force on adherent cells, we obtained numerical solutions of the velocity and stress fields around bovine aortic endothelial cells during various stages of spreading and calculated the force required to detach the cells. Morphometric parameters were obtained from light and scanning electron microscopy measurements. Cells were assumed to have a constant volume, but the surface area increased during spreading until the membrane was stretched taut. Two-dimensional models of steady flow were generated using the software packages ANSYS (mesh generation) and FIDAP (problem solution). The validity of the numerical results was tested by comparison with published results for a semicircle in contact with the surface. The drag force and torque were greatest for round cells making initial contact with the surface. During spreading, the drag force and torque declined by factors of 2 and 20, respectively. The calculated forces and moments were used in adhesion models to predict the wall shear stress at which the cells detached. Based upon published values for the bond force and receptor number, round cells should detach at shear stresses between 2.5 and 6 dyn/cm(2), whereas substantially higher stresses are needed to detach spreading and fully spread cells. Results from the simulations indicate that (1) the drag force varies little with cell shape whereas the torque is very sensitive to cell shape, and (2) the increase in the strength of adhesion during spreading is due to increased contact area and receptor densities within the contact area. (c) 1993 John Wiley & Sons, Inc.

Accelerated cell-sheet recovery from a surface successively grafted with polyacrylamide and poly(N-isopropylacrylamide).

PubMed

Akiyama, Yoshikatsu; Kikuchi, Akihiko; Yamato, Masayuki; Okano, Teruo

2014-08-01

A double polymeric nanolayer consisting of poly(N-isopropylacrylamide) (PIPAAm) and hydrophilic polyacrylamide (PAAm) was deposited on tissue culture polystyrene (TCPS) surfaces using electron beam irradiation to form a new temperature-responsive cell culture surface in which the basal hydrophilic PAAm component in the double polymeric layer promotes the hydration of the upper PIPAAm layer and induces rapid cell detachment compared to a conventional temperature-responsive cell culture surface, PIPAAm-grafted TCPS (PIPAAm-TCPS). Take-off angle-dependent X-ray photoelectron spectroscopy spectral analysis demonstrated that the grafted PIPAAm and PAAm components were located in the upper and basal regions of the double polymeric layer, respectively, suggesting that the double polymeric layer forms an inter-penetrating-network-like structure with PAAm at the basal portion of the PIPAAm grafted chains. The wettability of the temperature-responsive cell culture surfaces with the double polymeric layer tended to be more hydrophilic, with an increase in the basal PAAm graft density at a constant PIPAAm graft density. However, when the graft densities of the upper PIPAAm and basal PAAm were optimized, the resulting temperature-responsive cell culture surface with the double polymeric layer exhibited rapid cell detachment while maintaining cell adhesive character comparable to that of PIPAAm-TCPS. The cell adhesive character was altered from cell-adhesive to cell-repellent with increasing PAAm or PIPAAm graft density. The cell adhesive character of the temperature-responsive cell culture surfaces was relatively consistent with their contact angles. These results strongly suggest that the basal PAAm surface properties affect the degree of hydration and dehydration of the subsequently grafted PIPAAm. In addition, the roles of the hydrophilic component in accelerating cell detachment are further discussed in terms of the mobility of the grafted PIPAAm chains. Applications of this insight might be useful for designing temperature-responsive cell culture surfaces for achieving efficient cell culture and quick target cell detachment. Copyright © 2014 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Vertical repositioning accuracy of magnetic mounting systems on 4 articulator models.

PubMed

Lee, Wonsup; Kwon, Ho-Beom

2018-03-01

Research of the ability of a cast mounted on an articulator on maintaining the identical position of a cast mounted on an articulator after repeated repositioning is lacking, despite the possible effects this may have on the occlusion of a mounted cast. The purpose of this in vitro study was to verify and compare the vertical repositioning accuracy of 4 different, commercially available articulator magnetic mounting plate systems. Four articulators and their associated magnetic mounting plates were selected for the study. These were the Artex AR articulator (Amann Girrbach AG), the Denar Mark II articulator (Whip Mix Corp), the Kavo Protar Evo articulator (Kavo Dental GmbH), and the SAM3 articulator (SAM Präzisionstechnik GmbH). Three new magnetic mounting plates were prepared for each articulator system. The repositioning accuracy of each mounting plate was evaluated by comparing the standard deviation of the vertical distances measured between the mounting plate and a laser displacement sensor. The lower arm of the articulator was secured, and the vertical distance was measured by positioning the laser displacement sensor positioned vertically above the mounting plate. Once the vertical distance was measured, the mounting plate was detached from the articulator and reattached manually to prepare for the next measurement. This procedure was repeated 30 times for each of the 3 magnetic mounting plates. Data were analyzed by ANOVA for 2-stage nested design and the Levene test (α=.05). Significant differences were detected among articulator systems and between magnetic mounting plates of the same type. The standard deviations of the measurements made with the Artex AR articulator, Denar Mark II articulator, Kavo Protar Evo articulator, and SAM3 articulator were 0.0027, 0.0308, 0.0214, and 0.0215 mm, respectively. Thus, the repositioning accuracy could be ranked in the order as follows: Artex AR, Kavo Protar Evo, SAM3, and Denar Mark II. The position of the magnetic mounting plate after repositioning did not maintain an identical position in the vertical dimension on any of the 4 articulator models tested. The repositioning accuracy of the mounting plates showed significant differences among the articulators tested in this study. Copyright © 2017 Editorial Council for the Journal of Prosthetic Dentistry. Published by Elsevier Inc. All rights reserved.

Surface coating for prevention of metallic seed migration in tissues

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

Lee, Hyunseok; Park, Jong In; Lee, Won Seok

Purpose: In radiotherapy, metallic implants often detach from their deposited sites and migrate to other locations. This undesirable migration could cause inadequate dose coverage for permanent brachytherapy and difficulties in image-guided radiation delivery for patients. To prevent migration of implanted seeds, the authors propose a potential strategy to use a biocompatible and tissue-adhesive material called polydopamine. Methods: In this study, nonradioactive dummy seeds that have the same geometry and composition as commercial I-125 seeds were coated in polydopamine. Using scanning electron microscopy and x-ray photoelectron spectroscopy, the surface of the polydopamine-coated and noncoated seeds was characterized. The detachment stress betweenmore » the two types of seeds and the tissue was measured. The efficacy of polydopamine-coated seed was investigated through in vitro migration tests by tracing the seed location after tissue implantation and shaking for given times. The cytotoxicity of the polydopamine coating was also evaluated. Results: The results of the coating characterization have shown that polydopamine was successfully coated on the surface of the seeds. In the adhesion test, the polydopamine-coated seeds had 2.1-fold greater detachment stress than noncoated seeds. From the in vitro test, it was determined that the polydopamine-coated seed migrated shorter distances than the noncoated seed. This difference was increased with a greater length of time after implantation. Conclusions: The authors suggest that polydopamine coating is an effective technique to prevent migration of implanted seeds, especially for permanent prostate brachytherapy.« less

Batchwise growth of silica cone patterns via self-assembly of aligned nanowires.

PubMed

Luo, Shudong; Zhou, Weiya; Chu, Weiguo; Shen, Jun; Zhang, Zengxing; Liu, Lifeng; Liu, Dongfang; Xiang, Yanjuan; Ma, Wenjun; Xie, Sishen

2007-03-01

Silica-cone patterns self-assembled from well-aligned nanowires are synthesized using gallium droplets as the catalyst and silicon wafers as the silicon source. The cones form a triangular pattern array radially on almost the whole surface of the molten Ga ball. Detailed field-emission scanning electron microscopy (SEM) analysis shows that the cone-pattern pieces frequently slide off and are detached from the molten Ga ball surface, which leads to the exposure of the catalyst surface and the growth of a new batch of silicon oxide nanowires as well as the cone patterns. The processes of growth and detachment alternate, giving rise to the formation of a volcano-like or a flower-like structure with bulk-quantity pieces of cone patterns piled up around the Ga ball. Consequently, the cone-patterned layer grows batch by batch until the reaction is terminated. Different to the conventional metal-catalyzed growth model, the batch-by-batch growth of the triangular cone patterns proceeds on the molten Ga balls via alternate growth on and detachment from the catalyst surface of the patterns; the Ga droplet can be used continuously and circularly as an effective catalyst for the growth of amorphous SiO(x) nanowires during the whole growth period. The intriguing batchwise growth phenomena may enrich our understanding of the vapour-liquid-solid (VLS) growth mechanism for the catalyst growth of nanowires or other nanostructures and may offer a different way of self-assembling novel silica nanostructures.

