Split-face vitamin C consumer preference study.

Science.gov (United States)

Baumann, Leslie; Duque, Deysi K; Schirripa, Michael J

2014-10-01

Vitamin C is commonly used to treat aged skin. It has shown regenerative effects on skin wrinkles, texture, strength, and evenness of tone through its roles as an antioxidant, tyrosinase inhibitor, and inducer of collagen synthesis. Available vitamin C formulations on the anti-aging skin care market vary by their pH, packaging, and vehicle, which may decrease absorption, and therefore, the efficacy of the product. The purpose of this study was to assess the subjective efficacy, wearability, tolerance and overall preference of two professional vitamin C topical serums and sunscreens in Caucasian females using a split face method. A virtual split-face study of 39 Caucasian women compared two popular vitamin C and SPF product combinations - C-ESTA® Face Serum and Marini Physical Protectant SPF 45 (Jan Marini Skin, San Jose, CA; Products A) and CE Ferulic® and Physical Fusion UV Defense SPF 50 (Products B; SkinCeuticals Inc, Garland, TX). The products were assigned to each subject's left or right side of the face, and subjects rated and compared products through 5 online surveys at baseline, 24 hours, days 3, 7, and 14. Over 86% of the 35 subjects who completed the study preferred the smell and 83% preferred the feel and application of vitamin C Serum A over Serum B. Seventy-one percent of subjects preferred the feel and application of Sunscreen A over Sunscreen B. Results also showed a significant skin texture improvement and skin tone with Products A vs Product B. Products A trended higher for multiple additional categories. Products A exhibited superior anti-aging benefits than Products B. Subjects preferred the smell, feel, and application of Products A and experienced significantly less irritation than Products B. Overall, Products A were preferred over Products B with subjects willing to pay more for Products A over Products B.

More symmetrical gait after split-belt treadmill walking does not modify dynamic and postural balance in individuals post-stroke.

Science.gov (United States)

Miéville, Carole; Lauzière, Séléna; Betschart, Martina; Nadeau, Sylvie; Duclos, Cyril

2018-04-24

Spontaneous gait is often asymmetrical in individuals post-stroke, despite their ability to walk more symmetrically on demand. Given the sensorimotor deficits in the paretic limb, this asymmetrical gait may facilitate balance maintenance. We used a split-belt walking protocol to alter gait asymmetry and determine the effects on dynamic and postural balance. Twenty individuals post-stroke walked on a split-belt treadmill. In two separate periods, the effects of walking with the non-paretic leg, and then the paretic one, on the faster belt on spatio-temporal symmetry and balance were compared before and after these perturbation periods. Kinematic and kinetic data were collected using a motion analysis system and an instrumented treadmill to determine symmetry ratios of spatiotemporal parameters and dynamic and postural balance. Balance, quantified by the concepts of stabilizing and destabilizing forces, was compared before and after split-belt walking for subgroups of participants who improved and worsened their symmetry. The side on the slow belt during split-belt walking, but not the changes in asymmetry, affected balance. Difficulty in maintaining balance was higher during stance phase of the leg that was on the slow belt and lower on the contralateral side after split-belt walking, mostly because the center of pressure was closer (higher difficulty) or further (lower difficulty) from the limit of the base of support, respectively. Changes in spatiotemporal parameters may be sought without additional alteration of balance during gait post-stroke. Copyright © 2018 Elsevier Ltd. All rights reserved.

Sleep inertia during a simulated 6-h on/6-h off fixed split duty schedule.

Science.gov (United States)

Hilditch, Cassie J; Short, Michelle; Van Dongen, Hans P A; Centofanti, Stephanie A; Dorrian, Jillian; Kohler, Mark; Banks, Siobhan

Sleep inertia is a safety concern for shift workers returning to work soon after waking up. Split duty schedules offer an alternative to longer shift periods, but introduce additional wake-ups and may therefore increase risk of sleep inertia. This study investigated sleep inertia across a split duty schedule. Sixteen participants (age range 21-36 years; 10 females) participated in a 9-day laboratory study with two baseline nights (10 h time in bed, [TIB]), four 24-h periods of a 6-h on/6-h off split duty schedule (5-h TIB in off period; 10-h TIB per 24 h) and two recovery nights. Two complementary rosters were evaluated, with the timing of sleep and wake alternating between the two rosters (2 am/2 pm wake-up roster versus 8 am/8 pm wake-up roster). At 2, 17, 32 and 47 min after scheduled awakening, participants completed an 8-min inertia test bout, which included a 3-min psychomotor vigilance test (PVT-B), a 3-min Digit-Symbol Substitution Task (DSST), the Karolinska Sleepiness Scale (KSS), and the Samn-Perelli Fatigue Scale (SP-Fatigue). Further testing occurred every 2 h during scheduled wakefulness. Performance was consistently degraded and subjective sleepiness/fatigue was consistently increased during the inertia testing period as compared to other testing times. Morning wake-ups (2 am and 8 am) were associated with higher levels of sleep inertia than later wake-ups (2 pm and 8 pm). These results suggest that split duty workers should recognise the potential for sleep inertia after waking, especially during the morning hours.

Zirconium and Titanium Propylene Polymerization Precatalysts Supported by a Fluxional C 2 -Symmetric Bis(anilide)pyridine Ligand

KAUST Repository

Tonks, Ian A.

2012-03-12

Titanium and zirconium complexes supported by a bis(anilide)pyridine ligand (NNN = pyridine-2,6-bis(N-mesitylanilide)) have been synthesized and crystallographically characterized. C 2-symmetric bis(dimethylamide) complexes were generated from aminolysis of M(NMe 2) 4 with the neutral, diprotonated NNN ligand or by salt metathesis of the dipotassium salt of NNN with M(NMe 2) 2Cl 2. In contrast to the case for previously reported pyridine bis(phenoxide) complexes, the ligand geometry of these complexes appears to be dictated by chelate ring strain rather than metal-ligand π bonding. The crystal structures of the five-coordinate dihalide complexes (NNN)MCl 2 (M = Ti, Zr) display a C 1-symmetric geometry with a stabilizing ipso interaction between the metal and the anilido ligand. Coordination of THF to (NNN)ZrCl 2 generates a six-coordinate C 2-symmetric complex. Facile antipode interconversion of the C 2 complexes, possibly via flat C 2v intermediates, has been investigated by variable-temperature 1H NMR spectroscopy for (NNN)MX 2(THF) n (M = Ti, Zr; X = NMe 2, Cl) and (NNN)Zr(CH 2Ph) 2. These complexes were tested as propylene polymerization precatalysts, with most complexes giving low to moderate activities (10 2-10 4 g/(mol h)) for the formation of stereoirregular polypropylene. © 2012 American Chemical Society.

The vibration-rotation-tunneling levels of N2-H2O and N2-D2O

Science.gov (United States)

Wang, Xiao-Gang; Carrington, Tucker

2015-07-01

In this paper, we report vibration-rotation-tunneling levels of the van der Waals clusters N2-H2O and N2-D2O computed from an ab initio potential energy surface. The only dynamical approximation is that the monomers are rigid. We use a symmetry adapted Lanczos algorithm and an uncoupled product basis set. The pattern of the cluster's levels is complicated by splittings caused by H-H exchange tunneling (larger splitting) and N-N exchange tunneling (smaller splitting). An interesting result that emerges from our calculation is that whereas in N2-H2O, the symmetric H-H tunnelling state is below the anti-symmetric H-H tunnelling state for both K = 0 and K = 1, the order is reversed in N2-D2O for K = 1. The only experimental splitting measurements are the D-D exchange tunneling splittings reported by Zhu et al. [J. Chem. Phys. 139, 214309 (2013)] for N2-D2O in the v2 = 1 region of D2O. Due to the inverted order of the split levels, they measure the sum of the K = 0 and K = 1 tunneling splittings, which is in excellent agreement with our calculated result. Other splittings we predict, in particular those of N2-H2O, may guide future experiments.

Hematite photoanode co-functionalized with self-assembling melanin and C-phycocyanin for solar water splitting at neutral pH

Energy Technology Data Exchange (ETDEWEB)

Schrantz, Krisztina; Wyss, Pradeep P.; Ihssen, Julian; Toth, Rita; Bora, Debajeet K.; Vitol, Elina A.; Rozhkova, Elena A.; Pieles, Uwe; Thöny-Meyer, Linda; Braun, Artur

2017-04-01

tNature provides functional units which can be integrated in inorganic solar cell materials, such as lightharvesting antenna proteins and photosynthetic molecular machineries, and thus help in advancing artifi-cial photosynthesis. Their integration needs to address mechanical adhesion, light capture, charge transferand corrosion resistance. We showed recently how enzymatic polymerization of melanin can immobi-lize the cyanobacterial light harvesting protein C-phycocyanin on the surface of hematite, a prospectivemetal oxide photoanode for solar hydrogen production by water splitting in photoelectrochemical cells.After the optimization of the functionalization procedure, in this work we show reproducible hydrogenproduction, measured parallel to the photocurrent on this bio-hybrid electrode in benign neutral pHphosphate. Over 90% increase compared to the photocurrent of the pristine hematite could be achieved.The hydrogen evolution was monitored during the photoelectrochemical measurement in an improvedphotoelectrochemical cell. The C-phycocyanin-melanin coating on the hematite was shown to exhibit acomb-like fractal pattern. Raman spectroscopy supported the presence of the protein on the hematiteanode surface. The stability of the protein coating is demonstrated during the 2 h GC measurement andthe 24 h operando current density measurement

Succinic acid dihydrazide: a convenient N,N-double block for the synthesis of symmetrical and non-symmetrical succinyl-bis[5-trifluoro(chloro)methyl-1H-pyrazoles

International Nuclear Information System (INIS)

Bonacorso, Helio G.; Cechinel, Cleber A.; Pittaluga, Everton P.; Ferla, Adriana; Porte, Liliane M.F; Martins, Marcos A.P; Zanatta, Nilo

2010-01-01

This paper describes the conventional regioselective synthesis of a series of new succinyl spacer bis-(3,5-substituted 2-pyrazolines and 1H-pyrazoles), namely; 1,4-bis[5-(trifluoromethyl)-5- hydroxy-4,5-dihydro-1H-pyrazol-1-yl]butane-1,4-diones (46-88%) and the respective dehydrated system (60-78%), new 1-[5-(trifluoromethyl)-5-hydroxy-4,5-dihydro-1H-pyrazol-1-yl]-4- oxobutane hydrazides (52-81%) and the non-symmetrical 2-pyrazolines derivatives thereof as 1-[5-(trifluoromethyl)- 5-hydroxy-4,5-dihydro-1H-pyrazol-1-yl)-4-(5-(trichloromethyl)-5-hydroxy- 4,5-dihydro-1H-pyrazol-1-yl]butane-1,4-diones (75-91%). All succinyl substituted bispyrazoles were obtained from the cyclocondensation reactions of 4-substituted 4-alkoxy-1,1,1-trihaloalk-3- en-2-ones, where the 4-substituents are H, Me, Ph, 4-FC 6 H 4 , 4-ClC 6 H 4 , 4-OMeC 6 H 4 , 4-NO 2 C 6 H 4 , 1-naphthyl and 2-furyl, with succinic acid dihydrazide in ethanol as solvent under controlled reaction conditions. (author)

Theoretical study of AlH+: spin splitting, core polarization, and interstellar chemistry

International Nuclear Information System (INIS)

Cooper, D.L.; Black, J.H.; Everard, M.A.L.; Richards, W.G.

1983-01-01

The spin splitting constant for the X 2 μ + state of AlH + is calculated to be ν 0 = 0.058 cm - 1 . The favorable comparison of this result with experiment indicates that the uncertainty in the previously calculated spin splitting in MgH is likely to be of the order of a few percent. Calculations are presented of the so-called core polarization contribution to the spin-orbit coupling constant in the A 2 Pi/sub r/ state of AlH + . Results are also given for MgH and SiH. Astronomical applications of such calculations are discussed and the abundances of aluminum-bearing molecules in interstellar clouds are estimated

A Novel Symmetrical Split Ring Resonator Based on Microstrip for Microwave Sensors

Directory of Open Access Journals (Sweden)

Alahnomi Rammah A.

2016-02-01

Full Text Available In this paper, novel symmetrical split ring resonator (SSRR is proposed as a suitable component for performance enhancement of microwave sensors. SSRR has been employed for enhancing the insertion loss of the microwave sensors. Using the same device area, we can achieve a high Q-factor of 141.54 from the periphery enhancement using Quasi-linear coupling SSRR, whereas loose coupling SSRR can achieve a Q-factor of 33.98 only. Using Quasi-linear coupling SSRR, the Q-factor is enhanced 4.16 times the loose coupling SSRR using the same device area. After the optimization was made, the SSRR sensor with loose coupling scheme has achieved a very high Qfactor value around 407.34 while quasi-linear scheme has achieved high Q-factor value of 278.78 at the same operating frequency with smaller insertion loss. Spurious passbands at 1st, 2nd, 3rd, and 4th harmonics have been completely suppressed well above -20 dB rejection level without visible changes in the passband filter characteristics. The most significant of using SSRR is to be used for various industrial applications such as food industry, quality control, bio-sensing medicine and pharmacy. The simulation result that Quasi-linear coupling SSRR is a viable candidate for the performance enhancement of microwave sensors has been verified.

Hypercyclic operators on algebra of symmetric snalytic functions on $\\ell_p$

Directory of Open Access Journals (Sweden)

Z. H. Mozhyrovska

2016-06-01

Full Text Available In the paper, it is proposed a method of construction of hypercyclic composition operators on $H(\\mathbb{C}^n$ using polynomial automorphisms of $\\mathbb{C}^n$ and symmetric analytic functions on $\\ell_p.$ In particular, we show that an ``symmetric translation'' operator is hypercyclic on a Frechet algebra of symmetric entire functions on $\\ell_p$ which are bounded on bounded subsets.

Torsion-rotation structure and quasi-symmetric-rotor behaviour for the CH3SH asymmetric CH3-bending and C-H stretching bands of E parentage

Science.gov (United States)

Lees, R. M.; Xu, Li-Hong; Guislain, B. G.; Reid, E. M.; Twagirayezu, S.; Perry, D. S.; Dawadi, M. B.; Thapaliya, B. P.; Billinghurst, B. E.

2018-01-01

High-resolution Fourier transform spectra of the asymmetric methyl-bending and methyl-stretching bands of CH3SH have been recorded employing synchrotron radiation at the FIR beamline of the Canadian Light Source. Analysis of the torsion-rotation structure and relative intensities has revealed the novel feature that for both bend and stretch the in-plane and out-of-plane modes behave much like a Coriolis-coupled l-doublet pair originating from degenerate E modes of a symmetric top. As the axial angular momentum K increases, the energies of the coupled "l = ±1" modes diverge linearly, with effective Coriolis ζ constants typical for symmetric tops. For the methyl-stretching states, separated at K = 0 by only about 1 cm-1, the assigned sub-bands follow a symmetric top Δ(K - l) = 0 selection rule, with only ΔK = -1 transitions observed to the upper l = -1 in-plane A‧ component and only ΔK = +1 transitions to the lower l = +1 out-of-plane A″ component. The K = 0 separation of the CH3-bending states is larger at 9.1 cm-1 with the l-ordering reversed. Here, both ΔK = +1 and ΔK = -1 transitions are seen for each l-component but with a large difference in relative intensity. Term values for the excited state levels have been fitted to J(J + 1) power-series expansions to obtain substate origins. These have then been fitted to a Fourier model to characterize the torsion-K-rotation energy patterns. For both pairs of vibrational states, the torsional energies display the customary oscillatory behaviour as a function of K and have inverted torsional splittings relative to the ground state. The spectra show numerous perturbations, indicating local resonances with the underlying bath of high torsional levels and vibrational combination and overtone states. The overall structure of the two pairs of bands represents a new regime in which the vibrational energy separations, torsional splittings and shifts due to molecular asymmetry are all of the same order, creating a

Photochemical water splitting mediated by a C1 shuttle

KAUST Repository

Alderman, N. P.

2016-10-31

The possibility of performing photochemical water splitting in a two-stage system, separately releasing the H and O components, has been probed with two separate catalysts and in combination with a formaldehyde/formate shuttling redox couple. In the first stage, formaldehyde releases hydrogen vigorously in the presence of an Na[Fe(CN)]·10HO catalyst, selectively affording the formate anion. In the second stage, the formate anion is hydro-genated back to formaldehyde by water and in the presence of a BiWO photocatalyst whilst releasing oxygen. Both stages operate at room temperature and under visible light irradiation. The two separate photocatalysts are compatible since water splitting can also be obtained in one-pot experiments with simultaneous H/O evolution.

Photochemical water splitting mediated by a C1 shuttle

KAUST Repository

Alderman, N. P.; Sommers, J. M.; Viasus, C. J.; Wang, C. H T; Peneau, V.; Gambarotta, S.; Vidjayacoumar, B.; Al-Bahily, K. A.

2016-01-01

The possibility of performing photochemical water splitting in a two-stage system, separately releasing the H and O components, has been probed with two separate catalysts and in combination with a formaldehyde/formate shuttling redox couple. In the first stage, formaldehyde releases hydrogen vigorously in the presence of an Na[Fe(CN)]·10HO catalyst, selectively affording the formate anion. In the second stage, the formate anion is hydro-genated back to formaldehyde by water and in the presence of a BiWO photocatalyst whilst releasing oxygen. Both stages operate at room temperature and under visible light irradiation. The two separate photocatalysts are compatible since water splitting can also be obtained in one-pot experiments with simultaneous H/O evolution.

Triosmium cluster compounds containing isocyanide and hydride ligands. Crystal and molecular structure of (μ-H)(μ-eta1-C==N(H)(t-C4H9))Os3(CO)10

International Nuclear Information System (INIS)

Adams, R.D.; Golembeski, N.M.

1979-01-01

The crystal and molecular structure of the compound (μ-H)(μ-eta 1 -C==N(H)(t-C 4 H 9 ))Os 3 (CO) 10 has been determined by X-ray crystallographic methods. The compound crystallizes in the centrosymmetric monoclinic space group P2 1 /n[C/sub 2h/ 5 ]:a = 13.651 (4) A, b = 9.156 (4) A, c = 18.275 (5) A, β = 111.42 (2) 0 , V = 2126.3 (25) A 3 , Z = 4, rho/sub calcd/ = 2.92 g cm -3 . A uniform triangular cluster of three osmium atoms contains ten linear carbonyl groups and a μ-eta 1 -C==N(H)(t-C 4 H 9 ) iminyl ligand. The carbon atom of the iminyl ligand symmetrically bridges one osmium-osmium bond, as is shown by the internuclear separations Os(2)-C(11) = 2.066 (8) A and Os(3)-C(11) = 2.043 (8) A. The iminyl bond, C(11)-N, is double with the C-N distance being 1.298 (10) A

One-loop triple collinear splitting amplitudes in QCD

Energy Technology Data Exchange (ETDEWEB)

Badger, Simon; Buciuni, Francesco; Peraro, Tiziano [Higgs Centre for Theoretical Physics, School of Physics and Astronomy, University of Edinburgh,Edinburgh EH9 3JZ, Scotland (United Kingdom)

2015-09-28

We study the factorisation properties of one-loop scattering amplitudes in the triple collinear limit and extract the universal splitting amplitudes for processes initiated by a gluon. The splitting amplitudes are derived from the analytic Higgs plus four partons amplitudes. We present compact results for primitive helicity splitting amplitudes making use of super-symmetric decompositions. The universality of the collinear factorisation is checked numerically against the full colour six parton squared matrix elements.

Mechano-chemical pathways to H2O and CO2 splitting

Science.gov (United States)

Vedadi, Mohammad H.; Haas, Stephan

2011-10-01

The shock-induced collapse of CO2-filled nanobubbles is investigated using molecular dynamics simulations based on a reactive force field. The energetic nanojet and high-pressure water hammer shock formed during and after collapse of the nanobubble trigger mechano-chemical H2O-CO2 reactions, some of which lead to splitting of water and formation of O2 molecules. The dominant pathways through which splitting of water molecules occur are identified.

Axial zero-field splitting in mononuclear Co(ii) 2-N substituted N-confused porphyrin: Co(2-NC3H5-21-Y-CH2C6H4CH3-NCTPP)Cl (Y = o, m, p) and Co(2-NC3H5-21-CH2C6H5-NCTPP)Cl.

Science.gov (United States)

Lai, Ya-Yuan; Chang, Yu-Chang; Chen, Jyh-Horung; Wang, Shin-Shin; Tung, Jo-Yu

2016-03-21

The inner C-benzyl- and C-o-xylyl (or m-xylyl, p-xylyl)-substituted cobalt(ii) complexes of a 2-N-substituted N-confused porphyrin were synthesized from the reaction of 2-NC3H5NCTPPH (1) and CoCl2·6H2O in toluene (or o-xylene, m-xylene, p-xylene). The crystal structures of diamagnetic chloro(2-aza-2-allyl-5,10,15,20-tetraphenyl-21-hydrogen-21-carbaporphyrinato-N,N',N'')zinc(ii) [Zn(2-NC3H5-21-H-NCTPP)Cl; 3 ] and paramagnetic chloro(2-aza-2-allyl-5,10,15,20-tetraphenyl-21-benzyl-21-carbaporphyrinato-N,N',N'')cobalt(ii) [Co(2-NC3H5-21-CH2C6H5NCTPP)Cl; 7], and chloro(2-aza-2-allyl-5,10,15,20-tetraphenyl-21-Y-xylyl-21-carbaporphyrinato-N,N',N'')cobalt(ii) [Co(2-NC3H5-21-Y-CH2C6H4CH3NCTPP)Cl] [Y = o (8), m (9), p (10)] were determined. The coordination sphere around the Zn(2+) (or Co(2+)) ion in 3 (or 7-10) is a distorted tetrahedron (DT). The free energy of activation at the coalescence temperature Tc for the exchange of phenyl ortho protons o-H (26) with o-H (22) in 3 in a CDCl3 solvent is found to be ΔG = 61.4 kJ mol(-1) through (1)H NMR temperature-dependent measurements. The axial zero-field splitting parameter |D| was found to vary from 35.6 cm(-1) in 7 (or 30.7 cm(-1) in 8) to 42.0 cm(-1) in 9 and 46.9 cm(-1) in 10 through paramagnetic susceptibility measurements. The magnitude of |D| can be related to the coordination sphere at the cobalt sites.

One-dimensional Confinement Effect on the Self-assembly of Symmetric H-shaped Copolymers in a Thin Film.

Science.gov (United States)

Mu, Dan; Li, Jian-Quan; Feng, Sheng-Yu

2017-10-19

The self-assembly of a reformed symmetric H-shaped copolymer with four hydrophilic branches and one hydrophobic stem was systematically investigated. The existence of vacancies is vital to regulate the sizes of self-assembled cylinders to be able to form a hexagonal arrangement. With the introduction of horizontal-orientated confinement, a micellar structure is formed through a coalescence mechanism. The short acting distance and large influencing area of the confinement produces numerous small-sized micelles. Additionally, the cycled "contraction-expansion" change helps achieve hexagonal arrangement. In contrast, the introduction of lateral-oriented confinement with long acting distance and small influencing area cannot change the cylindrical structure. Under the fission mechanism, in which the larger cylinder splits into smaller ones, it is quite efficient to generate hierarchical-sized cylinders from larger-sized cylinders in the middle region and smaller-sized cylinders near both walls. The results indicate the possibility of regulating the characteristics of a nanomaterial by tuning the molecular structure of the copolymer and the parameters of the introduced confinement, which are closely related to the self-assembly structure.

SiC MOSFETs based split output half bridge inverter

DEFF Research Database (Denmark)

Li, Helong; Munk-Nielsen, Stig; Beczkowski, Szymon

2014-01-01

output. The double pulse test shows the devices' current during commutation process and the reduced switching losses of SiC MOSFETs compared to that of the traditional half bridge. The efficiency comparison is presented with experimental results of half bridge power inverter with split output...... and traditional half bridge inverter, from switching frequency 10 kHz to 100 kHz. The experimental results comparison shows that the half bridge with split output has an efficiency improvement of more than 0.5% at 100 kHz switching frequency....

Ternary electrocatalysts for oxidizing ethanol to carbon dioxide: making ir capable of splitting C-C bond.

Science.gov (United States)

Li, Meng; Cullen, David A; Sasaki, Kotaro; Marinkovic, Nebojsa S; More, Karren; Adzic, Radoslav R

2013-01-09

Splitting the C-C bond is the main obstacle to electrooxidation of ethanol (EOR) to CO(2). We recently demonstrated that the ternary PtRhSnO(2) electrocatalyst can accomplish that reaction at room temperature with Rh having a unique capability to split the C-C bond. In this article, we report the finding that Ir can be induced to split the C-C bond as a component of the ternary catalyst. We characterized and compared the properties of several carbon-supported nanoparticle (NP) electrocatalysts comprising a SnO(2) NP core decorated with multimetallic nanoislands (MM' = PtIr, PtRh, IrRh, PtIrRh) prepared using a seeded growth approach. An array of characterization techniques were employed to establish the composition and architecture of the synthesized MM'/SnO(2) NPs, while electrochemical and in situ infrared reflection absorption spectroscopy studies elucidated trends in activity and the nature of the reaction intermediates and products. Both EOR reactivity and selectivity toward CO(2) formation of several of these MM'/SnO(2)/C electrocatalysts are significantly higher compared to conventional Pt/C and Pt/SnO(2)/C catalysts. We demonstrate that the PtIr/SnO(2)/C catalyst with high Ir content shows outstanding catalytic properties with the most negative EOR onset potential and reasonably good selectivity toward ethanol complete oxidation to CO(2).

Generation of H2 and CO by solar thermochemical splitting of H2O and CO2 by employing metal oxides

International Nuclear Information System (INIS)

Rao, C.N.R.; Dey, Sunita

2016-01-01

Generation of H 2 and CO by splitting H 2 O and CO 2 respectively constitutes an important aspect of the present-day concerns with energy and environment. The solar thermochemical route making use of metal oxides is a viable means of accomplishing these reduction reactions. The method essentially involves reducing a metal oxide by heating and passing H 2 O or CO 2 over the nonstoichiometric oxide to cause reverse oxidation by abstracting oxygen from H 2 O or CO 2 . While ceria, perovskites and other oxides have been investigated for this purpose, recent studies have demonstrated the superior performance of perovskites of the type Ln 1−x A x Mn 1−y M y O 3 (Ln=rare earth, A=alkaline earth, M=various +2 and +3 metal ions), in the thermochemical generation of H 2 and CO. We present the important results obtained hitherto to point out how the alkaine earth and the Ln ions, specially the radius of the latter, determine the performance of the perovskites. The encouraging results obtained are exemplefied by Y 0.5 Sr 0.5 MnO 3 which releases 483 µmol/g of O 2 at 1673 K and produces 757 µmol/g of CO from CO 2 at 1173 K. The production of H 2 from H 2 O is also quite appreciable. Modification of the B site ion of the perovskite also affects the performance. In addition to perovskites, we present the generation of H 2 based on the Mn 3 O 4 /NaMnO 2 cycle briefly. - Graphical abstract: Ln 0.5 A 0.5 Mn 1−x M x O 3 (Ln=lanthanide; A=Ca, Sr; M=Al, Ga, Sc, Mg, Cr, Fe, Co) perovskites are employed for the two step thermochemical splitting of CO 2 and H 2 O for the generation of CO and H 2 . - Highlights: • Perovskite oxides based on Mn are ideal for the two-step thermochemical splitting of CO 2 and H 2 O. • In Ln 1−x A x MnO 3 perovskite (Ln=rare earth, A=alkaline earth) both Ln and A ions play major roles in the thermochemical process. • H 2 O splitting is also achieved by the use of the Mn 3 O 4 -sodium carbonate system. • Thermochemical splitting of CO 2 and H

Synthesis and Structure of D3h-Symmetric Triptycene Trimaleimide

Directory of Open Access Journals (Sweden)

Anthony Linden

2010-01-01

Full Text Available A new D3h symmetric triptycene derivative has been synthesized with the aim of obtaining molecules that are able to assemble into porous structures, and can be used in the development of new ligands. The synthesis involves a Diels-Alder reaction as the key step, followed by an oxidation and the formation of a maleimide ring. Triptycene trimaleimide furnished single crystals which have been analyzed by means of X-ray diffraction.

A C{sub 2}-symmetric ratiometric fluorescence and colorimetric anion sensor based on pyrrole derivative

Energy Technology Data Exchange (ETDEWEB)

Liu Ge [Department of Chemistry, Chifeng University, Chifeng 024000 (China); Shao Jie, E-mail: njshao@live.c [Department of Chemistry and Materials Science, Nanjing Forestry University, Nanjing 210037 (China)

2011-07-15

A C{sub 2}-symmetric fluorescence and colorimetric anion sensor (1) based on pyrrole derivative was designed and synthesized according to binding site-signaling subunit approach. The compound 1 was easily prepared by reaction of pyrrole-2,5-dicarboxaldehyde with 4-nitrophenylhydrazine in ethanol (yield=78%). In DMSO, the sensor 1 exhibited a visible color change from red to brown upon exposure to anions such as AcO{sup -} and F{sup -}; however, no obvious color changes were observed when the other tested anions (e. g. H{sub 2}PO{sub 4}{sup -}, Cl{sup -}, Br{sup -} and I{sup -}) were added. There was a significant redshift ({Delta}{lambda}{sub max}=160 nm) in UV-vis spectrum during UV-vis spectral titrations. In particular, the sensor 1 showed ratiometric fluorescence responses to anions. - Highlights: {yields} C{sub 2}-symmetric fluorescence and colorimetric anion sensor based on pyrrole derivative was designed and synthesized according to binding site-signaling subunit approach. {yields} The sensor was easily prepared by reaction of pyrrole-2,5-dicarboxaldehyde with 4-nitrophenylhydrazine in ethanol (yield=78%). {yields} In DMSO, the sensor exhibited a visible color change from red to brown upon exposure to anions such as AcO{sup -} and F{sup -}, however, no obvious color changes were observed when the other anions tested (e. g. H{sub 2}PO{sub 4}{sup -}, Cl{sup -}, Br{sup -} and I{sup -}) were added. {yields} The sensor showed ratiometric fluorescence responses to anions.

Tunneling splitting of magnetic levels in Fe8 detected by 1H NMR cross relaxation

Science.gov (United States)

Furukawa, Y.; Aizawa, K.; Kumagai, K.; Ullu, R.; Lascialfari, A.; Borsa, F.

2003-05-01

Measurements of proton NMR and the spin lattice relaxation rate 1/T1 in the octanuclear iron (III) cluster [Fe8(N3C6H15)6O2(OH)12]ṡ[Br8ṡ9H2O], in short Fe8, have been performed at 1.5 K in a powder sample aligned along the main anisotropy z axis, as a function of a transverse magnetic field (i.e., perpendicular to the main easy axis z). A big enhancement of 1/T1 is observed over a wide range of fields (2.5-5 T), which can be attributed to the tunneling dynamics; in fact, when the tunneling splitting of the pairwise degenerate m=±10 states of the Fe8 molecule becomes equal to the proton Larmor frequency a very effective spin lattice relaxation channel for the nuclei is opened. The experimental results are explained satisfactorily by considering the distribution of tunneling splitting resulting from the distribution of the angles in the hard xy plane for the aligned powder, and the results of the direct diagonalization of the model Hamiltonian.

Infrared rovibrational spectroscopy of OH–C2H2 in 4He nanodroplets: Parity splitting due to partially quenched electronic angular momentum

International Nuclear Information System (INIS)

Douberly, Gary E.; Liang, Tao; Raston, Paul L.; Marshall, Mark D.

2015-01-01

The T-shaped OH–C 2 H 2 complex is formed in helium droplets via the sequential pick-up and solvation of the monomer fragments. Rovibrational spectra of the a-type OH stretch and b-type antisymmetric CH stretch vibrations contain resolved parity splitting that reveals the extent to which electronic angular momentum of the OH moiety is quenched upon complex formation. The energy difference between the spin-orbit coupled 2 B 1 (A″) and 2 B 2 (A′) electronic states is determined spectroscopically to be 216 cm −1 in helium droplets, which is 13 cm −1 larger than in the gas phase [Marshall et al., J. Chem. Phys. 121, 5845 (2004)]. The effect of the helium is rationalized as a difference in the solvation free energies of the two electronic states. This interpretation is motivated by the separation between the Q(3/2) and R(3/2) transitions in the infrared spectrum of the helium-solvated 2 Π 3/2 OH radical. Despite the expectation of a reduced rotational constant, the observed Q(3/2) to R(3/2) splitting is larger than in the gas phase by ≈0.3 cm −1 . This observation can be accounted for quantitatively by assuming the energetic separation between 2 Π 3/2 and 2 Π 1/2 manifolds is increased by ≈40 cm −1 upon helium solvation

Safety and immunogenicity of adjuvanted inactivated split-virion and whole-virion influenza A (H5N1) vaccines in children: a phase I-II randomized trial.

Science.gov (United States)

Wu, Jiang; Liu, Shu-Zhen; Dong, Shan-Shan; Dong, Xiao-Ping; Zhang, Wu-Li; Lu, Min; Li, Chang-Gui; Zhou, Ji-Chen; Fang, Han-Hua; Liu, Yan; Liu, Li-Ying; Qiu, Yuan-Zheng; Gao, Qiang; Zhang, Xiao-Mei; Chen, Jiang-Ting; Zhong, Xiang; Yin, Wei-Dong; Feng, Zi-Jian

2010-08-31

Highly pathogenic avian influenza A virus H5N1 has the potential to cause a pandemic. Many prototype pandemic influenza A (H5N1) vaccines had been developed and well evaluated in adults in recent years. However, data in children are limited. Herein we evaluate the safety and immunogenicity of adjuvanted split-virion and whole-virion H5N1 vaccines in children. An open-labelled phase I trial was conducted in children aged 3-11 years to receive aluminum-adjuvated, split-virion H5N1 vaccine (5-30 microg) and in children aged 12-17 years to receive aluminum-adjuvated, whole-virion H5N1 vaccine (5-15 microg). Safety of the two formulations was assessed. Then a randomized phase II trial was conducted, in which 141 children aged 3-11 years received the split-virion vaccine (10 or 15 microg) and 280 children aged 12-17 years received the split-virion vaccine (10-30 microg) or the whole-virion vaccine (5 microg). Serum samples were collected for hemagglutination-inhibition (HI) assays. 5-15 microg adjuvated split-virion vaccines were well tolerated in children aged 3-11 years and 5-30 microg adjuvated split-virion vaccines and 5 microg adjuvated whole-virion vaccine were well tolerated in children aged 12-17 years. Most local and systemic reactions were mild or moderate. Before vaccination, all participants were immunologically naïve to H5N1 virus. Immune responses were induced after the first dose and significantly boosted after the second dose. In 3-11 years children, the 10 and 15 microg split-virion vaccine induced similar responses with 55% seroconversion and seroprotection (HI titer >or=1:40) rates. In 12-17 years children, the 30 microg split-virion vaccine induced the highest immune response with 71% seroconversion and seroprotection rates. The 5 microg whole-virion vaccine induced higher response than the 10 microg split-virion vaccine did. The aluminum-adjuvanted, split-virion prototype pandemic influenza A (H5N1) vaccine showed good safety and immunogenicity in

Recombination reduction at the c-Si/RCA oxide interface through Ar-H2 plasma treatment

NARCIS (Netherlands)

Landheer, K.; Bronsveld, P.C.P.; Poulios, I.; Tichelaar, F.D.; Kaiser, M.; Schropp, R.E.I.; Rath, J.K.