Probing the Vibrational Spectroscopy of the Deprotonated Thymine Radical by Photodetachment and State-Selective Autodetachment Photoelectron Spectroscopy via Dipole-Bound States

NASA Astrophysics Data System (ADS)

Huang, Dao-Ling; Zhu, Guo-Zhu; Wang, Lai-Sheng

2016-06-01

Deprotonated thymine can exist in two different forms, depending on which of its two N sites is deprotonated: N1[T-H]^- or N3[T-H]^-. Here we report a photodetachment study of the N1[T-H]^- isomer cooled in a cryogenic ion trap and the observation of an excited dipole-bound state. Eighteen vibrational levels of the dipole-bound state are observed, and its vibrational ground state is found to be 238 ± 5 wn below the detachment threshold of N1[T-H]^-. The electron affinity of the deprotonated thymine radical (N1[T-H]^.) is measured accruately to be 26 322 ± 5 wn (3.2635 ± 0.0006 eV). By tuning the detachment laser to the sixteen vibrational levels of the dipole-bound state that are above the detachment threshold, highly non-Franck-Condon resonant-enhanced photoelectron spectra are obtained due to state- and mode-selective vibrational autodetachment. Much richer vibrational information is obtained for the deprotonated thymine radical from the photodetachment and resonant-enhanced photoelectron spectroscopy. Eleven fundamental vibrational frequencies in the low-frequency regime are obtained for the N1[T-H]^. radical, including the two lowest-frequency internal rotational modes of the methyl group at 70 ± 8 wn and 92 ± 5 wn. D. L. Huang, H. T. Liu, C. G. Ning, G. Z. Zhu and L. S. Wang, Chem. Sci., 6, 3129-3138 (2015)

Comparisons of ionospheric electron density distributions reconstructed by GPS computerized tomography, backscatter ionograms, and vertical ionograms

NASA Astrophysics Data System (ADS)

Zhou, Chen; Lei, Yong; Li, Bofeng; An, Jiachun; Zhu, Peng; Jiang, Chunhua; Zhao, Zhengyu; Zhang, Yuannong; Ni, Binbin; Wang, Zemin; Zhou, Xuhua

2015-12-01

Global Positioning System (GPS) computerized ionosphere tomography (CIT) and ionospheric sky wave ground backscatter radar are both capable of measuring the large-scale, two-dimensional (2-D) distributions of ionospheric electron density (IED). Here we report the spatial and temporal electron density results obtained by GPS CIT and backscatter ionogram (BSI) inversion for three individual experiments. Both the GPS CIT and BSI inversion techniques demonstrate the capability and the consistency of reconstructing large-scale IED distributions. To validate the results, electron density profiles obtained from GPS CIT and BSI inversion are quantitatively compared to the vertical ionosonde data, which clearly manifests that both methods output accurate information of ionopsheric electron density and thereby provide reliable approaches to ionospheric soundings. Our study can improve current understanding of the capability and insufficiency of these two methods on the large-scale IED reconstruction.

Decreased photochemical efficiency of photosystem II following sunlight exposure of shade-grown leaves of avocado: because of, or in spite of, two kinetically distinct xanthophyll cycles?

PubMed

Jia, Husen; Förster, Britta; Chow, Wah Soon; Pogson, Barry James; Osmond, C Barry

2013-02-01

This study resolved correlations between changes in xanthophyll pigments and photosynthetic properties in attached and detached shade-grown avocado (Persea americana) leaves upon sun exposure. Lutein epoxide (Lx) was deepoxidized to lutein (L), increasing the total pool by ΔL over 5 h, whereas violaxanthin (V) conversion to antheraxanthin (A) and zeaxanthin (Z) ceased after 1 h. During subsequent dark or shade recovery, de novo synthesis of L and Z continued, followed by epoxidation of A and Z but not of L. Light-saturated nonphotochemical quenching (NPQ) was strongly and linearly correlated with decreasing [Lx] and increasing [L] but showed a biphasic correlation with declining [V] and increasing [A+Z] separated when V deepoxidation ceased. When considering [ΔL+Z], the monophasic linear correlation was restored. Photochemical efficiency of photosystem II (PSII) and photosystem (PSI; deduced from the delivery of electrons to PSI in saturating single-turnover flashes) showed a strong correlation in their continuous decline in sunlight and an increase in NPQ capacity. This decrease was also reflected in the initial reduction of the slope of photosynthetic electron transport versus photon flux density. Generally longer, stronger sun exposures enhanced declines in both slope and maximum photosynthetic electron transport rates as well as photochemical efficiency of PSII and PSII/PSI more severely and prevented full recovery. Interestingly, increased NPQ capacity was accompanied by slower relaxation. This was more prominent in detached leaves with closed stomata, indicating that photorespiratory recycling of CO(2) provided little photoprotection to avocado shade leaves. Sun exposure of these shade leaves initiates a continuum of photoprotection, beyond full engagement of the Lx and V cycle in the antenna, but ultimately photoinactivated PSII reaction centers.

Role of Outer Membrane C-Type Cytochromes MtrC and OmcA in Shewanella Oneidensis MR-1 Cell Production, Accumulation, and Detachment During Respiration on Hematite

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

Mitchell, Andrew C.; Peterson, L.; Reardon, Catherine L.

2012-07-01

Solid phase iron oxides are considered to be important terminal electron acceptors for microbial respiration in many anoxic environments. Besides the knowledge that cells attach to and reduce these substrates, other aspects of surface-associated cell behavior and the related cell surface components that influence cell-mineral interactions are not well understood. In the present study, wild-type cells of the dissimilatory iron-reducing bacterium Shewanella oneidensis MR-1 formed thin biofilms one-to-two cell layers in thickness when respiring on natural specular hematite under flow conditions similar to those which exist in aquatic sediments and subsurface environments. The distribution of cells within the biofilm indicatedmore » that direct contact was not required for electron transfer from cells to the mineral surface. Detached biomass in the form of single cells represented >99% of the surface-associated wild-type cell production from respiration on hematite over the biofilm life cycle. A mutant deficient in the outer membrane c35 type cytochrome OmcA, while still able to respire and replicate on hematite, established a lower steady-state cell density on the mineral surface than that of the wild-type strain. A mutant deficient in MtrC, another outer membrane c-type cytochrome, and a mutant deficient in both cytochromes were unable to reduce sufficient amounts of hematite to support detectable growth on the mineral surface. When considered in the context of previous work, the results support a growing body of evidence that the relative importance of OmcA and MtrC to cell respiration and replication depends on the form of iron oxide available as terminal electron acceptor.« less

Decreased Photochemical Efficiency of Photosystem II following Sunlight Exposure of Shade-Grown Leaves of Avocado: Because of, or in Spite of, Two Kinetically Distinct Xanthophyll Cycles?1[W

PubMed Central

Jia, Husen; Förster, Britta; Chow, Wah Soon; Pogson, Barry James; Osmond, C. Barry