2017-01-01

An Ar‑H2 plasma treatment was applied on an ultrathin RCA oxide to create well-passivated silicon wafers with symmetric c‑Si/SiOx:H/a‑Si:H passivation layer stacks. The effective lifetime of these samples increased from 10 μs to 4 ms after annealing at 200 °C through Ar‑H2 plasma treatment of the

Optical detection of symmetric and antisymmetric states in double quantum wells at room temperature

Science.gov (United States)

Marchewka, M.; Sheregii, E. M.; Tralle, I.; Marcelli, A.; Piccinini, M.; Cebulski, J.

2009-09-01

We studied the optical reflectivity of a specially grown double quantum well (DQW) structure characterized by a rectangular shape and a high electron density at room temperature. Assuming that the QWs depth is known, reflectivity spectra in the mid-IR range allow to carry out the precise measurements of the SAS-gap values (the energy gap between the symmetric and anti-symmetric states) and the absolute energies of both symmetric and antisymmetric electron states. The results of our experiments are in favor of the existence of the SAS splitting in the DQWs at room temperature. Here we have shown that the SAS gap increases proportionally to the subband quantum number and the optical electron transitions between symmetric and antisymmetric states belonging to different subbands are allowed. These results were used for interpretation of the beating effect in the Shubnikov-de Haas (SdH) oscillations at low temperatures (0.6 and 4.2 K). The approach to the calculation of the Landau-levels energies for DQW structures developed earlier [D. Ploch , Phys. Rev. B 79, 195434 (2009)] is used for the analysis and interpretation of the experimental data related to the beating effect. We also argue that in order to explain the beating effect in the SdH oscillations, one should introduce two different quasi-Fermi levels characterizing the two electron subsystems regarding symmetry properties of their wave functions, symmetric and antisymmetric ones. These states are not mixed neither by electron-electron interaction nor probably by electron-phonon interaction.

10kV SiC MOSFET split output power module

DEFF Research Database (Denmark)

Beczkowski, Szymon; Li, Helong; Uhrenfeldt, Christian

2015-01-01

The poor body diode performance of the first generation of 10kV SiC MOSFETs and the parasitic turn-on phenomenon limit the performance of SiC based converters. Both these problems can potentially be mitigated using a split output topology. In this paper we present a comparison between a classical...

Intrinsic optical conductivity of a {{\\rm{C}}}_{2v} symmetric topological insulator

Science.gov (United States)

Sengupta, Parijat; Matsubara, Masahiko; Bellotti, Enrico; Shi, Junxia

2017-07-01

In this work we analytically investigate the longitudinal optical conductivity of the {{{C}}}2v symmetric topological insulator. The conductivity expressions at T = 0 are derived using the Kubo formula and expressed as a function of the ratio of the Dresselhaus and Rashba parameters that characterize the low-energy Hamiltonian. We find that the longitudinal inter-band conductivity vanishes when Dresselhaus and Rashba parameters are equal in strength, also called the persistent spin helix state. The calculations are extended to obtain the frequency-dependent real and imaginary components of the optical conductivity for the topological Kondo insulator SmB6 which exhibits {{{C}}}2v symmetric and anisotropic Dirac cones hosting topological states at \\overline{X} point on the surface Brillouin zone.

Recombination reduction at the c-Si/RCA oxide interface through Ar-H2 plasma treatment

Science.gov (United States)

Landheer, Kees; Bronsveld, Paula C. P.; Poulios, Ioannis; Tichelaar, Frans D.; Kaiser, Monja; Schropp, Ruud E. I.; Rath, Jatin K.

2017-02-01

An Ar-H2 plasma treatment was applied on an ultrathin RCA oxide to create well-passivated silicon wafers with symmetric c-Si/SiOx:H/a-Si:H passivation layer stacks. The effective lifetime of these samples increased from 10 μs to 4 ms after annealing at 200 °C through Ar-H2 plasma treatment of the oxide. The results indicate that the plasma treatment can modify the RCA oxide and this enables atomic hydrogen diffusion at low annealing temperature, leading to a well passivated c-Si/SiOx:H interface. This might provide new possibilities to use wet chemical oxides in c-Si solar cells, for example as tunnel contacts.

Functional characterization of Kv11.1 (hERG) potassium channels split in the voltage-sensing domain.

Science.gov (United States)

de la Peña, Pilar; Domínguez, Pedro; Barros, Francisco

2018-03-23

Voltage-dependent KCNH family potassium channel functionality can be reconstructed using non-covalently linked voltage-sensing domain (VSD) and pore modules (split channels). However, the necessity of a covalent continuity for channel function has not been evaluated at other points within the two functionally independent channel modules. We find here that by cutting Kv11.1 (hERG, KCNH2) channels at the different loops linking the transmembrane spans of the channel core, not only channels split at the S4-S5 linker level, but also those split at the intracellular S2-S3 and the extracellular S3-S4 loops, yield fully functional channel proteins. Our data indicate that albeit less markedly, channels split after residue 482 in the S2-S3 linker resemble the uncoupled gating phenotype of those split at the C-terminal end of the VSD S4 transmembrane segment. Channels split after residues 514 and 518 in the S3-S4 linker show gating characteristics similar to those of the continuous wild-type channel. However, breaking the covalent link at this level strongly accelerates the voltage-dependent accessibility of a membrane impermeable methanethiosulfonate reagent to an engineered cysteine at the N-terminal region of the S4 transmembrane helix. Thus, besides that of the S4-S5 linker, structural integrity of the intracellular S2-S3 linker seems to constitute an important factor for proper transduction of VSD rearrangements to opening and closing the cytoplasmic gate. Furthermore, our data suggest that the short and probably rigid characteristics of the extracellular S3-S4 linker are not an essential component of the Kv11.1 voltage sensing machinery.

Conduction-band valley spin splitting in single-layer H-T l2O

Science.gov (United States)

Ma, Yandong; Kou, Liangzhi; Du, Aijun; Huang, Baibiao; Dai, Ying; Heine, Thomas

2018-02-01

Despite numerous studies, coupled spin and valley physics is currently limited to two-dimensional (2D) transition-metal dichalcogenides (TMDCs). Here, we predict an exceptional 2D valleytronic material associated with the spin-valley coupling phenomena beyond 2D TMDCs—single-layer (SL) H-T l2O . It displays large valley spin splitting (VSS), significantly larger than that of 2D TMDCs, and a finite band gap, which are both critically attractive for the integration of valleytronics and spintronics. More importantly, in sharp contrast to all the experimentally confirmed 2D valleytronic materials, where the strong valence-band VSS (0.15-0.46 eV) supports the spin-valley coupling, the VSS in SL H-T l2O is pronounced in its conduction band (0.61 eV), but negligibly small in its valence band (21 meV), thus opening a way for manipulating the coupled spin and valley physics. Moreover, SL H-T l2O possesses extremely high carrier mobility, as large as 9.8 ×103c m2V-1s-1 .

Tunneling and energy splitting in an asymmetric double-well potential

International Nuclear Information System (INIS)

Song, Dae-Yup

2008-01-01

An asymmetric double-well potential is considered, assuming that the minima of the wells are quadratic with a frequency ω and the difference of the minima is close to a multiple of hω. A WKB wave function is constructed on both sides of the local maximum between the wells, by matching the WKB function to the exact wave functions near the classical turning points. The continuities of the wave function and its first derivative at the local maximum then give the energy-level splitting formula, which not only reproduces the instanton result for a symmetric potential, but also elucidates the appearance of resonances of tunneling in the asymmetric potential

Splitting method for the combined formulation of fluid-particle problem

International Nuclear Information System (INIS)

Choi, Hyung Gwon; Yoo, Jung Yul; Joseph, D. D.

2000-01-01

A splitting method for the direct numerical simulation of solid-liquid mixtures is presented, where a symmetric pressure equation is newly proposed. Through numerical experiment, it is found that the newly proposed splitting method works well with a matrix-free formulation for some bench mark problems avoiding an erroneous pressure field which appears when using the conventional pressure equation of a splitting method. When deriving a typical pressure equation of a splitting method, the motion of a solid particle has to be approximated by the 'intermediate velocity' instead of treating it as unknowns since it is necessary as a boundary condition. Therefore, the motion of a solid particle is treated in such an explicit way that a particle moves by the known form drag(pressure drag) that is calculated from the pressure equation in the previous step. From the numerical experiment, it was shown that this method gives an erroneous pressure field even for the very small time step size as a particle velocity increases. In this paper, coupling the unknowns of particle velocities in the pressure equation is proposed, where the resulting matrix is reduced to the symmetric one by applying the projector of the combined formulation. It has been tested over some bench mark problems and gives reasonable pressure fields

Dp spaces on bounded symmetric domains of Cn

International Nuclear Information System (INIS)

Shi Jihuai.

1989-06-01

In this paper, the space D p (Ω) of functions holomorphic on bounded symmetric domain of C m is defined. We prove that H p (Ω) is contained in D p (Ω) if 0 p (Ω) is contained in H p (Ω) if p ≥2, and both inclusions are proper. Further we find that some theorems on H p (Ω) can be extended to the wider class D p (Ω) for 0 < p ≤ 2. (author). 12 refs

Characterization of Generalized Young Measures Generated by Symmetric Gradients

Science.gov (United States)

De Philippis, Guido; Rindler, Filip

2017-06-01

This work establishes a characterization theorem for (generalized) Young measures generated by symmetric derivatives of functions of bounded deformation (BD) in the spirit of the classical Kinderlehrer-Pedregal theorem. Our result places such Young measures in duality with symmetric-quasiconvex functions with linear growth. The "local" proof strategy combines blow-up arguments with the singular structure theorem in BD (the analogue of Alberti's rank-one theorem in BV), which was recently proved by the authors. As an application of our characterization theorem we show how an atomic part in a BD-Young measure can be split off in generating sequences.

Microwave bio-sensor based on symmetrical split ring resonator with spurline filters for therapeutic goods detection.

Directory of Open Access Journals (Sweden)

Rammah A Alahnomi

Full Text Available A novel symmetrical split ring resonator (SSRR based microwave sensor with spurline filters for detecting and characterizing the properties of solid materials has been developed. Due to the weak perturbation in the interaction of material under test (MUT and planar microwave sensor, spurline filters were embedded to the SSRR microwave sensor which effectively enhanced Q-factor with suppressing the undesired harmonic frequency. The spurline filter structures force the presented sensor to resonate at a fundamental frequency of 2.2 GHz with the capabilities of suppressing rejected harmonic frequency and miniaturization in circuit size. A wide bandwidth rejection is achieved by using double spurlines filters with high Q-factor achievement (up to 652.94 compared to single spurline filter. The new SSRR sensor with spurline filters displayed desired properties such as high sensitivity, accuracy, and performance with a 1.3% typical percentage error in the measurement results. Furthermore, the sensor has been successfully applied for detecting and characterizing solid materials (such as Roger 5880, Roger 4350, and FR4 and evidently demonstrated that it can suppress the harmonic frequency effectively. This novel design with harmonic suppression is useful for various applications such as food industry (meat, fruit, vegetables, biological medicine (derived from proteins and other substances produced by the body, and Therapeutic goods (antiseptics, vitamins, anti-psychotics, and other medicines.

Ab initio/GIAO-CCSD(T) (13)C NMR study of the rearrangement and dynamic aspects of rapidly equilibrating tertiary carbocations, C6H13(+) and C7H15(+).

Science.gov (United States)

Olah, George A; Prakash, G K Surya; Rasul, Golam

2016-01-05

The rearrangement pathways of the equilibrating tertiary carbocations, 2,3-dimethyl-2-butyl cation (C6H13(+), 1), 2,3,3-trimethyl-2-butyl cation (C7H15(+), 5) and 2,3-dimethyl-2-pentyl cation (C7H15(+), 8 and 9) were investigated using the ab initio/GIAO-CCSD(T) (13)C NMR method. Comparing the calculated and experimental (13)C NMR chemical shifts of a series of carbocations indicates that excellent prediction of δ(13)C could be achieved through scaling. In the case of symmetrical equilibrating cations (1 and 5) the Wagner-Meerwein 1,2-hydride and 1,2-methide shifts, respectively, produce the same structure. This indicates that the overall (13)C NMR chemical shifts are conserved and independent of temperature. However, in the case of unsymmetrical equilibrating cations (8 and 9) the Wagner-Meerwein shift produces different tertiary structures, which have slightly different thermodynamic stabilities and, thus, different spectra. At the MP4(SDTQ)/cc-pVTZ//MP2/cc-pVTZ + ZPE level structure 8 is only 90 calories/mol more stable than structure 9. Based on computed (13)C NMR chemical shift calculations, mole fractions of these isomers were determined by assuming the observed chemical shifts are due to the weighted average of the chemical shifts of the static ions. © 2015 Wiley Periodicals, Inc.

Ferroelectric response in an achiral non-symmetric bent liquid crystal:C{sub 12}C{sub 10}

Energy Technology Data Exchange (ETDEWEB)

Subrahmanyam, S.V.; Chalapathi, P.V. [Department of Physics, University College of Engineering, Jawaharlal Nehru Technological University Kakinada, Kakinada 533003 (India); Mahabaleshwara, S.; Srinivasulu, M. [Department of Chemistry, Manipal Institute of Technology, Manipal University, Manipal 576104 (India); George, A.K. [Department of Physics, College of Sciences, Sultan Qaboos University, PO Box-36, PC-123, Muscat (Oman); Potukuchi, D.M., E-mail: potukuchidm@yahoo.com [Department of Physics, University College of Engineering, Jawaharlal Nehru Technological University Kakinada, Kakinada 533003 (India)

2014-10-01

An achiral Non-Symmetric Bent Liquid Crystal (BLC) with a Oxadiazole based hetero cyclic central moiety, abbreviated as C{sub 12}C{sub 10} viz., dodecyl[4-{5-(4′-decyloxy)biphenyl-4-yl}-1,2,4-oxadiazol-3-yl]benzoate, exhibiting FerroElectric (FE) response is reported. Product is confirmed by {sup 1}H NMR, {sup 13}C NMR and elemental analysis. Characterization of BLC phases is carried out by Polarized Optical Microscopy (POM), Differential Scanning Calorimetry (DSC), Spontaneous Polarization (P{sub S}) and Low Frequency (10 Hz–10 MHz) Dielectric Relaxation studies. C{sub 12}C{sub 10} exhibits enantiotropic LC SmA, FE B{sub 2}, SmG, SmE phase variance. I–SmA, B{sub 2}–SmG and SmG–SmE transitions are of first order nature. FE B{sub 2} phases exhibits a moderate P{sub S} of ∼80 nC cm{sup −2}. B{sub 2} phase exhibits Curie–Weiss behavior to confirm FE nature. Off-centered low frequency (KHz) dispersion infers a scissor mode and a high frequency (MHz) mode to reflect the distinct time-scale response. Dielectric Dispersion is relatively susceptible in lower frequency KHz region. Arrhenius shift in Relaxation Frequency (f{sub R}) infers higher activation energy (E{sub a}) in non-FE phases for HF mode and lower value for KHz mode. Trends of f{sub R}, dielectric strength Δε, α-parameter and E{sub a} are discussed in view of the data reported in other LC compounds.

Enhanced visible light photocatalytic H{sub 2} evolution of metal-free g-C{sub 3}N{sub 4}/SiC heterostructured photocatalysts

Energy Technology Data Exchange (ETDEWEB)

Wang, Biao, E-mail: wangbiao@fjirsm.ac.cn [Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China); University of the Chinese Academy of Sciences, Beijing 100049 (China); Zhang, Jingtao, E-mail: zhangjtao@mail.sysu.edu.cn [State Key Laboratory of Optoelectronic Materials and Technologies, School of Materials Science and Engineering, Sun Yat-sen University, Guangzhou 510006 (China); Huang, Feng, E-mail: huangfeng@mail.sysu.edu.cn [Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou, Fujian 350002 (China); State Key Laboratory of Optoelectronic Materials and Technologies, School of Materials Science and Engineering, Sun Yat-sen University, Guangzhou 510006 (China)

2017-01-01

Highlights: • Novel g-C{sub 3}N{sub 4}/SiC composite was prepared by synthesizing g-C{sub 3}N{sub 4} on the surface of SiC. • g-C{sub 3}N{sub 4}/SiC composites exhibit much higher H{sub 2} production activity than pure g-C{sub 3}N{sub 4}. • The g-C{sub 3}N{sub 4}/SiC heterojunction mainly accounts for improved photocatalytic activity. - Abstract: g-C{sub 3}N{sub 4} has been attracting much attention for application in visible light photocatalytic water splitting due to its suitable band structure, and high thermal and chemical stability. However, the rapid recombination of photogenerated carriers has inhibited its wide use. For this reason, novel g-C{sub 3}N{sub 4}/SiC composites were prepared via in situ synthesis of g-C{sub 3}N{sub 4} on the surface of SiC, with which g-C{sub 3}N{sub 4} shows tight interaction (chemical bonding). The g-C{sub 3}N{sub 4}/SiC composites exhibit high stability in H{sub 2} production under irradiation with visible light (λ ≥ 420 nm), demonstrating a maximum of 182 μmol g{sup −1} h{sup −1}, being 3.4 times higher than that of pure g-C{sub 3}N{sub 4}. The enhanced photocatalytic H{sub 2} production ability for g-C{sub 3}N{sub 4}/SiC photocatalysts is primarily ascribed to the combined effects of enhanced separation of photogenerated carriers through efficient migration of electron and enlarged surface areas, in addition to the possible contributions of increased hydrophilicity of SiC and polymerization degree of g-C{sub 3}N{sub 4}. This study may provide new insights into the development of g-C{sub 3}N{sub 4}-based composites as stable and efficient photocatalysts for H{sub 2} production from water splitting.

Exploring the effects of symmetrical and asymmetrical relative humidity on the performance of H{sub 2}/air PEM fuel cell at different temperatures

Energy Technology Data Exchange (ETDEWEB)

Saleh, Mahmoud M.; Okajima, Takeoshi; Kitamura, Fusao; Ohsaka, Takeo [Department of Electronic Chemistry, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8502 (Japan); Hayase, Masahiko [Development Department, NF Co., 6-3-20 Tsunashima-higashi, Kohoku-ku, Yokohama 223-8508 (Japan)

2007-02-10

This article is dedicated to study the interlinked effects of symmetric relative humidity (RH), and asymmetric RH on the performance of H{sub 2}/air PEM fuel cell at different temperatures. The symmetric and asymmetric RH were achieved by setting the cathode relative humidity (RHC) and anode relative humidity (RHA) as equal and unequal values, respectively. The cell performance was evaluated by collecting polarization curves of the cell at different RH, RHC and RHA and at different cell temperatures (T{sub cell}). The polarization curves along with the measured internal cell resistance (membrane resistance) were discussed in the light of the present fuel cell theory. The results showed that symmetric relative humidity has different impacts depending on the cell temperature. While at RH of 35% the cell can show considerable performance at T{sub cell} = 70 C, it is not so at T{sub cell} = 90 C. At T{sub cell} = 70 C, the cell potential increases with RH at lower and medium current densities but decreases with RH at higher currents. This was attributed to the different controlling processes at higher and lower current densities. This trend at 70 C is completely destroyed at 90 C. Operating our PEM fuel cell at dry H{sub 2} gas conditions (RHA = 0%) is not detrimental as operating the cell at dry Air (O{sub 2}) conditions (RHC = 0%). At RHA = 0% and humidified air, water transport by back diffusion from the cathode to the anode at the employed experimental conditions can support reasonable rehydration of the membrane and catalysts. At RHA = 0, a possible minimum RHC for considerable cell operation is temperature dependent. At RHC = 0 conditions, the cell can operate only at RHA = 100% with a loss that depends on T{sub cell}. It was found that the internal cell resistance depends on RH, RHA, RHC and T{sub cell} and it is consistent with the observed cell performance. (author)

Synthesis of C3-symmetric tri(alkylamino) guests and their interaction with cyclodextrins

Czech Academy of Sciences Publication Activity Database

Bednaříková, T.; Tošner, Z.; Horský, Jiří; Jindřich, J.

2015-01-01

Roč. 81, 1-2 (2015), s. 141-152 ISSN 0923-0750 Institutional support: RVO:61389013 Keywords : cyclodextrin * supramolecular interactions * C3-symmetric guests Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 1.253, year: 2015

Communication: Equivalence between symmetric and antisymmetric stretching modes of NH3 in promoting H + NH3 → H2 + NH2 reaction

Science.gov (United States)

Song, Hongwei; Yang, Minghui; Guo, Hua

2016-10-01

Vibrational excitations of reactants sometimes promote reactions more effectively than the same amount of translational energy. Such mode specificity provides insights into the transition-state modulation of reactivity and might be used to control chemical reactions. We report here a state-of-the-art full-dimensional quantum dynamical study of the hydrogen abstraction reaction H + NH3 → H2 + NH2 on an accurate ab initio based global potential energy surface. This reaction serves as an ideal candidate to study the relative efficacies of symmetric and degenerate antisymmetric stretching modes. Strong mode specificity, particularly for the NH3 stretching modes, is demonstrated. It is further shown that nearly identical efficacies of the symmetric and antisymmetric stretching modes of NH3 in promoting the reaction can be understood in terms of local-mode stretching vibrations of the reactant molecule.

Anomalous signature splitting of the πh11/2direct x νi13/2 band in A-160 odd-odd nuclei

International Nuclear Information System (INIS)

Yang Chunxiang; Zhou Hongyu

2003-01-01

Systematic features of anomalous signature splitting of the πh 11/2 direct x νi 13/2 band in A-160 odd-odd nuclei have been investigated. It is shown that the mechanism of anomalous signature splitting is similar to that of the normal signature splitting which is essentially caused by the Coriolis mixing of Ω=1/2 components into the nuclear wavefunction and the anomalous splitting in signature is mainly caused by the definition. The extensively observed anomalous signature splitting in this band might be an indication that the interaction between the h 11/2 proton and the i 13/2 neutron cannot be neglected. The new observation of high- and low-K bands based on the same πh 11/2 direct x νi 13/2 configuration in 164 Tm is also discussed

Direct selenylation of mixed Ni/Fe metal-organic frameworks to NiFe-Se/C nanorods for overall water splitting

Science.gov (United States)

Xu, Bo; Yang, He; Yuan, Lincheng; Sun, Yiqiang; Chen, Zhiming; Li, Cuncheng

2017-10-01

Development of low-cost, highly active bifunctional catalyst for efficient overall water splitting based on earth-abundant metals is still a great challenging task. In this work, we report a NiFe-Se/C composite nanorod as efficient non-precious-metal electrochemical catalyst derived from direct selenylation of a mixed Ni/Fe metal-organic framework. The as-obtained catalyst requires low overpotential to drive 10 mA cm-2 for HER (160 mV) and OER (240 mV) in 1.0 M KOH, respectively, and its catalytic activity is maintained for at least 20 h. Moreover, water electrolysis using this catalyst achieves high water splitting current density of 10 mA cm-2 at cell voltage of 1.68 V.

Rashba splitting of 100 meV in Au-intercalated graphene on SiC

Energy Technology Data Exchange (ETDEWEB)

Marchenko, D.; Varykhalov, A.; Sánchez-Barriga, J.; Rader, O. [Helmholtz-Zentrum Berlin für Materialien und Energie, Elektronenspeicherring BESSY II, Albert-Einstein-Straße 15, 12489 Berlin (Germany); Seyller, Th. [Institut für Physik, Technische Universität Chemnitz, Reichenhainer Strasse 70, 09126 Chemnitz (Germany)

2016-04-25

Intercalation of Au can produce giant Rashba-type spin-orbit splittings in graphene, but this has not yet been achieved on a semiconductor substrate. For graphene/SiC(0001), Au intercalation yields two phases with different doping. We observe a 100 meV Rashba-type spin-orbit splitting at 0.9 eV binding energy in the case of p-type graphene after Au intercalation. We show that this giant splitting is due to hybridization and much more limited in energy and momentum space than for Au-intercalated graphene on Ni.

Quenched spin tunneling and diabolical points in magnetic molecules. I. Symmetric configurations

Science.gov (United States)

Garg, Anupam

2001-09-01

The perfect quenching of spin tunneling that has previously been discussed in terms of interfering instantons, and has recently been observed in the magnetic molecule Fe8, is treated using a discrete phase integral (or Wentzel-Kramers-Brillouin) method. The simplest model Hamiltonian for the phenomenon leads to a Schrödinger equation that is a five-term recursion relation. This recursion relation is reflection symmetric when the magnetic field applied to the molecule is along the hard magnetic axis. A completely general Herring formula for the tunnel splittings for all reflection-symmetric five-term recursion relations is obtained. Using connection formulas for a nonclassical turning point that may be described as lying ``under the barrier,'' and which underlies the oscillations in the splitting as a function of magnetic field, this Herring formula is transformed into two other formulas that express the splittings in terms of a small number of action and actionlike integrals. These latter formulas appear to be generally valid, even for problems where the recursion contains more than five terms. The results for the model Hamiltonian are compared with experiment, numerics, previous instanton based approaches, and the limiting case of no magnetic field.

Generation of H{sub 2} and CO by solar thermochemical splitting of H{sub 2}O and CO{sub 2} by employing metal oxides

Energy Technology Data Exchange (ETDEWEB)

Rao, C.N.R., E-mail: cnrrao@jncasr.ac.in; Dey, Sunita

2016-10-15

Generation of H{sub 2} and CO by splitting H{sub 2}O and CO{sub 2} respectively constitutes an important aspect of the present-day concerns with energy and environment. The solar thermochemical route making use of metal oxides is a viable means of accomplishing these reduction reactions. The method essentially involves reducing a metal oxide by heating and passing H{sub 2}O or CO{sub 2} over the nonstoichiometric oxide to cause reverse oxidation by abstracting oxygen from H{sub 2}O or CO{sub 2}. While ceria, perovskites and other oxides have been investigated for this purpose, recent studies have demonstrated the superior performance of perovskites of the type Ln{sub 1−x}A{sub x}Mn{sub 1−y}M{sub y}O{sub 3} (Ln=rare earth, A=alkaline earth, M=various +2 and +3 metal ions), in the thermochemical generation of H{sub 2} and CO. We present the important results obtained hitherto to point out how the alkaine earth and the Ln ions, specially the radius of the latter, determine the performance of the perovskites. The encouraging results obtained are exemplefied by Y{sub 0.5}Sr{sub 0.5}MnO{sub 3} which releases 483 µmol/g of O{sub 2} at 1673 K and produces 757 µmol/g of CO from CO{sub 2} at 1173 K. The production of H{sub 2} from H{sub 2}O is also quite appreciable. Modification of the B site ion of the perovskite also affects the performance. In addition to perovskites, we present the generation of H{sub 2} based on the Mn{sub 3}O{sub 4}/NaMnO{sub 2} cycle briefly. - Graphical abstract: Ln{sub 0.5}A{sub 0.5}Mn{sub 1−x}M{sub x}O{sub 3} (Ln=lanthanide; A=Ca, Sr; M=Al, Ga, Sc, Mg, Cr, Fe, Co) perovskites are employed for the two step thermochemical splitting of CO{sub 2} and H{sub 2}O for the generation of CO and H{sub 2}. - Highlights: • Perovskite oxides based on Mn are ideal for the two-step thermochemical splitting of CO{sub 2} and H{sub 2}O. • In Ln{sub 1−x}A{sub x}MnO{sub 3} perovskite (Ln=rare earth, A=alkaline earth) both Ln and A ions play major roles

Weakly Interacting Symmetric and Anti-Symmetric States in the Bilayer Systems

Science.gov (United States)

Marchewka, M.; Sheregii, E. M.; Tralle, I.; Tomaka, G.; Ploch, D.

We have studied the parallel magneto-transport in DQW-structures of two different potential shapes: quasi-rectangular and quasi-triangular. The quantum beats effect was observed in Shubnikov-de Haas (SdH) oscillations for both types of the DQW structures in perpendicular magnetic filed arrangement. We developed a special scheme for the Landau levels energies calculation by means of which we carried out the necessary simulations of beating effect. In order to obtain the agreement between our experimental data and the results of simulations, we introduced two different quasi-Fermi levels which characterize symmetric and anti-symmetric states in DQWs. The existence of two different quasi Fermi-Levels simply means, that one can treat two sub-systems (charge carriers characterized by symmetric and anti-symmetric wave functions) as weakly interacting and having their own rate of establishing the equilibrium state.

An efficient synthesis of symmetric and unsymmetric bis-(β-aminoamides) via Ugi multicomponent reaction.

Science.gov (United States)

La Spisa, Fabio; Feo, Alberto; Mossetti, Riccardo; Tron, Gian Cesare

2012-12-07

A library of symmetrical and unsymmetrical bis-(β-aminoamides) has been prepared starting from symmetrical secondary diamines by using a double Ugi four-component reaction. A sacrifical Mumm rearrangement, thanks to the use of 2-hydroxymethyl benzoic acid, is necessary to suppress the competing split-Ugi reaction, increasing the yield and simplifying the purification step. The scope, the reaction conditions, and the role of water in trapping the nitrilium intermediate are also discussed.

Radon transformation on reductive symmetric spaces:Support theorems

DEFF Research Database (Denmark)

Kuit, Job Jacob

2013-01-01

We introduce a class of Radon transforms for reductive symmetric spaces, including the horospherical transforms, and derive support theorems for these transforms. A reductive symmetric space is a homogeneous space G/H for a reductive Lie group G of the Harish-Chandra class, where H is an open sub...... is based on the relation between the Radon transform and the Fourier transform on G/H, and a Paley–Wiener-shift type argument. Our results generalize the support theorem of Helgason for the Radon transform on a Riemannian symmetric space....

Explicit Gaussian quadrature rules for C^1 cubic splines with symmetrically stretched knot sequence

KAUST Repository

Ait-Haddou, Rachid; Barton, Michael; Calo, Victor M.

2015-01-01

We provide explicit expressions for quadrature rules on the space of C^1 cubic splines with non-uniform, symmetrically stretched knot sequences. The quadrature nodes and weights are derived via an explicit recursion that avoids an intervention

C-NAP1 and rootletin restrain DNA damage-induced centriole splitting and facilitate ciliogenesis.

Science.gov (United States)

Conroy, Pauline C; Saladino, Chiara; Dantas, Tiago J; Lalor, Pierce; Dockery, Peter; Morrison, Ciaran G

2012-10-15

Cilia are found on most human cells and exist as motile cilia or non-motile primary cilia. Primary cilia play sensory roles in transducing various extracellular signals, and defective ciliary functions are involved in a wide range of human diseases. Centrosomes are the principal microtubule-organizing centers of animal cells and contain two centrioles. We observed that DNA damage causes centriole splitting in non-transformed human cells, with isolated centrioles carrying the mother centriole markers CEP170 and ninein but not kizuna or cenexin. Loss of centriole cohesion through siRNA depletion of C-NAP1 or rootletin increased radiation-induced centriole splitting, with C-NAP1-depleted isolated centrioles losing mother markers. As the mother centriole forms the basal body in primary cilia, we tested whether centriole splitting affected ciliogenesis. While irradiated cells formed apparently normal primary cilia, most cilia arose from centriolar clusters, not from isolated centrioles. Furthermore, C-NAP1 or rootletin knockdown reduced primary cilium formation. Therefore, the centriole cohesion apparatus at the proximal end of centrioles may provide a target that can affect primary cilium formation as part of the DNA damage response.

Facial One-Pot Synthesis of D 3h Symmetric Bicyclocalix[2]arene[2]triazines and Their Layered Comb Self-Assembly

KAUST Repository

Chen, Yin

2017-11-23

A number of D3h symmetric bicyclocalix[2]arene[2]triazine core compounds were synthesized via a general and good-yielding (43-48% yield) facile protocol starting from cyanuric halides, phloroglucinol and K2CO3 under very mild reaction conditions. These cage-like compounds are tolerate with different reaction conditions and can be derived with other functional groups in high yield. The X-ray crystal structures show these compounds have slightly distorted D3h symmetric structures. Due to the unique molecular topological structure, bicyclocalix[2]arene[2]triazine molecules form unique layered comb networks when hydrogen bond groups exist (such as CO2H, B(OH)2), which represent a new kind of building block unit for supramolecular architectures.

Symmetric Assembly of a Sterically Encumbered Allyl Complex: Mechanochemical and Solution Synthesis of the Tris(allylberyllate, K[BeA′3] (A′ = 1,3-(SiMe32C3H3

Directory of Open Access Journals (Sweden)

Nicholas C. Boyde

2017-05-01

Full Text Available The ball milling of beryllium chloride with two equivalents of the potassium salt of bis(1,3-trimethylsilylallyl anion, K[A′] (A′ = [1,3-(SiMe32C3H3], produces the tris(allylberyllate K[BeA’3] (1 rather than the expected neutral BeA’2. The same product is obtained from reaction in hexanes; in contrast, although a similar reaction conducted in Et2O was previously shown to produce the solvated species BeA’2(OEt2, it can produce 1 if the reaction time is extended (16 h. The tris(allylberyllate is fluxional in solution, and displays the strongly downfield 9Be NMR shift expected for a three-coordinate Be center (δ22.8 ppm. A single crystal X-ray structure reveals that the three allyl ligands are bound to beryllium in an arrangement with approximate C3 symmetry (Be–C (avg = 1.805(10 Å, with the potassium cation engaging in cation–π interactions with the double bonds of the allyl ligands. Similar structures have previously been found in complexes of zinc and tin, i.e., M[M′A′3L] (M′ = Zn, M = Li, Na, K; M′ = Sn, M = K; L = thf. Density functional theory (DFT calculations indicate that the observed C3-symmetric framework of the isolated anion ([BeA′3]− is 20 kJ·mol−1 higher in energy than a C1 arrangement; the K+ counterion evidently plays a critical role in templating the final conformation.

Node-Splitting Generalized Linear Mixed Models for Evaluation of Inconsistency in Network Meta-Analysis.

Science.gov (United States)

Yu-Kang, Tu

2016-12-01

Network meta-analysis for multiple treatment comparisons has been a major development in evidence synthesis methodology. The validity of a network meta-analysis, however, can be threatened by inconsistency in evidence within the network. One particular issue of inconsistency is how to directly evaluate the inconsistency between direct and indirect evidence with regard to the effects difference between two treatments. A Bayesian node-splitting model was first proposed and a similar frequentist side-splitting model has been put forward recently. Yet, assigning the inconsistency parameter to one or the other of the two treatments or splitting the parameter symmetrically between the two treatments can yield different results when multi-arm trials are involved in the evaluation. We aimed to show that a side-splitting model can be viewed as a special case of design-by-treatment interaction model, and different parameterizations correspond to different design-by-treatment interactions. We demonstrated how to evaluate the side-splitting model using the arm-based generalized linear mixed model, and an example data set was used to compare results from the arm-based models with those from the contrast-based models. The three parameterizations of side-splitting make slightly different assumptions: the symmetrical method assumes that both treatments in a treatment contrast contribute to inconsistency between direct and indirect evidence, whereas the other two parameterizations assume that only one of the two treatments contributes to this inconsistency. With this understanding in mind, meta-analysts can then make a choice about how to implement the side-splitting method for their analysis. Copyright © 2016 International Society for Pharmacoeconomics and Outcomes Research (ISPOR). Published by Elsevier Inc. All rights reserved.