2013-01-01

This study resolved correlations between changes in xanthophyll pigments and photosynthetic properties in attached and detached shade-grown avocado (Persea americana) leaves upon sun exposure. Lutein epoxide (Lx) was deepoxidized to lutein (L), increasing the total pool by ΔL over 5 h, whereas violaxanthin (V) conversion to antheraxanthin (A) and zeaxanthin (Z) ceased after 1 h. During subsequent dark or shade recovery, de novo synthesis of L and Z continued, followed by epoxidation of A and Z but not of L. Light-saturated nonphotochemical quenching (NPQ) was strongly and linearly correlated with decreasing [Lx] and increasing [∆L] but showed a biphasic correlation with declining [V] and increasing [A+Z] separated when V deepoxidation ceased. When considering [ΔL+∆Z], the monophasic linear correlation was restored. Photochemical efficiency of photosystem II (PSII) and photosystem (PSI; deduced from the delivery of electrons to PSI in saturating single-turnover flashes) showed a strong correlation in their continuous decline in sunlight and an increase in NPQ capacity. This decrease was also reflected in the initial reduction of the slope of photosynthetic electron transport versus photon flux density. Generally longer, stronger sun exposures enhanced declines in both slope and maximum photosynthetic electron transport rates as well as photochemical efficiency of PSII and PSII/PSI more severely and prevented full recovery. Interestingly, increased NPQ capacity was accompanied by slower relaxation. This was more prominent in detached leaves with closed stomata, indicating that photorespiratory recycling of CO2 provided little photoprotection to avocado shade leaves. Sun exposure of these shade leaves initiates a continuum of photoprotection, beyond full engagement of the Lx and V cycle in the antenna, but ultimately photoinactivated PSII reaction centers. PMID:23213134

Impact of Cross-field Drifts on Detachment in DIII-D

NASA Astrophysics Data System (ADS)

Jaervinen, A. E.; Allen, S. L.; McLean, A. G.; Rognlien, T. D.; Samuell, C. M.; Porter, G. D.; Groth, M.; Hill, D. N.; Leonard, A. W.

2017-10-01

Simulations of DIII-D plasmas have revealed the strong role of E ×B-drifts in the low field side (LFS) detachment structure. High confinement modes (H-mode) with the ∇B-drift towards the X-point (fwd BT) enter detachment at 20% higher upstream density, ne,sep, than plasmas with the ∇B-drift away from the X-point (rev BT). In contrast, low confinement modes (L-mode) enter detachment at 10% lower ne,sep in fwd BT. Despite this, both L- and H-modes detached plasmas show strong target flux, JSAT, reduction with increasing ne,sep in fwd BT, while only a modest reduction occurs in rev BT. In fwd BT H-mode, a step-wise transition from attached to strongly detached conditions is observed with increasing ne,sep. UEDGE simulations indicate that the strong poloidal E ×B-drift in the private flux region in H-mode drives the difference for the detachment onset relative to L-mode. In fwd BT, the dependence of this poloidal E ×B-drift on the divertor conditions can reinforce the plasma into either attached or strongly detached state. In rev BT, radial E ×B-drift depletes strike-line ne, limiting the degree of detachment. Work supported by the US DOE under DE-FC02-04ER54698, DE-AC52-07NA27344, and LLNL LDRD project 17-ERD-020.

Risk of progression in macula-on rhegmatogenous retinal detachment.

PubMed

Callizo, Josep; Pfeiffer, Sebastian; Lahme, Eva; van Oterendorp, Christian; Khattab, Mohammed; Bemme, Sebastian; Kulanga, Miroslav; Hoerauf, Hans; Feltgen, Nicolas

2017-08-01

To identify factors that may lead to a rapid progression in macula-on rhegmatogenous retinal detachment (RRD), in particular, those that may lead to macular involvement. Observational, prospective, single-center study. Patients referred for surgery due to primary rhegmatogenous retinal detachment with the macula on between 2009 and 2013 were included. Relevant factors analyzed included age, time delay until surgery, lens status, myopia, the detachment's location and configuration as well as number, size and type of retinal breaks. Eyes underwent optical coherence tomography to detect macular detachment. A multivariate analysis was performed to investigate the effect of several factors in the progression of retinal detachment. A total of 116 eyes of 116 patients were included. Mean time delay between admission and surgery was 1.8 ± 1.4 days. Progression was observed in 19.8% of the eyes. Of those, 47.8% presented macular detachment. Ten of the 11 (90.9%) eyes presenting progression involving the macula also exhibited a bullous configuration, which was the only parameter that correlated significantly with detachment progression in patients with (p = 0.0036) and without (p = 0.0014) macular involvement. For the first time in a prospective trial, a bullous configuration was found to be a highly significant predictor for progression in macula-on detachments. Our data support prompt surgery in patients diagnosed with bullous macula-on RRD.

Selective scanning tunnelling microscope electron-induced reactions of single biphenyl molecules on a Si(100) surface.

PubMed

Riedel, Damien; Bocquet, Marie-Laure; Lesnard, Hervé; Lastapis, Mathieu; Lorente, Nicolas; Sonnet, Philippe; Dujardin, Gérald

2009-06-03

Selective electron-induced reactions of individual biphenyl molecules adsorbed in their weakly chemisorbed configuration on a Si(100) surface are investigated by using the tip of a low-temperature (5 K) scanning tunnelling microscope (STM) as an atomic size source of electrons. Selected types of molecular reactions are produced, depending on the polarity of the surface voltage during STM excitation. At negative surface voltages, the biphenyl molecule diffuses across the surface in its weakly chemisorbed configuration. At positive surface voltages, different types of molecular reactions are activated, which involve the change of adsorption configuration from the weakly chemisorbed to the strongly chemisorbed bistable and quadristable configurations. Calculated reaction pathways of the molecular reactions on the silicon surface, using the nudge elastic band method, provide evidence that the observed selectivity as a function of the surface voltage polarity cannot be ascribed to different activation energies. These results, together with the measured threshold surface voltages and the calculated molecular electronic structures via density functional theory, suggest that the electron-induced molecular reactions are driven by selective electron detachment (oxidation) or attachment (reduction) processes.

31 CFR 358.6 - What is the procedure for converting bearer corpora and detached bearer coupons to book-entry?

Code of Federal Regulations, 2011 CFR

2011-07-01

... bearer corpora and detached bearer coupons to book-entry? 358.6 Section 358.6 Money and Finance: Treasury... PUBLIC DEBT REGULATIONS GOVERNING BOOK-ENTRY CONVERSION OF BEARER CORPORA AND DETACHED BEARER COUPONS § 358.6 What is the procedure for converting bearer corpora and detached bearer coupons to book-entry...

Identifying the role of cytochromes upon the attachment, growth and detachment of Shewanella oneidensis MR-1 on hematite during dissimilatory iron reduction under natural- flow conditions

NASA Astrophysics Data System (ADS)

Mitchell, A. C.; Geesey, G. G.

2006-12-01

Current understanding of bacterial respiration by dissimilatory iron (Fe) reduction is based primarily on studies of closed systems using soluble Fe(III). However, natural environments likely to support Fe reduction are typically open systems and contain Fe(III) primarily in the form of crystalline (hydr)oxides. Mechanisms by which electrons are transported between bacteria and mineral terminal electron acceptors (TEAs) under open system conditions are still poorly understood. However, a number of cytochromes have been identified as potentially playing a critical role in the electron transport system of some Fe reducing bacteria. Experiments were performed using (i) omcA, (ii) mtrC, or (iii) omcA and mtrC cytochrome deficient mutants of the Fe-reducing bacteria, Shewanella oneidensis MR-1, in transparent-window flow- reactors containing hematite as the only TEA. These were operated under defined hydrodynamic and anaerobic conditions. Cells expressed green fluorescent protein (gfp), allowing real time measurement of cells at the mineral surface by epifluorescence microscopy. Cytochromes which play a critical role in the anaerobic growth of S. Oneidensis by Fe reduction under open system natural-flow conditions could then be identified. Differences in the accumulation, maximum density, detachment and total production of surface-associated cells growing on hematite surfaces were apparent between the mutants, and between the mutants and the wild-type. Mutants deficient in cytochromes grew to a lower max density by up to 2 orders of magnitude than the wild-type, and exhibited no reduced Fe in the reactor effluent or at the surface of the hematite at the conclusion of the experiment, as revealed by X-Ray photoelectron spectroscopy (XPS). Therefore omcA and / or mtrC cytochromes appear critical for electron shuttling and anaerobic growth of S. Oneidensis on hematite under natural-flow conditions.