Valley-symmetric quasi-1D transport in ballistic graphene

Science.gov (United States)

Lee, Hu-Jong

We present our recent studies on gate-defined valley-symmetric one-dimensional (1D) carrier guiding in ballistic monolayer graphene and valley-symmetry-protected topological 1D transport in ballistic bilayer graphene. Successful carrier guiding was realized in ballistic monolayer graphene even in the absence of a band gap by inducing a high distinction ( more than two orders of magnitude) in the carrier density between the region of a quasi-1D channel and the rest of the top-gated regions. Conductance of a channel shows quantized values in units of 4e2/ h, suggesting that the valley symmetry is preserved. For the latter, the topological 1D conduction was realized between two closely arranged insulating regions with inverted band gaps, induced under a pair of split dual gating with polarities opposite to each other. The maximum conductance along the boundary channel showed 4e2/ h, again with the preserved valley symmetry. The 1D topological carrier guiding demonstrated in this study affords a promising route to robust valleytronic applications and sophisticated valley-associated functionalities based on 2D materials. This work was funded by the National Research Foundation of Korea.

Determination of symmetrical index for 3H in river waters

International Nuclear Information System (INIS)

Jankovic, M.; Todorovic, D.; Jankovic, B.; Nikolic, J.; Sarap, N.

2011-01-01

The paper presents the results of determining the symmetric index, which describes the magnitude of the tritium content changes with time, for samples of Sava and Danube river waters and Mlaka creek water. The results cover the period from 2003 to 2008. It was shown that the value of the symmetric index is the highest for Mlaka samples, which is in accordance with the fact that in these samples the highest concentration of tritium was found in comparison with samples of the Sava and Danube. [sr

Analysis and modeling of wafer-level process variability in 28 nm FD-SOI using split C-V measurements

Science.gov (United States)

Pradeep, Krishna; Poiroux, Thierry; Scheer, Patrick; Juge, André; Gouget, Gilles; Ghibaudo, Gérard

2018-07-01

This work details the analysis of wafer level global process variability in 28 nm FD-SOI using split C-V measurements. The proposed approach initially evaluates the native on wafer process variability using efficient extraction methods on split C-V measurements. The on-wafer threshold voltage (VT) variability is first studied and modeled using a simple analytical model. Then, a statistical model based on the Leti-UTSOI compact model is proposed to describe the total C-V variability in different bias conditions. This statistical model is finally used to study the contribution of each process parameter to the total C-V variability.

Evaluating efficiency of split VMAT plan for prostate cancer radiotherapy involving pelvic lymph nodes

Energy Technology Data Exchange (ETDEWEB)

Mun, Jun Ki; Son, Sang Jun; Kim, Dae Ho; Seo, Seok Jin [Dept. of Radiation Oncology, Seoul National University Hospital, Seoul (Korea, Republic of)

2015-12-15

The purpose of this study is to evaluate the efficiency of Split VMAT planning(Contouring rectum divided into an upper and a lower for reduce rectum dose) compare to Conventional VMAT planning(Contouring whole rectum) for prostate cancer radiotherapy involving pelvic lymph nodes. A total of 9 cases were enrolled. Each case received radiotherapy with Split VMAT planning to the prostate involving pelvic lymph nodes. Treatment was delivered using TrueBeam STX(Varian Medical Systems, USA) and planned on Eclipse(Ver. 10.0.42, Varian, USA), PRO3(Progressive Resolution Optimizer 10.0.28), AAA(Anisotropic Analytic Algorithm Ver. 10.0.28). Lower rectum contour was defined as starting 1 cm superior and ending 1 cm inferior to the prostate PTV, upper rectum is a part, except lower rectum from the whole rectum. Split VMAT plan parameters consisted of 10 MV coplanar 360° arcs. Each arc had 30° and 30° collimator angle, respectively. An SIB(Simultaneous Integrated Boost) treatment prescription was employed delivering 50.4 Gy to pelvic lymph nodes and 63- 70 Gy to the prostate in 28 fractions. D{sub mean} of whole rectum on Split VMAT plan was applied for DVC(Dose Volume Constraint) of the whole rectum for Conventional VMAT plan. In addition, all parameters were set to be the same of existing treatment plans. To minimize the dose difference that shows up randomly on optimizing, all plans were optimized and calculated twice respectively using a 0.2 cm grid. All plans were normalized to the prostate PTV{sub 100%} = 90% or 95%. A comparison of D{sub mean} of whole rectum, upperr ectum, lower rectum, and bladder, V{sub 50%} of upper rectum, total MU and H.I.(Homogeneity Index) and C.I.(Conformity Index) of the PTV was used for technique evaluation. All Split VMAT plans were verified by gamma test with portal dosimetry using EPID. Using DVH analysis, a difference between the Conventional and the Split VMAT plans was demonstrated. The Split VMAT plan demonstrated better in the D

Magnetospectroscopy of symmetric and anti-symmetric states in double quantum wells

Science.gov (United States)

Marchewka, M.; Sheregii, E. M.; Tralle, I.; Ploch, D.; Tomaka, G.; Furdak, M.; Kolek, A.; Stadler, A.; Mleczko, K.; Zak, D.; Strupinski, W.; Jasik, A.; Jakiela, R.

2008-02-01

The experimental results obtained for magnetotransport in the InGaAs/InAlAs double quantum well (DQW) structures of two different shapes of wells are reported. A beating effect occurring in the Shubnikov-de Haas (SdH) oscillations was observed for both types of structures at low temperatures in the parallel transport when the magnetic field was perpendicular to the layers. An approach for the calculation of the Landau level energies for DQW structures was developed and then applied to the analysis and interpretation of the experimental data related to the beating effect. We also argue that in order to account for the observed magnetotransport phenomena (SdH and integer quantum Hall effect), one should introduce two different quasi-Fermi levels characterizing two electron subsystems regarding the symmetry properties of their states, symmetric and anti-symmetric ones, which are not mixed by electron-electron interaction.

C(3i)-symmetric octanuclear cadmium cages: double-anion-templated synthesis, formation mechanism, and properties.

Science.gov (United States)

Sun, Jie; Sun, Di; Yuan, Shuai; Tian, Dongxu; Zhang, Liangliang; Wang, Xingpo; Sun, Daofeng

2012-12-14

A series of C(3i)-symmetric bicapped trigonal antiprismatic Cd(8) cages [2X@Cd(8)L(6)(H(2)O)(6)]⋅n Y⋅solvents (X = Cl(-), Y = NO(3)(-), n = 2: MOCC-4; X = Br(-), Y = NO(3)(-), n = 2: MOCC-5; X = NO(3)(-), Y = NO(3)(-), n = 2: MOCC-6; X = NO(3)(-), Y = BF(4)(-), n = 2: MOCC-7; X = NO(3)(-), Y = ClO(4)(-), n = 2: MOCC-8; X = CO(3)(2-), n = 0: MOCC-9), doubly anion templated by different anions, were solvothermally synthesized by means of a flexible ligand. Interestingly, the CO(3)(2-) template for MOCC-9 was generated in situ by two-step decomposition of DMF solvent. For other MOCCs, spherical or trigonal monovalent anions could also play the role of template in their formation. The template abilities of these anions in the formation of the cages were experimentally studied and are discussed for the first time. Anion exchange of MOCC-8 was carried out and showed anion-size selectivity. All of the cage-like compounds emit strong luminescence at room temperature. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Some curvature properties of quarter symmetric metric connections

International Nuclear Information System (INIS)

Rastogi, S.C.

1986-08-01

A linear connection Γ ji h with torsion tensor T j h P i -T i h P j , where T j h is an arbitrary (1,1) tensor field and P i is a 1-form, has been called a quarter-symmetric connection by Golab. Some properties of such connections have been studied by Rastogi, Mishra and Pandey, and Yano and Imai. In this paper based on the curvature tensor of quarter-symmetric metric connection we define a tensor analogous to conformal curvature tensor and study some properties of such a tensor. (author)

Student paper competition: Splitting the determinants of upper Hessenberg matrices and the Hyman method

Energy Technology Data Exchange (ETDEWEB)

Zou, Xiulin [Michigan State Univ., East Lansing, MI (United States)

1996-12-31

In this article, an iterative algorithm is established that splits the evaluation of determinant of an upper Hessenberg matrix into two independent parts so that the evaluation can be done in parallel. This algorithm has application in parallel non-symmetric eigenvalue problems.

Stabilization of self-mode-locked quantum dash lasers by symmetric dual-loop optical feedback

Science.gov (United States)

Asghar, Haroon; Wei, Wei; Kumar, Pramod; Sooudi, Ehsan; McInerney, John. G.

2018-02-01

We report experimental studies of the influence of symmetric dual-loop optical feedback on the RF linewidth and timing jitter of self-mode-locked two-section quantum dash lasers emitting at 1550 nm. Various feedback schemes were investigated and optimum levels determined for narrowest RF linewidth and low timing jitter, for single-loop and symmetric dual-loop feedback. Two symmetric dual-loop configurations, with balanced and unbalanced feedback ratios, were studied. We demonstrate that unbalanced symmetric dual loop feedback, with the inner cavity resonant and fine delay tuning of the outer loop, gives narrowest RF linewidth and reduced timing jitter over a wide range of delay, unlike single and balanced symmetric dual-loop configurations. This configuration with feedback lengths 80 and 140 m narrows the RF linewidth by 4-67x and 10-100x, respectively, across the widest delay range, compared to free-running. For symmetric dual-loop feedback, the influence of different power split ratios through the feedback loops was determined. Our results show that symmetric dual-loop feedback is markedly more effective than single-loop feedback in reducing RF linewidth and timing jitter, and is much less sensitive to delay phase, making this technique ideal for applications where robustness and alignment tolerance are essential.

1,4-Iron Migration for Expedient Allene Annulations through Iron-Catalyzed C-H/N-H/C-O/C-H Functionalizations.

Science.gov (United States)

Mo, Jiayu; Müller, Thomas; Oliveira, João C A; Ackermann, Lutz

2018-06-25

C-H activation bears great potential for enabling sustainable molecular syntheses in a step- and atom-economical manner, with major advances having been realized with precious 4d and 5d transition metals. In contrast, we employed earth abundant, nontoxic iron catalysts for versatile allene annulations through a unique C-H/N-H/C-O/C-H functionalization sequence. The powerful iron catalysis occurred under external-oxidant-free conditions even at room temperature, while detailed mechanistic studies revealed an unprecedented 1,4-iron migration regime for facile C-H activations. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanotrumpets and circularly polarized luminescent nanotwists hierarchically self-assembled from an achiral C3-symmetric ester.

Science.gov (United States)

Sang, Yutao; Duan, Pengfei; Liu, Minghua

2018-04-17

An achiral C3-symmetric molecule was found to self-assemble into various hierarchical nanostructures such as nanotwists, nanotrumpets and nanobelts, in which the twisted fibers showed supramolecular chirality as well as circularly polarized luminescence although the compound is achiral.

Permutation 2-groups I: structure and splitness

OpenAIRE

Elgueta, Josep

2013-01-01

By a 2-group we mean a groupoid equipped with a weakened group structure. It is called split when it is equivalent to the semidirect product of a discrete 2-group and a one-object 2-group. By a permutation 2-group we mean the 2-group $\\mathbb{S}ym(\\mathcal{G})$ of self-equivalences of a groupoid $\\mathcal{G}$ and natural isomorphisms between them, with the product given by composition of self-equivalences. These generalize the symmetric groups $\\mathsf{S}_n$, $n\\geq 1$, obtained when $\\mathca...

Optimization of operating parameters for gas-phase photocatalytic splitting of H2S by novel vermiculate packed tubular reactor.

Science.gov (United States)

Preethi, V; Kanmani, S

2016-10-01

Hydrogen production by gas-phase photocatalytic splitting of Hydrogen Sulphide (H2S) was investigated on four semiconductor photocatalysts including CuGa1.6Fe0.4O2, ZnFe2O3, (CdS + ZnS)/Fe2O3 and Ce/TiO2. The CdS and ZnS coated core shell particles (CdS + ZnS)/Fe2O3 shows the highest rate of hydrogen (H2) production under optimized conditions. Packed bed tubular reactor was used to study the performance of prepared photocatalysts. Selection of the best packing material is a key for maximum removal efficiency. Cheap, lightweight and easily adsorbing vermiculate materials were used as a novel packing material and were found to be effective in splitting H2S. Effect of various operating parameters like flow rate, sulphide concentration, catalyst dosage, light irradiation were tested and optimized for maximum H2 conversion of 92% from industrial waste H2S. Copyright © 2016 Elsevier Ltd. All rights reserved.

Split of the superconducting transition and magnetism in UPt3

International Nuclear Information System (INIS)

Marikhin, V.G.

1992-01-01

A possible reason for splitting the superconducting phase transition in UPt 3 is discussed. The strong coupling of conduction electrons with uranium atom magnetic moments may be such a cause. The given assertion is based on the simple model described by the two-component order parameter φ Ginzburg -Landau functional. The Ginzburg - Landau functional without coupling has the whole symmetry D 6h of hexagonal crystal. Due to the presence of uranium atom magnetic moments M the symmetry is broken locally with the coupling term γ|Mφ| 2 in the Ginzburg - Landau functional. Averaging over the vector M configurations with the involment of the finite correlation radius a is performed. The inequality a 6h . This means that in a real crystal the hexagonal symmetry is not broken at the scales larger ξ. In the framework of the given theory the expressions for the specific heat jumps and equation combining the upper critical field H c2 and the phase transition split ΔT c with the pressure variation are obtained. The difficulties connencted with the small experimental magnitude of uranium atom magnetic moments are discussed

Design of a dual linear polarization antenna using split ring resonators at X-band

Science.gov (United States)

Ahmed, Sadiq; Chandra, Madhukar

2017-11-01

Dual linear polarization microstrip antenna configurations are very suitable for high-performance satellites, wireless communication and radar applications. This paper presents a new method to improve the co-cross polarization discrimination (XPD) for dual linear polarized microstrip antennas at 10 GHz. For this, three various configurations of a dual linear polarization antenna utilizing metamaterial unit cells are shown. In the first layout, the microstrip patch antenna is loaded with two pairs of spiral ring resonators, in the second model, a split ring resonator is placed between two microstrip feed lines, and in the third design, a complementary split ring resonators are etched in the ground plane. This work has two primary goals: the first is related to the addition of metamaterial unit cells to the antenna structure which permits compensation for an asymmetric current distribution flow on the microstrip antenna and thus yields a symmetrical current distribution on it. This compensation leads to an important enhancement in the XPD in comparison to a conventional dual linear polarized microstrip patch antenna. The simulation reveals an improvement of 7.9, 8.8, and 4 dB in the E and H planes for the three designs, respectively, in the XPD as compared to the conventional dual linear polarized patch antenna. The second objective of this paper is to present the characteristics and performances of the designs of the spiral ring resonator (S-RR), split ring resonator (SRR), and complementary split ring resonator (CSRR) metamaterial unit cells. The simulations are evaluated using the commercial full-wave simulator, Ansoft High-Frequency Structure Simulator (HFSS).

Study of the unimolecular decompositions of the (C3H6)+2 and (c-C3H6)+2 complexes

International Nuclear Information System (INIS)

Tzeng, W.; Ono, Y.; Linn, S.H.; Ng, C.Y.

1985-01-01

The major product channels identified in the unimolecular decompositions ofC 3 H + 6 xC 3 H 6 and c-C 3 H + 6 xc-C 3 H 6 in the total energy [neutral (C 3 H 6 ) 2 or (c-C 3 H 6 ) 2 heat of formation plus excitation energy] range of approx.230--450 kcal/mol are C 3 H + 7 +C 3 H 5 , C 4 H + 7 +C 2 H 5 , C 4 H + 8 +C 2 H 4 , and C 5 H + 9 +CH 3 . The measured appearance energy for C 4 H + 7 (9.54 +- 0.04 eV) from (C 3 H 6 ) 2 is equal to the thermochemical threshold for the formation of C 4 H + 7 +C 2 H 5 from (C 3 H 6 ) 2 , indicating that the exit potential energy barrier for the ion--molecule reaction C 3 H + 6 +C 3 H 6 →C 4 H + 7 +C 2 H 5 is negligible. There is evidence that the formations of C 4 H + 7 +C 2 H 4 +H from (C 3 H 6 ) + 2 and (c-C 3 H 6 ) + 2 also proceed with high probabilities when they are energetically allowed. The variations of the relative abundances for C 4 H + 7 ,C 4 H + 8 , and C 5 H + 9 from (C 3 H 6 ) + 2 and (c-C 3 H 6 ) + 2 as a function of ionizing photon energy are in qualitative agreement, suggesting that (C 3 H 6 ) + 2 and (c-C 3 H 6 ) + 2 rearrange to similar C 6 H + 12 isomers prior to fragmentation. The fact that C 6 H + 11 is found to be a primary ion from the unimolecular decomposition of (c-C 3 H 6 ) + 2 but not (C 3 H 6 ) + 2 supports the conclusion that the distribution of C 6 H + 12 collision complexes involved in the C 3 H + 6 +C 3 H 6 reactions is different from that in the cyclopropane ion--molecule reactions

Reaction mechanism for the symmetric breakup of 24Mg following an interaction with 12C

International Nuclear Information System (INIS)

Gyapong, G.J.; Watson, D.L.; Catford, W.N.; Clarke, N.M.; Bennett, S.J.; Freer, M.; Fulton, B.R.; Jones, C.D.; Leddy, M.; Murgatroyd, J.T.; Rae, W.D.M.; Simmons, P.

1994-01-01

Data on the yield of the symmetric breakup of 24 Mg as a function of beam energy are presented and compared with detailed calculations of the energy dependence. The 24 Mg states seen in symmetric breakup agree with previously observed breakup states having spin and parities J π =4 + ,(6 + ),8 + . The data allow the variations of yield for indivual states to be judged, as the beam energy is varied. The variation in the yield of the 4 + states is compared in detail with calculations assuming several possible compound nuclear or direct reaction mechanisms. It is concluded that a massive ( 12 C) transfer or a simple statistical compound process are unlikely mechanisms, but that each of several other mechanisms is consistent with the data. ((orig.))

Evaluating C-RAN Fronthaul Functional Splits in Terms of Network Level Energy and Cost Savings

DEFF Research Database (Denmark)

Checko, Aleksandra; Popovska Avramova, Andrijana; Berger, Michael Stübert

2016-01-01

The placement of the complete baseband processing in a centralized pool results in high data rate requirement and inflexibility of the fronthaul network, which challenges the energy and cost effectiveness of the cloud radio access network (C-RAN). Recently, redesign of the C-RAN through functional...... split in the baseband processing chain has been proposed to overcome these challenges. This paper evaluates, by mathematical and simulation methods, different splits with respect to network level energy and cost efficiency having in the mind the expected quality of service.The proposed mathematical...... model quantifies the multiplexing gains and the trade-offs between centralization and decentralization concerning the cost of the pool, fronthaul network capacity and resource utilization. The event-based simulation captures the influence of the traffic load dynamics and traffic type variation...

Capacity Bounds on the Downlink of Symmetric, Multi-Relay, Single-Receiver C-RAN Networks

Directory of Open Access Journals (Sweden)

Shirin Saeedi Bidokhti

2017-11-01

Full Text Available The downlink of symmetric Cloud Radio Access Networks (C-RANs with multiple relays and a single receiver is studied. Lower and upper bounds are derived on the capacity. The lower bound is achieved by Marton’s coding, which facilitates dependence among the multiple-access channel inputs. The upper bound uses Ozarow’s technique to augment the system with an auxiliary random variable. The bounds are studied over scalar Gaussian C-RANs and are shown to meet and characterize the capacity for interesting regimes of operation.

Mobility-Aware Modeling and Analysis of Dense Cellular Networks With $C$ -Plane/ $U$ -Plane Split Architecture

KAUST Repository

Ibrahim, Hazem

2016-09-19

The unrelenting increase in the population of mobile users and their traffic demands drive cellular network operators to densify their network infrastructure. Network densification shrinks the footprint of base stations (BSs) and reduces the number of users associated with each BS, leading to an improved spatial frequency reuse and spectral efficiency, and thus, higher network capacity. However, the densification gain comes at the expense of higher handover rates and network control overhead. Hence, user’s mobility can diminish or even nullifies the foreseen densification gain. In this context, splitting the control plane ( C -plane) and user plane ( U -plane) is proposed as a potential solution to harvest densification gain with reduced cost in terms of handover rate and network control overhead. In this paper, we use stochastic geometry to develop a tractable mobility-aware model for a two-tier downlink cellular network with ultra-dense small cells and C -plane/ U -plane split architecture. The developed model is then used to quantify the effect of mobility on the foreseen densification gain with and without C -plane/ U -plane split. To this end, we shed light on the handover problem in dense cellular environments, show scenarios where the network fails to support certain mobility profiles, and obtain network design insights.

Symmetrical analysis of the defect level splitting in two-dimensional photonic crystals

International Nuclear Information System (INIS)

Malkova, N; Kim, S; Gopalan, V

2003-01-01

In this paper doubly degenerate defect states in the band gap of the two-dimensional photonic crystal are studied. These states can be split by a convenient distortion of the lattice. Through analogy with the Jahn-Teller effect in solids, we present a group theoretical analysis of the lifting of the degeneracy of doubly degenerate states in a square lattice by different vibronic modes. The effect is supported by the supercell plane-wave model and by the finite difference time domain technique. We suggest ways for using the effect in photonic switching devices and waveguides

InGaAs/InAlAs Double Quantum Wells as Starting Structures for Quantum Logic Gates

Science.gov (United States)

Marchewka, M.; Sheregii, E. M.

2011-12-01

The detection of both symmetric and anti-symmetric electron states in DQWs by an optical method is described in this paper. Values of the symmetric and anti-symmetric splitting (SAS-gap) determined in this way are used for interpretation of the beating effect in the SdH oscillations observed at low temperatures in the external magnetic field. SAS-splitting of electron states in DQWs clearly exists at room temperature and electrons in symmetric and anti-symmetric states have different statistics so these states can be identified in electron transport.

Facial One-Pot Synthesis of D 3h Symmetric Bicyclocalix[2]arene[2]triazines and Their Layered Comb Self-Assembly

KAUST Repository

Chen, Yin; Jiahui, Wang; Xu, Hai; Qianqian, Li; Jing, Jiang

2017-01-01

A number of D3h symmetric bicyclocalix[2]arene[2]triazine core compounds were synthesized via a general and good-yielding (43-48% yield) facile protocol starting from cyanuric halides, phloroglucinol and K2CO3 under very mild reaction conditions

New metal-organic frameworks of [M(C6H5O7)(C6H6O7)(C6H7O7)(H2O)] . H2O (M=La, Ce) and [Ce2(C2O4)(C6H6O7)2] . 4H2O

International Nuclear Information System (INIS)

Weng Shengfeng; Wang, Yun-Hsin; Lee, Chi-Shen

2012-01-01

Two novel materials, [M(C 6 H 5 O 7 )(C 6 H 6 O 7 )(C 6 H 7 O 7 )(H 2 O)] . H 2 O (M=La(1a), Ce(1b)) and [Ce 2 (C 2 O 4 )(C 6 H 6 O 7 ) 2 ] . 4H 2 O (2), with a metal-organic framework (MOF) were prepared with hydrothermal reactions and characterized with photoluminescence, magnetic susceptibility, thermogravimetric analysis and X-ray powder diffraction in situ. The crystal structures were determined by single-crystal X-ray diffraction. Compound 1 crystallized in triclinic space group P1-bar (No. 2); compound 2 crystallized in monoclinic space group P2 1 /c (No. 14). The structure of 1 is built from a 1D MOF, composed of deprotonated citric ligands of three kinds. Compound 2 contains a 2D MOF structure consisting of citrate and oxalate ligands; the oxalate ligand arose from the decomposition in situ of citric acid in the presence of Cu II ions. Photoluminescence spectra of compounds 1b and 2 revealed transitions between the 5d 1 excited state and two levels of the 4f 1 ground state ( 2 F 5/2 and 2 F 7/2 ). Compounds 1b and 2 containing Ce III ion exhibit a paramagnetic property with weak antiferromagnetic interactions between the two adjacent magnetic centers. - Graphical Abstract: [M(C 6 H 5 O 7 )(C 6 H 6 O 7 )(C 6 H 7 O 7 )(H 2 O)] . H 2 O (M=La(1a), Ce(1b)) and [Ce 2 (C 2 O 4 )(C 6 H 6 O 7 ) 2 ] . 4H 2 O (2)—with 1D and 2D structures were synthesized and characterized. Highlights: ► Two MOF – [M(C 6 H 5 O 7 )(C 6 H 6 O 7 )(C 6 H 7 O 7 )(H 2 O)] . H 2 O (M=La(1a), Ce(1b)) and [Ce 2 (C 2 O 4 )(C 6 H 6 O 7 ) 2 ] . 4H 2 O (2) – with 1D and 2D structures. ► The adjacent chains of the 1D framework were correlated with each other through an oxalate ligand to form a 2D layer structure. ► The source of the oxalate ligand was the decomposition in situ of citric acid oxidized in the presence of Cu II ions.

Explicit Gaussian quadrature rules for C^1 cubic splines with symmetrically stretched knot sequence

KAUST Repository

Ait-Haddou, Rachid

2015-06-19

We provide explicit expressions for quadrature rules on the space of C^1 cubic splines with non-uniform, symmetrically stretched knot sequences. The quadrature nodes and weights are derived via an explicit recursion that avoids an intervention of any numerical solver and the rule is optimal, that is, it requires minimal number of nodes. Numerical experiments validating the theoretical results and the error estimates of the quadrature rules are also presented.

EPR study of gamma irradiated N-methyl taurine (C 3H 9NO 3S) and sodium hydrogen sulphate monohydrate (NaHSO 3·H 2O) single crystals

Science.gov (United States)

Yıldırım, İlkay; Karabulut, Bünyamin

2011-03-01

EPR study of gamma irradiated C 3H 9NO 3S and NaHSO 3.H 2O single crystals have been carried out at room temperature. There is one site for the radicals in C 3H 9NO 3S and two magnetically distinct sites for the radicals in NaHSO 3. The observed lines in the EPR spectra have been attributed to the species of SO3- and RH radicals for N-methyl taurine, and to the SO3- and OH radicals for sodium hydrogen sulfate monohydrate single crystals. The principal values of the g for SO3-, the hyperfine values of RH and OH proton splitting have been calculated and discussed.

Effect of intermolecular dipole-dipole interactions on interfacial supramolecular structures of C3-symmetric hexa-peri-hexabenzocoronene derivatives.

Science.gov (United States)

Mu, Zhongcheng; Shao, Qi; Ye, Jun; Zeng, Zebing; Zhao, Yang; Hng, Huey Hoon; Boey, Freddy Yin Chiang; Wu, Jishan; Chen, Xiaodong

2011-02-15

Two-dimensional (2D) supramolecular assemblies of a series of novel C(3)-symmetric hexa-peri-hexabenzocoronene (HBC) derivatives bearing different substituents adsorbed on highly oriented pyrolytic graphite were studied by using scanning tunneling microscopy at a solid-liquid interface. It was found that the intermolecular dipole-dipole interactions play a critical role in controlling the interfacial supramolecular assembly of these C(3)-symmetric HBC derivatives at the solid-liquid interface. The HBC molecule bearing three -CF(3) groups could form 2D honeycomb structures because of antiparallel dipole-dipole interactions, whereas HBC molecules bearing three -CN or -NO(2) groups could form hexagonal superstructures because of a special trimeric arrangement induced by dipole-dipole interactions and weak hydrogen bonding interactions ([C-H···NC-] or [C-H···O(2)N-]). Molecular mechanics and dynamics simulations were performed to reveal the physics behind the 2D structures as well as detailed functional group interactions. This work provides an example of how intermolecular dipole-dipole interactions could enable fine control over the self-assembly of disklike π-conjugated molecules.

Kinetics of the reactions H+C2H4->C2H5, H+C2H5->2CH3 and CH3+C2H5->products studies by pulse radiolysis combined with infrared diode laser spectroscopy

DEFF Research Database (Denmark)

Sillesen, A.; Ratajczak, E.; Pagsberg, P.

1993-01-01

Formation of methyl radicals via the consecutive reactions H+C2H4+M-->C2H5+M (1) and H+C2H5-->CH3+CH3 (2a) was initiated by pulse radiolysis of 10-100 mbar H-2 in the presence of ethylene. The kinetics of CH3 Were studied by monitoring the transient infrared absorption at the Q(3, 3) line of the ...

Systematic theoretical investigation of the zero-field splitting in Gd(III) complexes: Wave function and density functional approaches

Energy Technology Data Exchange (ETDEWEB)

Khan, Shehryar, E-mail: sherkhan@fysik.su.se; Odelius, Michael, E-mail: odelius@fysik.su.se [Department of Physics, Stockholm University, AlbaNova University Center, S-106 91 Stockholm (Sweden); Kubica-Misztal, Aleksandra [Institute of Physics, Jagiellonian University, ul. Reymonta 4, PL-30-059 Krakow (Poland); Kruk, Danuta [Faculty of Mathematics and Computer Science, University of Warmia and Mazury in Olsztyn, Sloneczna 54, Olsztyn PL-10710 (Poland); Kowalewski, Jozef [Department of Materials and Environmental Chemistry, Arrhenius Laboratory, Stockholm University, S-106 91 Stockholm (Sweden)

2015-01-21

The zero-field splitting (ZFS) of the electronic ground state in paramagnetic ions is a sensitive probe of the variations in the electronic and molecular structure with an impact on fields ranging from fundamental physical chemistry to medical applications. A detailed analysis of the ZFS in a series of symmetric Gd(III) complexes is presented in order to establish the applicability and accuracy of computational methods using multiconfigurational complete-active-space self-consistent field wave functions and of density functional theory calculations. The various computational schemes are then applied to larger complexes Gd(III)DOTA(H{sub 2}O){sup −}, Gd(III)DTPA(H{sub 2}O){sup 2−}, and Gd(III)(H{sub 2}O){sub 8}{sup 3+} in order to analyze how the theoretical results compare to experimentally derived parameters. In contrast to approximations based on density functional theory, the multiconfigurational methods produce results for the ZFS of Gd(III) complexes on the correct order of magnitude.

Tungsten carbide nanoparticles as efficient cocatalysts for photocatalytic overall water splitting

KAUST Repository

Garcia Esparza, Angel T.

2012-12-17

Tungsten carbide exhibits platinum-like behavior, which makes it an interesting potential substitute for noble metals in catalytic applications. Tungsten carbide nanocrystals (≈5 nm) are directly synthesized through the reaction of tungsten precursors with mesoporous graphitic C3N 4 (mpg-C3N4) as the reactive template in a flow of inert gas at high temperatures. Systematic experiments that vary the precursor compositions and temperatures used in the synthesis selectively generate different compositions and structures for the final nanocarbide (W 2C or WC) products. Electrochemical measurements demonstrate that the WC phase with a high surface area exhibits both high activity and stability in hydrogen evolution over a wide pH range. The WC sample also shows excellent hydrogen oxidation activity, whereas its activity in oxygen reduction is poor. These tungsten carbides are successful cocatalysts for overall water splitting and give H2 and O2 in a stoichiometric ratio from H 2O decomposition when supported on a Na-doped SrTiO3 photocatalyst. Herein, we present tungsten carbide (on a small scale) as a promising and durable catalyst substitute for platinum and other scarce noble-metal catalysts in catalytic reaction systems used for renewable energy generation. Platinum replacement: The phase-controlled synthesis of tungsten carbide nanoparticles from the nanoconfinement of a mesoporous graphite C 3N4 (mpg-C3N4) reactive template is shown. The nanomaterials catalyze hydrogen evolution/oxidation reactions, but are inactive in the oxygen reduction reaction. Tungsten carbide is an effective cocatalyst for photocatalytic overall water splitting (see picture). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tungsten carbide nanoparticles as efficient cocatalysts for photocatalytic overall water splitting

KAUST Repository

Garcia Esparza, Angel T.; Cha, Dong Kyu; Ou, Yiwei; Kubota, Jun; Domen, Kazunari; Takanabe, Kazuhiro

2012-01-01

Tungsten carbide exhibits platinum-like behavior, which makes it an interesting potential substitute for noble metals in catalytic applications. Tungsten carbide nanocrystals (≈5 nm) are directly synthesized through the reaction of tungsten precursors with mesoporous graphitic C3N 4 (mpg-C3N4) as the reactive template in a flow of inert gas at high temperatures. Systematic experiments that vary the precursor compositions and temperatures used in the synthesis selectively generate different compositions and structures for the final nanocarbide (W 2C or WC) products. Electrochemical measurements demonstrate that the WC phase with a high surface area exhibits both high activity and stability in hydrogen evolution over a wide pH range. The WC sample also shows excellent hydrogen oxidation activity, whereas its activity in oxygen reduction is poor. These tungsten carbides are successful cocatalysts for overall water splitting and give H2 and O2 in a stoichiometric ratio from H 2O decomposition when supported on a Na-doped SrTiO3 photocatalyst. Herein, we present tungsten carbide (on a small scale) as a promising and durable catalyst substitute for platinum and other scarce noble-metal catalysts in catalytic reaction systems used for renewable energy generation. Platinum replacement: The phase-controlled synthesis of tungsten carbide nanoparticles from the nanoconfinement of a mesoporous graphite C 3N4 (mpg-C3N4) reactive template is shown. The nanomaterials catalyze hydrogen evolution/oxidation reactions, but are inactive in the oxygen reduction reaction. Tungsten carbide is an effective cocatalyst for photocatalytic overall water splitting (see picture). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Measurement of 2J(H,C)- and 3J(H,C)-coupling constants by α/β selective HC(C)H-TOCSY

International Nuclear Information System (INIS)

Duchardt, Elke; Richter, Christian; Reif, Bernd; Glaser, Steffen J.; Engels, Joachim W.; Griesinger, Christian; Schwalbe, Harald

2001-01-01

A new heteronuclear NMR pulse sequence for the measurement of n J(C,H) coupling constants, the α/βselective HC(C)H-TOCSY, is described. It is shown that the S 3 E element (Meissner et al., 1997a,b) can be used to obtain spin state selective coherence transfer in molecules, in which adjacent CH moieties are labeled with 13 C. Application of the α/β selective HC(C)H-TOCSY to a 10nt RNA tetraloop 5'-CGCUUUUGCG-3', in which the four uridine residues are 13 C labeled in the sugar moiety, allowed measurement of two bond and three bond J(C,H) coupling constants, which provide additional restraints to characterize the sugar ring conformation of RNA in cases of conformational averaging

EPR and optical absorption studies of VO2+ doped L-alanine (C3H7NO2) single crystals

International Nuclear Information System (INIS)

Biyik, Recep

2009-01-01

VO 2+ doped L-alanine (C 3 H 7 NO 2 ) single crystals and powders are examined by electron paramagnetic resonance (EPR) and optical absorption spectroscopy. Three magnetically different sites are resolved from angular variations of L-alanine single crystal EPR spectra. In some specific orientations each VO 2+ line splits into three superhyperfine lines with intensities of 1:2:1 and maximum splitting value of 2.23 mT. The local symmetries of VO 2+ complex sites are nearly axial. The optical absorption spectra show three bands. Spin Hamiltonian parameters are measured and molecular orbital coefficients are calculated by correlating EPR and optical absorption data for the central vanadyl ion.