Improved Crystal Quality By Detached Solidification in Microgravity

NASA Technical Reports Server (NTRS)

Regel, Liya L.; Wilcox, William R.; Wang, Yaz-Hen; Wang, Jian-Bin

2003-01-01

Many microgravity directional solidification experiments yielded ingots with portions that grew without contacting the ampoule wall, leading to greatly improved crystallographic perfection. Our long term goals have been: (1) To develop a complete understanding of all of the phenomena of detached solidification.; (2) To make it possible to achieve detached solidification reproducibly; (3) To increase crystallographic perfection through detached solidification. We have three major achievements to report here: (1) We obtained a new material balance solution for the Moving Meniscus Model of detached solidification. This solution greatly clarifies the physics as well as the roles of the parameters in the system; (2) We achieved detached solidification of InSb growing on earth in BN-coated ampoules; (3) We performed an extensive series of experiments on freezing water that showed how to form multiple gas bubbles or tubes on the ampoule wall. However, these did not propagate around the wall and lead to fully detached solidification unless the ampoule wall was extremely rough and non-wetted.

The Death Valley turtlebacks reinterpreted as Miocene­ Pliocene folds of a major detachment surface

USGS Publications Warehouse

Holm, Daniel K.; Fleck, Robert J.; Lux, Daniel R.

1994-01-01

Determining the origin of extension parallel folds in metamorphic core complexes is fundamental to understanding the development of detachment faults. An excellent example of such a feature occurs in the Death Valley region of California where a major, undulatory, detachment fault is exposed along the well-known turtleback (antiformal) surfaces of the Black Mountains. In the hanging wall of this detachment fault are deformed strata of the Copper Canyon Formation. New age constraints indicate that the Copper Canyon Formation was deposited from ~6 to 3 Ma. The formation was folded during deposition into a SE-plunging syncline with an axial surface coplanar with that of a synform in the underlying detachment. This relation suggests the turtlebacks are a folded detachment surface formed during large-scale extension in an overall constrictional strain field. The present, more planar, Black Mountains frontal fault system may be the result of out-stepping of a normal fault system away from an older detachment fault that was deactivated by folding.

Photoexcitation and ionization in carbon dioxide - Theoretical studies in the separated-channel static-exchange approximation

NASA Technical Reports Server (NTRS)

Padial, N.; Csanak, G.; Mckoy, B. V.; Langhoff, P. W.

1981-01-01

Vertical-electronic static-exchange photoexcitation and ionization cross sections are reported which provide a first approximation to the complete dipole spectrum of CO2. Separated-channel static-exchange calculations of vertical-electronic transition energies and oscillator strengths, and Stieltjes-Chebyshev moment methods were used in the development. Detailed comparisons were made of the static-exchange excitation and ionization spectra with photoabsorption, electron-impact excitation, and quantum-defect estimates of discrete transition energies and intensities, and with partial-channel photoionization cross sections obtained from fluorescence measurements and from tunable-source and (e, 2e) photoelectron spectroscopy. Results show that the separate-channel static-exchange approximation is generally satisfactory in CO2.

Direct versus indirect many-body methods for calculating vertical electron affinities: applications to F -, OH - , NH 2-, CN -, Cl -, SH - and PH 2-

NASA Astrophysics Data System (ADS)

Ortiz, J. V.

1987-05-01

Electron propagator theory (EPT) is applied to calculating vertical ionization energies of the anions F -, Cl -, OH -,SH -, NH 2-, PH 2- and CN -. Third-order and outer valence approximation (OVA) quasiparticle calculations are compared with ΔMBPT(4) (MBPT, many-body perturbation theory) results using the same basis sets. Agreement with experiment is satisfactory for EPT calculations except for F - and OH -, while the ΔMBPT treatments fail for CN -. EPT(OVA) estimates are reliable when the discrepancy between second- and third-order results is small. Computational aspects are discussed, showing relative merits of direct and indirect methods for evaluating electron binding energies.

Vertically grown nanowire crystals of dibenzotetrathienocoronene (DBTTC) on large-area graphene

DOE PAGES

Kim, B.; Chiu, C. -Y.; Kang, S. J.; ...

2016-06-01

Here we demonstrate controlled growth of vertical organic crystal nanowires on single layer graphene. Using Scanning Electron Microscopy (SEM), high-resolution transition electron microscopy (TEM), and Grazing Incidence X-ray Diffraction (GIXD), we probe the microstructure and morphology of dibenzotetrathienocoronene (DBTTC) nanowires epitaxially grown on graphene. The investigation is performed at both the ensemble and single nanowire level, and as function of growth parameters, providing insight of and control over the formation mechanism. Finally, the size, density and height of the nanowires can be tuned via growth conditions, opening new avenues for tailoring three-dimensional (3-D) nanostructured architectures for organic electronics with improvedmore » functional performance.« less

RELATIONSHIP BETWEEN ISOKINETIC KNEE STRENGTH AND JUMP CHARACTERISTICS FOLLOWING ANTERIOR CRUCIATE LIGAMENT RECONSTRUCTION.

PubMed

Laudner, Kevin; Evans, Daniel; Wong, Regan; Allen, Aaron; Kirsch, Tom; Long, Brian; Meister, Keith

2015-06-01

Clinicians are often challenged when making return-to-play decisions following anterior cruciate ligament reconstruction (ACL-R). Isokinetic strength and jump performance testing are common tools used to make this decision. Unfortunately, vertical jump performance standards have not been clearly established and many clinicians do not have access to isokinetic testing equipment. To establish normative jump and strength characteristics in ACL-R patients cleared by an orthopedic physician to return-to-play and to determine if relationships exist between knee isokinetic strength measurements and jump characteristics described using an electronic jump map system. Descriptive laboratory study. Thirty-three ACL-R patients who had been cleared to return to athletic competition participated in this study. Twenty-six of these ACL-R participants were also matched to 26 asymptomatic athletes based on sex, limb, height, and mass to determine isokinetic strength and jump characteristic differences between groups. Jump tests consisted of single leg vertical, double leg vertical, and a 4-jump single leg vertical jump assessed using an electronic jump mat system. Independent t-tests were used to determine differences between groups and multiple regression analyses were used to identify any relationships between jump performance and knee strength (p<0.05). The ACL-R group had lower vertical jump capabilities and some bilateral knee strength deficiencies compared to the matched control group. The ACL-R group also showed several moderate-to-strong positive relationships for both knee extension and flexion strength with several jump performance characteristics, such as single and double leg vertical jump height. The current results indicate that ACL-R patients present with several knee strength and vertical jump differences compared to a matched control group at the time of return-to-play. Also, ACL-R patient's performance on an electronic jump mat system is strongly related to isokinetic knee strength measures. 2b.

Highly flexible electronics from scalable vertical thin film transistors.

PubMed

Liu, Yuan; Zhou, Hailong; Cheng, Rui; Yu, Woojong; Huang, Yu; Duan, Xiangfeng

2014-03-12

Flexible thin-film transistors (TFTs) are of central importance for diverse electronic and particularly macroelectronic applications. The current TFTs using organic or inorganic thin film semiconductors are usually limited by either poor electrical performance or insufficient mechanical flexibility. Here, we report a new design of highly flexible vertical TFTs (VTFTs) with superior electrical performance and mechanical robustness. By using the graphene as a work-function tunable contact for amorphous indium gallium zinc oxide (IGZO) thin film, the vertical current flow across the graphene-IGZO junction can be effectively modulated by an external gate potential to enable VTFTs with a highest on-off ratio exceeding 10(5). The unique vertical transistor architecture can readily enable ultrashort channel devices with very high delivering current and exceptional mechanical flexibility. With large area graphene and IGZO thin film available, our strategy is intrinsically scalable for large scale integration of VTFT arrays and logic circuits, opening up a new pathway to highly flexible macroelectronics.