Crystal-field splitting in coadsorbate systems: c (2x2) CO/K/Ni (100)

NARCIS (Netherlands)

Hasselström, J.; Föhlisch, A.; Denecke, R.; Nilsson, A.; Groot, F.M.F. de

2000-01-01

It is demonstrated how the crystal field splitting (CFS) fine structure can be used to characterize a coadsor-bate system. We have applied K 2p x-ray absorption spectroscopy (XAS) to the c(2x2) CO/K/Ni(100) system. The CFS fine structure is shown to be sensitive to the the local atomic

Redox Kinetics and Nonstoichiometry of Ce0.5Zr0.5O2−δ for Water Splitting and Hydrogen Production

KAUST Repository

Zhao, Zhenlong

2017-04-25

Water splitting and chemical fuel production as a promising carbon-neutral energy solution relies critically on an efficient electrochemical process over catalyst surfaces. The fundamentals within the surface redox pathways, including the complex interactions of mobile ions and electrons between the bulk and the surface, along with the role of adsorbates and electrostatic fields remain yet to be understood quantitatively. This work presents a detailed kinetics study and nonstoichiometry characterization of Ce0.5Zr0.5O2−δ (CZO), one of the most recognized catalysts for water splitting. The use of CZO leads to >60% improvement in the kinetic rates as compared with undoped ceria with twice the total yield at 700 °C, resulting from the improved reducibility. The peak H2 production rate is 95 μmol g–1 s–1 at 700 °C, and the total production is 750 μmol g–1. A threshold temperature of 650 °C is required to achieve significant H2 production at fast rates. The redox kinetics is modeled using two-step surface chemistry with bulk-to-surface transport equilibrium. Kinetics and equilibrium parameters are extracted, and the model predictions show good agreement with the measurements. The enthalpy of bulk defect formation for CZO is found to be 262 kJ/mol, >40% lower than that of undoped ceria. As oxygen vacancy is gradually filled up, the surface H2O splitting chemistry undergoes a transition from exothermic to endothermic, with the crossover around δ = 0.04 to 0.05, which constrains the further ion incorporation process. Our kinetics study reveals that the H2O splitting process with CZO is kinetics limited at low temperature and transitions to partial-equilibrium with significantly enhanced backward reaction at high temperature. The charge-transfer step is found to be the rate-limiting step for H2O splitting. The detailed kinetics and nonstoichiometric equilibria should be helpful in guiding the design and optimization of CZO as a catalyst, oxygen storage

Separator-Integrated, Reversely Connectable Symmetric Lithium-Ion Battery.

Science.gov (United States)

Wang, Yuhang; Zeng, Jiren; Cui, Xiaoqi; Zhang, Lijuan; Zheng, Gengfeng

2016-02-24

A separator-integrated, reversely connectable, symmetric lithium-ion battery is developed based on carbon-coated Li3V2(PO4)3 nanoparticles and polyvinylidene fluoride-treated separators. The Li3V2(PO4)3 nanoparticles are synthesized via a facile solution route followed by calcination in Ar/H2 atmosphere. Sucrose solution is used as the carbon source for uniform carbon coating on the Li3V2(PO4)3 nanoparticles. Both the carbon and the polyvinylidene fluoride treatments substantially improve the cycling life of the symmetric battery by preventing the dissolution and shuttle of the electroactive Li3V2(PO4)3. The obtained symmetric full cell exhibits a reversible capacity of ≈ 87 mA h g(-1), good cycling stability, and capacity retention of ≈ 70% after 70 cycles. In addition, this type of symmetric full cell can be operated in both forward and reverse connection modes, without any influence on the cycling of the battery. Furthermore, a new separator integration approach is demonstrated, which enables the direct deposition of electroactive materials for the battery assembly and does not affect the electrochemical performance. A 10-tandem-cell battery assembled without differentiating the electrode polarity exhibits a low thickness of ≈ 4.8 mm and a high output voltage of 20.8 V. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Analysis and experimental results of frequency splitting of underwater wireless power transfer

Directory of Open Access Journals (Sweden)

Wangqiang Niu

2017-06-01

Full Text Available Underwater wireless power transfer (UWPT is an important technique to power underwater devices while its frequency splitting phenomena are not fully elucidated. In this study, frequency splitting phenomena of a symmetrical planar two-coil wireless power transfer (WPT system resonated at 90 kHz are investigated in seawater and freshwater. A concise frequency splitting analysis of this WPT system in air based on circuit model is given first and then experimental data are reported to show there is little difference between power transfer in air, freshwater and seawater in the range of 40–140 kHz of this WPT system. Consequently, the frequency splitting analysis and observations in air are also applicable in freshwater and seawater. It is found a V-type frequency splitting pattern exists in this WPT system under seawater and freshwater. Frequency shift is observed in this UWPT system in overcoupled region, and no frequency shift is observed in undercoupled region. In undercoupled region, in the low frequency zone of 40–90 kHz the load voltage characteristics in three media are identical; in the high-frequency zone of 90–140 kHz, the load voltage in air is slightly larger than those in freshwater and seawater.

Electroweak splitting functions and high energy showering

Science.gov (United States)

Chen, Junmou; Han, Tao; Tweedie, Brock

2017-11-01

We derive the electroweak (EW) collinear splitting functions for the Standard Model, including the massive fermions, gauge bosons and the Higgs boson. We first present the splitting functions in the limit of unbroken SU(2) L × U(1) Y and discuss their general features in the collinear and soft-collinear regimes. These are the leading contributions at a splitting scale ( k T ) far above the EW scale ( v). We then systematically incorporate EW symmetry breaking (EWSB), which leads to the emergence of additional "ultra-collinear" splitting phenomena and naive violations of the Goldstone-boson Equivalence Theorem. We suggest a particularly convenient choice of non-covariant gauge (dubbed "Goldstone Equivalence Gauge") that disentangles the effects of Goldstone bosons and gauge fields in the presence of EWSB, and allows trivial book-keeping of leading power corrections in v/ k T . We implement a comprehensive, practical EW showering scheme based on these splitting functions using a Sudakov evolution formalism. Novel features in the implementation include a complete accounting of ultra-collinear effects, matching between shower and decay, kinematic back-reaction corrections in multi-stage showers, and mixed-state evolution of neutral bosons ( γ/ Z/ h) using density-matrices. We employ the EW showering formalism to study a number of important physical processes at O (1-10 TeV) energies. They include (a) electroweak partons in the initial state as the basis for vector-boson-fusion; (b) the emergence of "weak jets" such as those initiated by transverse gauge bosons, with individual splitting probabilities as large as O (35%); (c) EW showers initiated by top quarks, including Higgs bosons in the final state; (d) the occurrence of O (1) interference effects within EW showers involving the neutral bosons; and (e) EW corrections to new physics processes, as illustrated by production of a heavy vector boson ( W ') and the subsequent showering of its decay products.

Causal symmetric spaces

CERN Document Server

Olafsson, Gestur; Helgason, Sigurdur

1996-01-01

This book is intended to introduce researchers and graduate students to the concepts of causal symmetric spaces. To date, results of recent studies considered standard by specialists have not been widely published. This book seeks to bring this information to students and researchers in geometry and analysis on causal symmetric spaces.Includes the newest results in harmonic analysis including Spherical functions on ordered symmetric space and the holmorphic discrete series and Hardy spaces on compactly casual symmetric spacesDeals with the infinitesimal situation, coverings of symmetric spaces, classification of causal symmetric pairs and invariant cone fieldsPresents basic geometric properties of semi-simple symmetric spacesIncludes appendices on Lie algebras and Lie groups, Bounded symmetric domains (Cayley transforms), Antiholomorphic Involutions on Bounded Domains and Para-Hermitian Symmetric Spaces

Silicon nitride tri-layer vertical Y-junction and 3D couplers with arbitrary splitting ratio for photonic integrated circuits.

Science.gov (United States)

Shang, Kuanping; Pathak, Shibnath; Liu, Guangyao; Feng, Shaoqi; Li, Siwei; Lai, Weicheng; Yoo, S J B

2017-05-01

We designed and demonstrated a tri-layer Si3N4/SiO2 photonic integrated circuit capable of vertical interlayer coupling with arbitrary splitting ratios. Based on this multilayer photonic integrated circuit platform with each layer thicknesses of 150 nm, 50 nm, and 150 nm, we designed and simulated the vertical Y-junctions and 3D couplers with arbitrary power splitting ratios between 1:10 and 10:1 and with negligible(< -50 dB) reflection. Based on the design, we fabricated and demonstrated tri-layer vertical Y-junctions with the splitting ratios of 1:1 and 3:2 with excess optical losses of 0.230 dB. Further, we fabricated and demonstrated the 1 × 3 3D couplers with the splitting ratio of 1:1:4 for symmetric structures and variable splitting ratio for asymmetric structures.

Rhodium catalyzed regioselective arene homologation of aryl urea via double C-H bond activation and migratory insertion of alkyne

Institute of Scientific and Technical Information of China (English)

Yan Wang; Hao Zhou; Ke Xu; Mei-Hua Shen; Hua-Dong Xu

2017-01-01

A convenient rhodium catalyzed oxidative arene homologation of aniline derivatives with symmetrical or unsymmetrical alkynes using Cu(OAc)2 as oxidant is described.Urea group is shown to be effective as a directing group for initial ortho C-H activation.Two migratory insertion events of alkyne into Rh-C bond occur successively,both with complete regioselectivity.This method is particularly useful for synthesis of polyarenes with different substituents,which has not been reported with conventional protocol.A mechanism has been proposed to explain the observed data.

Si/C and H coadsorption at 4H-SiC{0001} surfaces

Energy Technology Data Exchange (ETDEWEB)

Wachowicz, E., E-mail: elwira@ifd.uni.wroc.pl [Institute of Experimental Physics, University of Wrocław, Plac M. Borna 9, PL-50-204 Wrocław (Poland); Interdisciplinary Centre for Mathematical and Computational Modelling, University of Warsaw, Pawińskiego 5a, PL-02-106 Warsaw (Poland)

2016-06-15

Highlights: • Si on C-terminated and C on Si-terminated surface adsorb in the H{sub 3} hollow site. • The preferred adsorption site is in contrary to the stacking order of bulk crystal. • The presence of hydrogen increases the adsorption energy of Si/C. • Hydrogen weakens the bonds between the adsorbed Si or C and the surface. • Carbon adsorbs on top of the surface carbon on the C-terminated surface. • With both C and H on Si-terminated surface the surface state vanishes. - Abstract: Density functional theory (DFT) study of adsorption of 0.25 monolayer of either Si or C on 4H-SiC{0001} surfaces is presented. The adsorption in high-symmetry sites on both Si- and C-terminated surfaces was examined and the influence of the preadsorbed 0.25 ML of hydrogen on the Si/C adsorption was considered. It was found out that for Si on C-terminated surface and C on Si-terminated the most favourable is threefolded adsorption site on both clean and H-precovered surface. This is contrary to the bulk crystal stacking order which would require adsorption on top of the topmost surface atom. In those cases, the presence of hydrogen weakens the bonding of the adsorbate. Carbon on the C-terminated surface, only binds on-top of the surface atom. The C−C bond-length is almost the same for the clean surface and for one with H and equals to ∼1.33 Å which is shorter by ∼0.2 than in diamond. The analysis of the electronic structure changes under adsorption is also presented.

Fourier transforms on a semisimple symmetric space

NARCIS (Netherlands)

Ban, E.P. van den; Schlichtkrull, H.

1994-01-01

Let G=H be a semisimple symmetric space, that is, G is a connected semisimple real Lie group with an involution ?, and H is an open subgroup of the group of xed points for ? in G. The main purpose of this paper is to study an explicit Fourier transform on G=H. In terms of general representation

Fourier transforms on a semisimple symmetric space

NARCIS (Netherlands)

Ban, E.P. van den; Carmona, J.; Delorme, P.

1997-01-01

Let G=H be a semisimple symmetric space, that is, G is a connected semisimple real Lie group with an involution ?, and H is an open subgroup of the group of xed points for ? in G. The main purpose of this paper is to study an explicit Fourier transform on G=H. In terms of general representation

Symmetric lithium-ion cell based on lithium vanadium fluorophosphate with ionic liquid electrolyte

International Nuclear Information System (INIS)

Plashnitsa, Larisa S.; Kobayashi, Eiji; Okada, Shigeto; Yamaki, Jun-ichi

2011-01-01

Lithium vanadium fluorophosphate, LiVPO 4 F, was utilized as both cathode and anode for fabrication of a symmetric lithium-ion LiVPO 4 F//LiVPO 4 F cell. The electrochemical evolution of the LiVPO 4 F//LiVPO 4 F cell with the commonly used organic electrolyte LiPF 6 /EC-DMC has shown that this cell works as a secondary battery, but exhibits poor durability at room temperature and absolutely does not work at increased operating temperatures. To improve the performance and safety of this symmetric battery, we substituted a non-flammable ionic liquid (IL) LiBF 4 /EMIBF 4 electrolyte for the organic electrolyte. The symmetric battery using the IL electrolyte was examined galvanostatically at different rates and operating temperatures within the voltage range of 0.01-2.8 V. It was demonstrated that the IL-based symmetric cell worked as a secondary battery with a Coulombic efficiency of 77% at 0.1 mA cm -2 and 25 o C. It was also found that the use of the IL electrolyte instead of the organic one resulted in the general reduction of the first discharge capacity by about 20-25% but provided much more stable behavior and a longer cycle life. Moreover, an increase of the discharge capacity of the IL-based symmetric battery up to 120 mA h g -1 was observed when the operating temperature was increased up to 80 o C at 0.1 mA cm -2 . The obtained electrochemical behavior of both symmetric batteries was confirmed by complex-impedance measurements at different temperatures and cycling states. The thermal stability of LiVPO 4 F with both the IL and organic electrolytes was also examined.

Nonadiabatic quantum wave packet dynamics of the H + H2 reaction ...

Indian Academy of Sciences (India)

Administrator

intersections of the two JT split component states. The energetically ... between the theory and experiment,. 1 there remains ..... overhead raises by a factor of two for each WP .... Herzberg G and Longuet-Higgins H C 1963 Disscuss. Faraday.

Modelling of phase equilibria in CH4–C2H6–C3H8–nC4H10–NaCl–H2O systems

International Nuclear Information System (INIS)

Li, Jun; Zhang, Zhigang; Luo, Xiaorong; Li, Xiaochun

2015-01-01

Highlights: • A new model was established for the phase equilibria of C1–C2–C3–nC4–brine systems. • The model can reproduce of hydrocarbon–brine equilibria to high T&P and salinity. • The model can well predict H 2 O solubility in light hydrocarbon rich phases. - Abstract: A thermodynamic model is presented for the mutual solubility of CH 4 –C 2 H 6 –C 3 H 8 –nC 4 H 10 –brine systems up to high temperature, pressure and salinity. The Peng–Robinson model is used for non-aqueous phase fugacity calculations, and the Pitzer model is used for aqueous phase activity calculations. The model can accurately reproduce the experimental solubilities of CH 4 , C 2 H 6 , C 3 H 8 and nC 4 H 10 in water or NaCl solutions and H 2 O solubility in the non-aqueous phase. The experimental data of mutual solubility for the CH 4 –brine subsystem are sufficient for temperatures exceeding 250 °C, pressures exceeding 1000 bar and NaCl molalities greater than 6 molal. Compared to the CH 4 –brine system, the mutual solubility data of C 2 H 6 –brine, C 3 H 8 –brine and nC 4 H 10 –brine are not sufficient. Based on the comparison with the experimental data of H 2 O solubility in C 2 H 6 -, C 3 H 8 - or nC 4 H 10 -rich phases, the model has an excellent capability for the prediction of H 2 O solubility in hydrocarbon-rich phases, as these experimental data were not used in the modelling. Predictions of hydrocarbon solubility (at temperatures up to 200 °C, pressures up to 1000 bar and NaCl molalities greater than 6 molal) were made for the C 2 H 6 –brine, C 3 H 8 –brine and nC 4 H 10 –brine systems. The predictions suggest that increasing pressure generally increases the hydrocarbon solubility in water or brine, especially in the lower-pressure region. Increasing temperature usually decreases the hydrocarbon solubility at lower temperatures but increases the hydrocarbon solubility at higher temperatures. Increasing water salinity dramatically decreases

ZrO2 nanoparticles' effects on split tensile strength of self compacting concrete

Directory of Open Access Journals (Sweden)

Ali Nazari

2010-12-01

Full Text Available In the present study, split tensile strength of self compacting concrete with different amount of ZrO2 nanoparticles has been investigated. ZrO2 nanoparticles with the average particle size of 15 nm were added partially to cement paste (Portland cement together with polycarboxylate superplasticizer and split tensile strength of the specimens has been measured. The results indicate that ZrO2 nanoparticles are able to improve split tensile strength of concrete and recover the negative effects of polycarboxylate superplasticizer. ZrO2 nanoparticle as a partial replacement of cement up to 4 wt. (% could accelerate C-S-H gel formation as a result of increased crystalline Ca(OH2 amount at the early age of hydration. The increased the ZrO2 nanoparticles' content more than 4 wt. (%, causes the reduced the split tensile strength because of unsuitable dispersion of nanoparticles in the concrete matrix.

Splitting of high power, cw proton beams

Directory of Open Access Journals (Sweden)

Alberto Facco

2007-09-01

Full Text Available A simple method for splitting a high power, continuous wave (cw proton beam in two or more branches with low losses has been developed in the framework of the EURISOL (European Isotope Separation On-Line Radioactive Ion Beam Facility design study. The aim of the system is to deliver up to 4 MW of H^{-} beam to the main radioactive ion beam production target, and up to 100 kW of proton beams to three more targets, simultaneously. A three-step method is used, which includes magnetic neutralization of a fraction of the main H^{-} beam, magnetic splitting of H^{-} and H^{0}, and stripping of H^{0} to H^{+}. The method allows slow raising and individual fine adjustment of the beam intensity in each branch.