Vertical Si nanowire arrays fabricated by magnetically guided metal-assisted chemical etching

NASA Astrophysics Data System (ADS)

Chun, Dong Won; Kim, Tae Kyoung; Choi, Duyoung; Caldwell, Elizabeth; Kim, Young Jin; Paik, Jae Cheol; Jin, Sungho; Chen, Renkun

2016-11-01

In this work, vertically aligned Si nanowire arrays were fabricated by magnetically guided metal-assisted directional chemical etching. Using an anodized aluminum oxide template as a shadow mask, nanoscale Ni dot arrays were fabricated on an Si wafer to serve as a mask to protect the Si during the etching. For the magnetically guided chemical etching, we deposited a tri-layer metal catalyst (Au/Fe/Au) in a Swiss-cheese configuration and etched the sample under the magnetic field to improve the directionality of the Si nanowire etching and increase the etching rate along the vertical direction. After the etching, the nanowires were dried with minimal surface-tension-induced aggregation by utilizing a supercritical CO2 drying procedure. High-resolution transmission electron microscopy (HR-TEM) analysis confirmed the formation of single-crystal Si nanowires. The method developed here for producing vertically aligned Si nanowire arrays could find a wide range of applications in electrochemical and electronic devices.

Magnetoresistance effect in Fe{sub 20}Ni{sub 80}/graphene/Fe{sub 20}Ni{sub 80} vertical spin valves

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

Entani, Shiro, E-mail: entani.shiro@qst.go.jp; Naramoto, Hiroshi; Sakai, Seiji

2016-08-22

Vertical spin valve devices with junctions of single- and bi-layer graphene interlayers sandwiched with Fe{sub 20}Ni{sub 80} (Permalloy) electrodes were fabricated by exploiting the direct growth of graphene on the Permalloy. The linear current-voltage characteristics indicated that ohmic contacts were realized at the interfaces. The systematic characterization revealed the significant modification of the electronic state of the interfacial graphene layer on the Permalloy surface, which indicates the strong interactions at the interface. The ohmic transport was attributable to the strong interface-interaction. The vertical resistivity of the graphene interlayer and the spin asymmetry coefficient at the graphene/Permalloy interface were obtained tomore » be 0.13 Ω cm and 0.06, respectively. It was found that the strong interface interaction modifies the electronic structure and metallic properties in the vertical spin valve devices with bi-layer graphene as well as single-layer graphene.« less

Tuning the Electronic, Optical, and Magnetic Properties of Monolayer GaSe with a Vertical Electric Field

NASA Astrophysics Data System (ADS)

Ke, Congming; Wu, Yaping; Guo, Guang-Yu; Lin, Wei; Wu, Zhiming; Zhou, Changjie; Kang, Junyong

2018-04-01

Inspired by two-dimensional material with their unique physical properties and innovative device applications, here we report a design framework on monolayer GaSe, an important member of the two-dimensional material family, in an effort to tune the electronic, optical, and magnetic properties through a vertical electric field. A transition from indirect to direct band gap in monolayer GaSe is found with an electric field of 0.09 V /Å . The giant Stark effect results in a reduction of the band gap with a Stark coefficient of 3.54 Å. Optical and dielectric properties of monolayer GaSe are dependent on the vertical electric field. A large regulation range for polarization E ∥c ^ is found for the static dielectric constant. The optical anisotropy with the dipole transition from E ∥c ^ to E ⊥c ^ is achieved. Induced by the spin-orbit coupling, spin-splitting energy at the valence band maximum increases linearly with the electric field. The effective mass of holes is highly susceptible to the vertical electric field. Switchable spin-polarization features in spin texture of monolayer GaSe are predicted. The tunable electronic, optical, and magnetic properties of monolayer GaSe hold great promise for applications in both the optoelectronic and spintronic devices.

Photoelectron spectroscopy of the doubly-charged anions [MIVO(mnt)2]2- (M = Mo, W; mnt = S2C2(CN)2(2-): access to the ground and excited states of the [MVO(mnt)2]- anion.

PubMed

Waters, Tom; Wang, Xue-Bin; Yang, Xin; Zhang, Lianyi; O'Hair, Richard A J; Wang, Lai-Sheng; Wedd, Anthony G

2004-04-28

Photodetachment photoelectron spectroscopy was used to investigate the electronic structure of the doubly charged complexes [MIVO(mnt)2]2- (M = Mo, W; mnt = 1,2-dicyanoethenedithiolato). These dianions are stable in the gas phase and are minimal models for the active sites of the dimethyl sulfoxide reductase family of molybdenum enzymes and of related tungsten enzymes. Adiabatic and vertical electron binding energies for both species were measured, providing detailed information about molecular orbital energy levels of the parent dianions as well as the ground and excited states of the product anions [MVO(mnt)2]-. Density functional theory calculations were used to assist assignment of the detachment features. Differences in energy between these features provided the energies of ligand-to-metal charge-transfer transitions from S(pi) and S(sigma) molecular orbitals to the singly occupied metal-based orbital of the products [MVO(mnt)2]-. These unique data for the M(V) species were obtained at the C(2)(v)() geometry of the parent M(IV) dianions. However, theoretical calculations and available condensed phase data suggested that a geometry featuring differentially folded dithiolene ligands (Cs point symmetry) was slightly lower in energy. The driving force for ligand folding is a favorable covalent interaction between the singly occupied metal-based molecular orbital (a1 in C2v) point symmetry; highest occupied molecular orbital (HOMO)) and the least stable of the occupied sulfur-based molecular orbitals (b1 in C2v point symmetry, HOMO-1) that is only possible upon reduction to the lower symmetry. This ligand folding induces a large increase in the intensity predicted for the a' S(pi) --> a' dx2 - y2 charge-transfer transition originating from the HOMO-2 of [MVO(mnt)2](-) under Cs point symmetry. Electronic absorption spectra are available for the related species [MoVO(bdt)2]- (bdt = 1,2-benzenedithiolato) and for the oxidized form of dimethyl sulfoxide reductase. The intense absorptions at approximately 1.7 eV have been assigned previously to S(sigma) --> Mo transitions, assuming C2v geometry. The present work indicates that the alternative a' S(pi) --> a' dx2 - y2 of Cs geometry must be considered. Overall, this study confirms that the electronic structure of the M-dithiolene units are exquisitely sensitive to dithiolene ligand folding, reinforcing the proposal that these units are tunable conduits for electron transfer in enzyme systems.

Rear Detachments: Capturing and Resourcing How the Army Fights

DTIC Science & Technology

2012-03-22

TDA ) for rear detachments to improve collective training and mission execution. 15. SUBJECT TERMS Rear Detachments, Doctrine, Organization, 16...as well as recommending that the Army establish a small Tables of Distribution and Allowances ( TDA ) for rear detachments to improve collective...and allowances ( TDA ), does not have substantive doctrine to guide its formation and operation, and generally organizes late in the ARFORGEN cycle

Light Scattering by Marine Particles: Modeling with Non-Spherical Shapes

DTIC Science & Technology

2011-04-15

scattering by nonspherical particles: application to coccoliths detached from Emiliania huxleyi. Limnology and Oceanography, 46. 1438— 1454,2001. H.R...application to coccoliths detached from Emiliania huxleyi," Limnol. Oceanogr. 46, 1438-1454 (2001). 5. H.R.Gordon, "Backscattering of light from...by coccoliths detached from Emiliania huxleyi," Applied Optics, 48, 6059-6073 (2009). Light scattering by coccoliths detached from Emiliania

Spectral domain optical coherence tomography and fundus autofluorescence findings in cytomegalovirus retinitis in HIV-infected patients.

PubMed

Yashiro, Shigeko; Nishijima, Takeshi; Yamamoto, Yuuka; Sekine, Yumi; Yoshida-Hata, Natsuyo; Iida, Tomohiro; Oka, Shinichi

2018-05-01

To assess the usefulness of spectral domain optical coherence tomography (SD-OCT) and fundus autofluorescence (FAF) findings in cytomegalovirus (CMV) retinitis. Observational case series. Thirteen eyes of 11 human immunodeficiency virus (HIV)-positive patients with CMV retinitis underwent full ophthalmologic examinations, SD-OCT, and 4 eyes of 4 patients underwent FAF. FAF images included short-wavelength autofluorescence (SW-AF) and near-infrared autofluorescence (IR-AF). CMV retinitis was classified into proposed categories of acute, subacute, remission, and recurrent; the acute stage was further subdivided into initial, early, and late stages. In the initial stage, vertical structural disruption of all retinal layers was observed by SD-OCT, and FAF showed hyperautofluorescence on SW-AF and hypoautofluorescence on IR-AF. In the early stage, SD-OCT showed significant retinal thickening; cells and debris from the retinal surface to the vitreous; enlarged vessels with/without thickened vessel walls; and highly complicated serous retinal detachment. In the late to subacute stage, features observed included rhegmatogenous retinal detachment with shrinking posterior hyaloid membrane and waving from the ellipsoid zone to the retinal pigment epithelium. In remission, FAF findings were hypoautofluorescence on SW-AF and hyperautofluorescence on IR-AF. Although the number of examined eyes was limited, SD-OCT and FAF provide new information in various stages of CMV retinitis in patients with HIV infection that is not obtainable by conventional examination and which may be of great benefit when screening for the initial stage of CMV retinitis.

Defect, Kinetics and Heat Transfer of CDTE Bridgman Growth without Wall Contact

NASA Technical Reports Server (NTRS)

Larson, D. J., Jr.; Zhang, H.

2003-01-01

A detached growth mechanism has been proposed, which is similar to that proposed by Duffar et al. and used to study the current detached growth system. From numerical results, we can conclude that detached growth will more likely appear if the growth and wetting angles are large and meniscus is flat. Detached thickness is dependent on growth angle, wetting angle, and gap width and shape of the fins. The model can also explain why the detached growth will not happen for metals in which the growth angle is almost zero. Since the growth angle of CdZnTe cannot be changed, to promote detached growth, the number density of the fins should be low and the wetting angle should be high. Also, a much smaller gap width of the fins should be used in the ground experiment and the detached gap width is much smaller. The shape of the fins has minor influence on detached growth. An integrated numerical model for detached solidification has been developed combining a global heat transfer sub-model and a wall contact sub-model. The global heat transfer sub-model accounts for heat and mass transfer in the multiphase system, convection in the melt, macro-segregation, and interface dynamics. The location and dynamics of the solidification interface are accurately tracked by a multizone adaptive grid generation scheme. The wall contact sub-model accounts for the meniscus dynamics at the three-phase boundary. Simulations have been performed for crystal growth in a conventional ampoule and a designed ampoule to understand the benefits of detached solidification and its impacts on crystalline structural quality, e.g., stoichiometry, macro-segregation, and stress. From simulation results, both the Grashof and Marangoni numbers will have significant effects on the shape of growth front, Zn concentration distribution, and radial segregation. The integrated model can be used in designing apparatus and determining the optimal geometry for detached solidification in space and on the ground.

Effects of low-Z and high-Z impurities on divertor detachment and plasma confinement

DOE PAGES

Wang, H. Q.; Guo, Houyang Y.; Petrie, Thomas W.; ...

2017-03-18

The impurity-seeded detached divertor is essential for heat exhaust in ITER and other reactor-relevant devices. Dedicated experiments with injection of N 2, Ne and Ar have been performed in DIII-D to assess the impact of the different impurities on divertor detachment and confinement. Seeding with N 2, Ne and Ar all promote divertor detachment, greatly reducing heat flux near the strike point. The upstream plasma density at the onset of detachment decreases with increasing impurity-puffing flow rates. For all injected impurity species, the confinement and pedestal pressure are correlated with the impurity content and the ratio of separatrix loss powermore » to the L-H transition threshold power. As the divertor plasma approaches detachment, the high-Z impurity seeding tends to degrade the core confinement owing to the increased core radiation. In particular, Ar injection leads to an increase in core radiation, up to 50% of the injected power, and a reduction in pedestal temperature over 60%, thus significantly degrading the confinement, i.e., with H 98 reducing from 1.1 to below 0.7. As for Ne seeding, H 98 near 0.8 can be maintained during the detachment phase with the pedestal temperature being reduced by about 50%. In contrast, in the N 2 seeded plasmas, radiation is predominately confined in the boundary plasma, with up to 50% of heating power being radiated in the divertor region and less than 25% in the core at the onset of detachment. In the case of strong N 2 gas puffing, the confinement recovers during the detachment, from ~20% reduction at the onset of the detachment to greater than that before the seeding. The core and pedestal temperatures feature a reduction of 30% from the initial attached phase and remain nearly constant during the detachment phase. The improvement in confinement appears to arise from the increase in pedestal and core density despite the temperature reduction.« less

Effect of 3D magnetic perturbations on divertor conditions and detachment in tokamak and stellarator

DOE PAGES

Ahn, J. -W.; Briesemester, A. R.; Kobayashi, M.; ...

2017-06-22

Enhanced perpendicular heat and momentum transport induces parallel pressure loss leading to divertor detachment, which can be produced by the increase of density in 2D tokamaks. However, in the 3D configurations such as tokamaks with 3D fields and stellarators, the fraction of perpendicular transport can be higher even in a lower density regime, which could lead to the early transition to detachment without passing through the high-recycling regime. 3D fields applied to the limiter tokamak plasmas produce edge stochastic layers close to the last closed flux surface (LCFS), which can allow for enhanced perpendicular transport and indeed the absence ofmore » high recycling regime and early detachment have been observed in TEXTOR and Tore Supra. However, in the X-point divertor tokamaks with the applied 3D fields, the parallel transport is still dominant and the detachment facilitation has not been observed yet. Rather, 3D fields affected detachment adversely under certain conditions, either by preventing detachment onset as seen in DIII-D or by re-attaching the existing detached plasma as shown in NSTX. The possible way for strong 3D effects to induce access to the early detachment in divertor tokamaks appears to be via significant perpendicular loss of parallel momentum by frictional force for the counter-streaming flows between neighboring flow channels in the divertor. In principle, the adjacent lobes in the 3D divertor tokamak may generate the counter-streaming flow channels. However, an EMC3-EIRENE simulation for ITER H-mode plasmas demonstrated that screened RMP leads to significantly reduced counter-flows near the divertor target, therefore the momentum loss effect leading to detachment facilitation is expected to be small. This is consistent with the observation in LHD, which showed screening (amplification) of RMP fields in the attachment (stable detachment) case. In conclusion, work for optimal parameter window for best divertor operation scenario is needed particularly for the 3D divertor tokamak configuration.« less

Effect of 3D magnetic perturbations on divertor conditions and detachment in tokamak and stellarator

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

Ahn, J. -W.; Briesemester, A. R.; Kobayashi, M.

Enhanced perpendicular heat and momentum transport induces parallel pressure loss leading to divertor detachment, which can be produced by the increase of density in 2D tokamaks. However, in the 3D configurations such as tokamaks with 3D fields and stellarators, the fraction of perpendicular transport can be higher even in a lower density regime, which could lead to the early transition to detachment without passing through the high-recycling regime. 3D fields applied to the limiter tokamak plasmas produce edge stochastic layers close to the last closed flux surface (LCFS), which can allow for enhanced perpendicular transport and indeed the absence ofmore » high recycling regime and early detachment have been observed in TEXTOR and Tore Supra. However, in the X-point divertor tokamaks with the applied 3D fields, the parallel transport is still dominant and the detachment facilitation has not been observed yet. Rather, 3D fields affected detachment adversely under certain conditions, either by preventing detachment onset as seen in DIII-D or by re-attaching the existing detached plasma as shown in NSTX. The possible way for strong 3D effects to induce access to the early detachment in divertor tokamaks appears to be via significant perpendicular loss of parallel momentum by frictional force for the counter-streaming flows between neighboring flow channels in the divertor. In principle, the adjacent lobes in the 3D divertor tokamak may generate the counter-streaming flow channels. However, an EMC3-EIRENE simulation for ITER H-mode plasmas demonstrated that screened RMP leads to significantly reduced counter-flows near the divertor target, therefore the momentum loss effect leading to detachment facilitation is expected to be small. This is consistent with the observation in LHD, which showed screening (amplification) of RMP fields in the attachment (stable detachment) case. In conclusion, work for optimal parameter window for best divertor operation scenario is needed particularly for the 3D divertor tokamak configuration.« less

Ammonia-hydrogen bromide and ammonia-hydrogen iodide complexes: anion photoelectron and ab initio studies.

PubMed

Eustis, S N; Whiteside, A; Wang, D; Gutowski, M; Bowen, K H

2010-01-28

The ammonia-hydrogen bromide and ammonia-hydrogen iodide, anionic heterodimers were studied by anion photoelectron spectroscopy. In complementary studies, these anions and their neutral counterparts were also investigated via ab initio theory at the coupled cluster level. In both systems, neutral NH(3)...HX dimers were predicted to be linear, hydrogen-bonded complexes, whereas their anionic dimers were found to be proton-transferred species of the form, (NH(4)(+)X(-))(-). Both experimentally measured and theoretically predicted vertical detachment energies (VDE) are in excellent agreement for both systems, with values for (NH(4)(+)Br(-))(-) being 0.65 and 0.67 eV, respectively, and values for (NH(4)(+)I(-))(-) being 0.77 and 0.81 eV, respectively. These systems are discussed in terms of our previous study of (NH(4)(+)Cl(-))(-).

Launch and capture of a single particle in a pulse-laser-assisted dual-beam fiber-optic trap

NASA Astrophysics Data System (ADS)

Fu, Zhenhai; She, Xuan; Li, Nan; Hu, Huizhu

2018-06-01

The rapid loading and manipulation of microspheres in optical trap is important for its applications in optomechanics and precision force sensing. We investigate the microsphere behavior under coaction of a dual-beam fiber-optic trap and a pulse laser beam, which reveals a launched microsphere can be effectively captured in a spatial region. A suitable order of pulse duration for launch is derived according to the calculated detachment energy threshold of pulse laser. Furthermore, we illustrate the effect of structural parameters on the launching process, including the spot size of pulse laser, the vertical displacement of beam waist and the initial position of microsphere. Our result will be instructive in the optimal design of the pulse-laser-assisted optical tweezers for controllable loading mechanism of optical trap.

Potentiostatic current and galvanostatic potential oscillations during electrodeposition of cadmium.

PubMed

López-Sauri, D A; Veleva, L; Pérez-Ángel, G

2015-09-14

Cathodic current and potential oscillations were observed during electrodeposition of cadmium from a cyanide electrolyte on a vertical platinum electrode, in potentiostatic and galvanostatic experiments. Electrochemical impedance spectroscopy experiments revealed a region of negative real impedance in a range of non-zero frequencies, in the second descending branch with a positive slope of the N-shape current-potential curve. This kind of dynamical behaviour is characteristic of the HN-NDR oscillators (oscillators with the N-Shape current-potential curve and hidden negative differential resistance). The oscillations could be mainly attributed to the changes in the real active cathodic area, due to the adsorption of hydrogen molecules and their detachment from the surface. The instabilities of the electrochemical processes were characterized by time series, Fast Fourier Transforms and 2-D phase portraits showing quasi-periodic oscillations.

Controlled tuning of the radiative lifetime in InAs self-assembled quantum dots through vertical ordering

NASA Astrophysics Data System (ADS)

Colocci, M.; Vinattieri, A.; Lippi, L.; Bogani, F.; Rosa-Clot, M.; Taddei, S.; Bosacchi, A.; Franchi, S.; Frigeri, P.

1999-01-01

Multilayer structures of InAs quantum dots have been studied by means of photoluminescence techniques. A strong increase of the radiative lifetime with increasing number of stacked dot layers has been observed at low temperatures. Moreover, a strong temperature dependence of the radiative lifetime, which is not present in the single layer samples, has been found in the multistacked structures. The observed effects are nicely explained as a consequence of the electronic coupling between electrons and holes induced by vertical ordering.

A Meta-Analysis on Antecedents and Outcomes of Detachment from Work.

PubMed

Wendsche, Johannes; Lohmann-Haislah, Andrea

2016-01-01

Detachment from work has been proposed as an important non-work experience helping employees to recover from work demands. This meta-analysis (86 publications, k = 91 independent study samples, N = 38,124 employees) examined core antecedents and outcomes of detachment in employee samples. With regard to outcomes, results indicated average positive correlations between detachment and self-reported mental (i.e., less exhaustion, higher life satisfaction, more well-being, better sleep) and physical (i.e., lower physical discomfort) health, state well-being (i.e., less fatigue, higher positive affect, more intensive state of recovery), and task performance (small to medium sized effects). However, average relationships between detachment and physiological stress indicators and work motivation were not significant while associations with contextual performance and creativity were significant, but negative. Concerning work characteristics, as expected, job demands were negatively related and job resources were positively related to detachment (small sized effects). Further, analyses revealed that person characteristics such as negative affectivity/neuroticism (small sized effect) and heavy work investment (medium sized effect) were negatively related to detachment whereas detachment and demographic variables (i.e., age and gender) were not related. Moreover, we found a medium sized average negative relationship between engagement in work-related activities during non-work time and detachment. For most of the examined relationships heterogeneity of effect sizes was moderate to high. We identified study design, samples' gender distribution, and affective valence of work-related thoughts as moderators for some of these aforementioned relationships. The results of this meta-analysis point to detachment as a non-work (recovery) experience that is influenced by work-related and personal characteristics which in turn is relevant for a range of employee outcomes.

Tauroursodeoxycholic Acid (TUDCA) Protects Photoreceptors from Cell Death after Experimental Retinal Detachment

PubMed Central

Mantopoulos, Dimosthenis; Murakami, Yusuke; Comander, Jason; Thanos, Aristomenis; Roh, Miin; Miller, Joan W.; Vavvas, Demetrios G.

2011-01-01

Background Detachment of photoreceptors from the underlying retinal pigment epithelium is seen in various retinal disorders such as retinal detachment and age-related macular degeneration and leads to loss of photoreceptors and vision. Pharmacologic inhibition of photoreceptor cell death may prevent this outcome. This study tests whether systemic administration of tauroursodeoxycholic acid (TUDCA) can protect photoreceptors from cell death after experimental retinal detachment in rodents. Methodology/Principal Findings Retinal detachment was created in rats by subretinal injection of hyaluronic acid. The animals were treated daily with vehicle or TUDCA (500 mg/kg). TUNEL staining was used to evaluate cell death. Photoreceptor loss was evaluated by measuring the relative thickness of the outer nuclear layer (ONL). Macrophage recruitment, oxidative stress, cytokine levels, and caspase levels were also quantified. Three days after detachment, TUDCA decreased the number of TUNEL-positive cells compared to vehicle (651±68/mm2 vs. 1314±68/mm2, P = 0.001) and prevented the reduction of ONL thickness ratio (0.84±0.03 vs. 0.65±0.03, P = 0.002). Similar results were obtained after 5 days of retinal detachment. Macrophage recruitment and expression levels of TNF-a and MCP-1 after retinal detachment were not affected by TUDCA treatment, whereas increases in activity of caspases 3 and 9 as well as carbonyl-protein adducts were almost completely inhibited by TUDCA treatment. Conclusions/Significance Systemic administration of TUDCA preserved photoreceptors after retinal detachment, and was associated with decreased oxidative stress and caspase activity. TUDCA may be used as a novel therapeutic agent for preventing vision loss in diseases that are characterized by photoreceptor detachment. PMID:21961034

A Meta-Analysis on Antecedents and Outcomes of Detachment from Work

PubMed Central

Wendsche, Johannes; Lohmann-Haislah, Andrea

2017-01-01

Detachment from work has been proposed as an important non-work experience helping employees to recover from work demands. This meta-analysis (86 publications, k = 91 independent study samples, N = 38,124 employees) examined core antecedents and outcomes of detachment in employee samples. With regard to outcomes, results indicated average positive correlations between detachment and self-reported mental (i.e., less exhaustion, higher life satisfaction, more well-being, better sleep) and physical (i.e., lower physical discomfort) health, state well-being (i.e., less fatigue, higher positive affect, more intensive state of recovery), and task performance (small to medium sized effects). However, average relationships between detachment and physiological stress indicators and work motivation were not significant while associations with contextual performance and creativity were significant, but negative. Concerning work characteristics, as expected, job demands were negatively related and job resources were positively related to detachment (small sized effects). Further, analyses revealed that person characteristics such as negative affectivity/neuroticism (small sized effect) and heavy work investment (medium sized effect) were negatively related to detachment whereas detachment and demographic variables (i.e., age and gender) were not related. Moreover, we found a medium sized average negative relationship between engagement in work-related activities during non-work time and detachment. For most of the examined relationships heterogeneity of effect sizes was moderate to high. We identified study design, samples' gender distribution, and affective valence of work-related thoughts as moderators for some of these aforementioned relationships. The results of this meta-analysis point to detachment as a non-work (recovery) experience that is influenced by work-related and personal characteristics which in turn is relevant for a range of employee outcomes. PMID:28133454

ERK-regulated αB-crystallin induction by matrix detachment inhibits anoikis and promotes lung metastasis in vivo.

PubMed

Malin, D; Strekalova, E; Petrovic, V; Rajanala, H; Sharma, B; Ugolkov, A; Gradishar, W J; Cryns, V L

2015-11-05

Evasion of extracellular matrix detachment-induced apoptosis ('anoikis') is a defining characteristic of metastatic tumor cells. The ability of metastatic carcinoma cells to survive matrix detachment and escape anoikis enables them to disseminate as viable circulating tumor cells and seed distant organs. Here we report that αB-crystallin, an antiapoptotic molecular chaperone implicated in the pathogenesis of diverse poor-prognosis solid tumors, is induced by matrix detachment and confers anoikis resistance. Specifically, we demonstrate that matrix detachment downregulates extracellular signal-regulated kinase (ERK) activity and increases αB-crystallin protein and messenger RNA (mRNA) levels. Moreover, we show that ERK inhibition in adherent cancer cells mimics matrix detachment by increasing αB-crystallin protein and mRNA levels, whereas constitutive ERK activation suppresses αB-crystallin induction during matrix detachment. These findings indicate that ERK inhibition is both necessary and sufficient for αB-crystallin induction by matrix detachment. To examine the functional consequences of αB-crystallin induction in anoikis, we stably silenced αB-crystallin in two different metastatic carcinoma cell lines. Strikingly, silencing αB-crystallin increased matrix detachment-induced caspase activation and apoptosis but did not affect cell viability of adherent cancer cells. In addition, silencing αB-crystallin in metastatic carcinoma cells reduced the number of viable circulating tumor cells and inhibited lung metastasis in two orthotopic models, but had little or no effect on primary tumor growth. Taken together, our findings point to αB-crystallin as a novel regulator of anoikis resistance that is induced by matrix detachment-mediated suppression of ERK signaling and promotes lung metastasis. Our results also suggest that αB-crystallin represents a promising molecular target for antimetastatic therapies.

Microstructural and fabric characterization of brittle-ductile transitional deformation of middle crustal rocks along the Jinzhou detachment fault zone, Northeast China

NASA Astrophysics Data System (ADS)

Zhang, Juyi; Jiang, Hao; Liu, Junlai

2017-04-01

Detachment fault zones (DFZs) of metamorphic core complexes generally root into the middle crust. Exhumed DFZs therefore generally demonstrate structural, microstructural and fabric features characteristic of middle to upper crustal deformation. The Jinzhou detachment fault zone from the Liaonan metamorphic core complex is characterized by the occurrence of a sequence of fault rocks due to progressive shearing along the fault zone during exhumation of the lower plate. From the exhumed fabric zonation, cataclastic rocks formed in the upper crust occur near the Jinzhou master detachment fault, and toward the lower plate gradually changed to mylonites, mylonitic gneisses and migmatitic gneisses. Correspondingly, these fault rocks have various structural, microstructural and fabric characteristics that were formed by different deformation and recrystallization mechanisms from middle to upper crustal levels. At the meanwhile, various structural styles for strain localization were formed in the DFZ. As strain localization occurs, rapid changes in deformation mechanisms are attributed to increases in strain rates or involvement of fluid phases during the brittle-ductile shearing. Optical microscopic studies reveal that deformed quartz aggregates in the lower part of the detachment fault zone are characterized by generation of dynamically recrystallized grains via SGR and BLG recrystallization. Quartz rocks from the upper part of the DFZ have quartz porphyroclasts in a matrix of very fine recrystallized grains. The porphyroclasts have mantles of sub-grains and margins grain boundary bulges. Electron backscattered diffraction technique (EBSD) quartz c-axis fabric analysis suggests that quartz grain aggregates from different parts of the DFZ possess distinct fabric complexities. The c-axis fabrics of deformed quartz aggregates from mylonitic rocks in the lower part of the detachment fault zone preserve Y-maxima which are ascribed to intermediate temperature deformation (500-630˚ C), whereas complicated fabric patterns (e.g. asymmetric single girdles) are formed in fault rocks from the upper part of the DFZ. The increasing fabric complexity is here interpreted as the result of progressive superposition of fault rocks by shearing either at relatively shallow levels or high rate of strain, during exhumation of the lower plate and shear zone rocks. The above observations and interpretations imply that dislocation creep processes contribute to the dynamic recrystallization of quartz in the middle crustal brittle-ductile transition. Progressive shearing as a consequence of exhumation of the lower plate of the MCC contributed to the obvious structural, microstructural and fabric superpositions. Strain localization occurs as the progressive shearing proceeded. Transition of mechanisms of deformation and dynamic recrystallization during strain localization may be resulted from changes in temperature conditions, in strain rates or addition of minor amount water.

Comparing the chlorine disinfection of detached biofilm clusters with those of sessile biofilms and planktonic cells in single- and dual-species cultures.

PubMed

Behnke, Sabrina; Parker, Albert E; Woodall, Dawn; Camper, Anne K

2011-10-01

Although the detachment of cells from biofilms is of fundamental importance to the dissemination of organisms in both public health and clinical settings, the disinfection efficacies of commonly used biocides on detached biofilm particles have not been investigated. Therefore, the question arises whether cells in detached aggregates can be killed with disinfectant concentrations sufficient to inactivate planktonic cells. Burkholderia cepacia and Pseudomonas aeruginosa were grown in standardized laboratory reactors as single species and in coculture. Cluster size distributions in chemostats and biofilm reactor effluent were measured. Chlorine susceptibility was assessed for planktonic cultures, attached biofilm, and particles and cells detached from the biofilm. Disinfection tolerance generally increased with a higher percentage of larger cell clusters in the chemostat and detached biofilm. Samples with a lower percentage of large clusters were more easily disinfected. Thus, disinfection tolerance depended on the cluster size distribution rather than sample type for chemostat and detached biofilm. Intact biofilms were more tolerant to chlorine independent of species. Homogenization of samples led to significantly increased susceptibility in all biofilm samples as well as detached clusters for single-species B. cepacia, B. cepacia in coculture, and P. aeruginosa in coculture. The disinfection efficacy was also dependent on species composition; coculture was advantageous to the survival of both species when grown as a biofilm or as clusters detached from biofilm but, surprisingly, resulted in a lower disinfection tolerance when they were grown as a mixed planktonic culture.