An optical spectrum of a large isolated gas-phase PAH cation: C78H26+

Science.gov (United States)

Zhen, Junfeng; Mulas, Giacomo; Bonnamy, Anthony; Joblin, Christine

2016-01-01

A gas-phase optical spectrum of a large polycyclic aromatic hydrocarbon (PAH) cation - C78H26+- in the 410-610 nm range is presented. This large all-benzenoid PAH should be large enough to be stable with respect to photodissociation in the harsh conditions prevailing in the interstellar medium (ISM). The spectrum is obtained via multi-photon dissociation (MPD) spectroscopy of cationic C78H26 stored in the Fourier Transform Ion Cyclotron Resonance (FT-ICR) cell using the radiation from a mid-band optical parametric oscillator (OPO) laser. The experimental spectrum shows two main absorption peaks at 431 nm and 516 nm, in good agreement with a theoretical spectrum computed via time-dependent density functional theory (TD-DFT). DFT calculations indicate that the equilibrium geometry, with the absolute minimum energy, is of lowered, nonplanar C2 symmetry instead of the more symmetric planar D2h symmetry that is usually the minimum for similar PAHs of smaller size. This kind of slightly broken symmetry could produce some of the fine structure observed in some diffuse interstellar bands (DIBs). It can also favor the folding of C78H26+ fragments and ultimately the formation of fullerenes. This study opens up the possibility to identify the most promising candidates for DIBs amongst large cationic PAHs. PMID:26942230

Determination of the spin orbit coupling and crystal field splitting in wurtzite InP by polarization resolved photoluminescence

Science.gov (United States)

Chauvin, Nicolas; Mavel, Amaury; Jaffal, Ali; Patriarche, Gilles; Gendry, Michel

2018-02-01

Excitation photoluminescence spectroscopy is usually used to extract the crystal field splitting (ΔCR) and spin orbit coupling (ΔSO) parameters of wurtzite (Wz) InP nanowires (NWs). However, the equations expressing the valence band splitting are symmetric with respect to these two parameters, and a choice ΔCR > ΔSO or ΔCR InP NWs grown on silicon. The experimental results combined with a theoretical model and finite difference time domain calculations allow us to conclude that ΔCR > ΔSO in Wz InP.

Neutron diffraction study of the formation of ordered antiphase domains in cubic titanium carbide TiC0.60

International Nuclear Information System (INIS)

Khidirov, I.; Parpiev, A. S.

2013-01-01

A series of superstructural reflections (described within the sp. gr. Fd3m) are found to be split into three symmetric parts in the neutron powder diffraction pattern of titanium carbide TiC 0.60 annealed at a temperature of 600°C. No splitting of superstructural reflections is observed in the neutron diffraction pattern of TiC 0.60 annealed at relatively high temperatures (780°C). This phenomenon can be explained by that fact that the ordering of carbon atoms at relatively high temperatures (780°C) is accompanied by the formation of randomly oriented rather large antiphase domains (APDs) (450 Å). At relatively low temperatures (600°C), stacking faults arise in the arrangement of partially ordered carbon atoms. In this case, relatively small ordered APDs (290 Å) are formed, along with disordered ones.

Enhancing co-production of H2 and syngas via water splitting and POM on surface-modified oxygen permeable membranes

KAUST Repository

Wu, Xiao-Yu

2016-09-26

In this article, we report a detailed study on co-production of H2 and syngas on La0.9Ca0.1FeO3−δ (LCF-91) membranes via water splitting and partial oxidation of methane, respectively. A permeation model shows that the surface reaction on the sweep side is the rate limiting step for this process on a 0.9 mm-thick dense membrane at 990°C. Hence, sweep side surface modifications such as adding a porous layer and nickel catalysts were applied; the hydrogen production rate from water thermolysis is enhanced by two orders of magnitude to 0.37 μmol/cm2•s compared with the results on the unmodified membrane. At the sweep side exit, syngas (H2/CO = 2) is produced and negligible solid carbon is found. Yet near the membrane surface on the sweep side, methane can decompose into solid carbon and hydrogen at the surface, or it may be oxidized into CO and CO2, depending on the oxygen permeation flux.

Symmetric large momentum transfer for atom interferometry with BECs

Science.gov (United States)

Abend, Sven; Gebbe, Martina; Gersemann, Matthias; Rasel, Ernst M.; Quantus Collaboration

2017-04-01

We develop and demonstrate a novel scheme for a symmetric large momentum transfer beam splitter for interferometry with Bose-Einstein condensates. Large momentum transfer beam splitters are a key technique to enhance the scaling factor and sensitivity of an atom interferometer and to create largely delocalized superposition states. To realize the beam splitter, double Bragg diffraction is used to create a superposition of two symmetric momentum states. Afterwards both momentum states are loaded into a retro-reflected optical lattice and accelerated by Bloch oscillations on opposite directions, keeping the initial symmetry. The favorable scaling behavior of this symmetric acceleration, allows to transfer more than 1000 ℏk of total differential splitting in a single acceleration sequence of 6 ms duration while we still maintain a fraction of approx. 25% of the initial atom number. As a proof of the coherence of this beam splitter, contrast in a closed Mach-Zehnder atom interferometer has been observed with up to 208 ℏk of momentum separation, which equals a differential wave-packet velocity of approx. 1.1 m/s for 87Rb. The presented work is supported by the CRC 1128 geo-Q and the DLR with funds provided by the Federal Ministry of Economic Affairs and Energy (BMWi) due to an enactment of the German Bundestag under Grant No. DLR 50WM1552-1557 (QUANTUS-IV-Fallturm).

Thermalization dynamics of two correlated bosonic quantum wires after a split

Science.gov (United States)

Huber, Sebastian; Buchhold, Michael; Schmiedmayer, Jörg; Diehl, Sebastian

2018-04-01

Cherently splitting a one-dimensional Bose gas provides an attractive, experimentally established platform to investigate many-body quantum dynamics. At short enough times, the dynamics is dominated by the dephasing of single quasiparticles, and well described by the relaxation towards a generalized Gibbs ensemble corresponding to the free Luttinger theory. At later times on the other hand, the approach to a thermal Gibbs ensemble is expected for a generic, interacting quantum system. Here, we go one step beyond the quadratic Luttinger theory and include the leading phonon-phonon interactions. By applying kinetic theory and nonequilibrium Dyson-Schwinger equations, we analyze the full relaxation dynamics beyond dephasing and determine the asymptotic thermalization process in the two-wire system for a symmetric splitting protocol. The major observables are the different phonon occupation functions and the experimentally accessible coherence factor, as well as the phase correlations between the two wires. We demonstrate that, depending on the splitting protocol, the presence of phonon collisions can have significant influence on the asymptotic evolution of these observables, which makes the corresponding thermalization dynamics experimentally accessible.

Development of a C3-symmetric benzohydroxamate tripod: Trimetallic complexation with Fe(III), Cr(III) and Al(III)

Science.gov (United States)

Baral, Minati; Gupta, Amit; Kanungo, B. K.

2016-06-01

The design, synthesis and physicochemical characterization of a C3-symmetry Benzene-1,3,5-tricarbonylhydroxamate tripod, noted here as BTHA, are described. The chelator was built from a benzene as an anchor, symmetrically extended by three hydroxamate as ligating moieties, each bearing O, O donor sites. A combination of absorption spectrophotometry, potentiometry and theoretical investigations are used to explore the complexation behavior of the ligand with some trivalent metal ions: Fe(III), Cr(III), and Al(III). Three protonation constants were calculated for the ligand in a pH range of 2-11 in a highly aqueous medium (9:1 H2O: DMSO). A high rigidity in the molecular structure restricts the formation of 1:1 (M/L) metal encapsulation but shows a high binding efficiency for a 3:1 metal ligand stoichiometry giving formation constant (in β unit) 28.73, 26.13 and 19.69 for [M3L]; Mdbnd Fe(III), Al(III) and Cr(III) respectively, and may be considered as an efficient Fe-carrier. The spectrophotometric study reveals of interesting electronic transitions occurred during the complexation. BTHA exhibits a peak at 238 nm in acidic pH and with the increase of pH, a new peak appeared at 270 nm. A substantial shifting in both of the peaks in presence of the metal ions implicates a s coordination between ligand and metal ions. Moreover, complexation of BTHA with iron shows three distinct colors, violet, reddish orange and yellow in different pH, enables the ligand to be considered for the use as colorimetric sensor.

Compression, splitting and switching of bright and dark solitons in nonlinear directional coupler

International Nuclear Information System (INIS)

Mandal, Basanti; Chowdhury, A. Roy

2006-01-01

A detailed numerical simulation of the switching, compression and splitting characteristics of various solitary pulses (bright, grey and dark) are carried out by a direct solution of the associated coupled NLS equation. Important physical parameters of the out going pulse such as, intensity distribution, root mean square spatial and temporal width and chirp are calculated. Both the cases of symmetric and asymmetric couplers are considered. The important phenomenon of periodic power transfer from one channel to the other unfolds. The compression varies with the type of pulse launched in the initial channel. It is observed that the chirping of the initial pulse has an optimum value and it vary quite noticeably with the character of the pulse and couplers, symmetric and asymmetric

Electromagnetically Induced Transparency in Symmetric Planar Metamaterial at THz Wavelengths

Directory of Open Access Journals (Sweden)

Abdelwaheb Ourir

2015-03-01

Full Text Available We report the experimental observation and the evidence of the analogue of electromagnetically-induced transparency (EIT in a symmetric planar metamaterial. This effect has been obtained in the THz range thanks to a destructive Fano-interference between the two first modes of an array of multi-gap split ring resonators deposited on a silicon substrate. This structure is a planar thin film material with four-fold symmetry. Thanks to this property, a polarization-independent transmission has been achieved. The proposed metamaterial is well adapted to variety of slow-light applications in the infrared and optical range.

Frequency splitting of polarization eigenmodes in microscopic Fabry–Perot cavities

International Nuclear Information System (INIS)

Uphoff, Manuel; Brekenfeld, Manuel; Rempe, Gerhard; Ritter, Stephan

2015-01-01

We study the frequency splitting of the polarization eigenmodes of the fundamental transverse mode in CO 2 laser-machined, high-finesse optical Fabry–Perot cavities and investigate the influence of the geometry of the cavity mirrors. Their highly reflective surfaces are typically not rotationally symmetric but have slightly different radii of curvature along two principal axes. We observe that the eccentricity of such elliptical mirrors lifts the degeneracy of the polarization eigenmodes. The impact of the eccentricity increases for smaller radii of curvature. A model derived from corrections to the paraxial resonator theory is in excellent agreement with the measurements, showing that geometric effects are the main source of the frequency splitting of polarization modes for the type of microscopic cavity studied here. By rotating one of the mirrors around the cavity axis, the splitting can be tuned. In the case of an identical differential phase shift per mirror, it can even be eliminated, despite a nonvanishing eccentricity of each mirror. We expect our results to have important implications for many experiments in cavity quantum electrodynamics, where Fabry–Perot cavities with small mode volumes are required. (paper)

Electrooxidative Rhodium-Catalyzed C-H/C-H Activation: Electricity as Oxidant for Cross-Dehydrogenative Alkenylation.

Science.gov (United States)

Qiu, Youai; Kong, Wei-Jun; Struwe, Julia; Sauermann, Nicolas; Rogge, Torben; Scheremetjew, Alexej; Ackermann, Lutz

2018-04-06

Rhodium(III) catalysis has enabled a plethora of oxidative C-H functionalizations, which predominantly employ stoichiometric amounts of toxic and/or expensive metal oxidants. In contrast, we describe the first electrochemical C-H activation by rhodium catalysis that avoids hazardous chemical oxidants. Thus, environmentally-benign twofold C-H/C-H functionalizations were accomplished with weakly-coordinating benzoic acids and benzamides, employing electricity as the terminal oxidant with H2 as the sole byproduct. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Splittings, coalescence, bunch and snake patterns in the 3D nonlinear Schrödinger equation with anisotropic dispersion

DEFF Research Database (Denmark)

Germaschewski, K.; Grauer, R.; Bergé, L.

2001-01-01

compression and are shown to split into two symmetric peaks. These peaks can sequentially decay into smaller-scale structures developing near the front edge of a shock, as long as their individual power remains above threshold, until the final dispersion of the wave. Their phase and amplitude dynamics...

Pseudo-Hermitian description of PT-symmetric systems defined on a complex contour

International Nuclear Information System (INIS)

Mostafazadeh, Ali

2005-01-01

We describe a method that allows for a practical application of the theory of pseudo-Hermitian operators to PT-symmetric systems defined on a complex contour. We apply this method to study the Hamiltonians H = p 2 + x 2 (ix) ν with ν ε (-2, ∞) that are defined along the corresponding anti-Stokes lines. In particular, we reveal the intrinsic non-Hermiticity of H for the cases that ν is an even integer, so that H p 2 ± x 2+ν , and give a proof of the discreteness of the spectrum of H for all ν ε (-2, ∞). Furthermore, we study the consequences of defining a square-well Hamiltonian on a wedge-shaped complex contour. This yields a PT-symmetric system with a finite number of real eigenvalues. We present a comprehensive analysis of this system within the framework of pseudo-Hermitian quantum mechanics. We also outline a direct pseudo-Hermitian treatment of PT-symmetric systems defined on a complex contour which clarifies the underlying mathematical structure of the formulation of PT-symmetric quantum mechanics based on the charge-conjugation operator. Our results provide conclusive evidence that pseudo-Hermitian quantum mechanics provides a complete description of general PT-symmetric systems regardless of whether they are defined along the real line or a complex contour

Isospin splittings of baryons

International Nuclear Information System (INIS)

Varga, Kalman; Genovese, Marco; Richard, Jean-Marc; Silvestre-Brac, Bernard

1998-01-01

We discuss the isospin-breaking mass differences among baryons, with particular attention in the charm sector to the Σ c + -Σ c 0 , Σ c ++ -Σ c 0 , and Ξ c + -Ξ c 0 splittings. Simple potential models cannot accommodate the trend of the available data on charm baryons. More precise measurements would offer the possibility of testing how well potential models describe the non-perturbative limit of QCD

Characterisation of point defects in SiC by microscopic optical spectroscopy

International Nuclear Information System (INIS)

Evans, G.A.

2001-09-01

Defects have a dramatic effect on the properties of semiconductors. In SiC, intrinsic defects can be introduced during growth or device-processing steps such as implantation. In this work electron irradiation has been used for the controlled generation of defects in SiC. The irradiated material has been annealed and subsequent low temperature photoluminescence (LTPL) measurements have been performed. A key element in this work has been the ability to perform both the irradiation and characterisation on a microscopic scale. These results have allowed a variety of new optical centres to be discovered, and have also significantly enhanced the pool of knowledge about other defect centres. Utilising low voltage irradiations has enabled the electron irradiation voltage displacement thresholds for Carbon and Silicon displacements to be investigated. In 4H-SiC the electron irradiation voltage displacement thresholds were found to be 88kV for C displacement and 225kV for Si displacement. A large number of previously unreported luminescence features have been measured in 4H, 6H and 15R-SiC material. The criteria used for comparison are the voltage threshold, annealing characteristics, spatial distribution with respect to the irradiated region, and the characteristics of associated local modes and vibronic structures. Compelling evidence has been found to support the assignment of centres in 4H and 6H-SiC to a C-C dumbbell split interstitial defect. Two high energy local modes at 133meV and 180meV are associated with these centres. In 13 C enriched 6H-SiC material the 180meV local mode splits into three components whilst the 133meV local mode splits into two components. This splitting is interpreted as being caused by isotopic substitutions between the components of the C-C dumbbell. The high energy local mode corresponds to the bonding between the two constituent atoms of the dumbbell whilst the low energy local mode is associated with the bonding between either a C 13 or 12

Charge transfer processes in collisions of H+ ions with H2, D2, CO, CO2 CH4, C2H2, C2H6 and C3H8 molecules below 10 keV

International Nuclear Information System (INIS)

Kusakabe, T.; Buenker, R.J.; Kimura, M.

2002-01-01

Charge transfer processes resulting from collisions of H + ions with H 2 , D 2 , CO, CO 2 CH 4 , C 2 H 2 , C 2 H 6 and C 3 H 8 molecules have been investigated in the energy range of 0.2 to 4.0 keV experimentally and theoretically. The initial growth rate method was employed in the experiment for studying the dynamics and cross sections. Theoretical analysis based on a molecular-orbital expansion method for H 2 , D 2 , CO, CH 4 and C 2 H 2 targets was also carried out. The present results for the H 2 , CO and CO 2 molecules by H + impact are found to be in excellent accord with most of previous measurements above 1 keV, but they show some differences below this energy where our result displays a stronger energy-dependence. For CH 4 , C 2 H 2 , C 2 H 6 and C 3 H 8 targets, both experimental and theoretical results indicate that if one assumes vibrationally excited molecular ions (CH 4 + , C 2 H 2 + , C 2 H 6 + and C 3 H 8 + ) formed in the exit channel, then charge transfer processes sometimes become more favorable since these vibrationally excited fragments meet an accidental resonant condition. This is a clear indication of the role of vibrational excited states for charge transfer, and is an important realization for general understanding. (author)

Multireference configuration interaction treatment of potential energy surfaces: symmetric dissociation of H/sub 2/O in a double-zeta basis

Energy Technology Data Exchange (ETDEWEB)

Brown, F B; Shavitt, I; Shepard, R

1984-03-23

Multiconfiguration self-consistent fields (SCF) and multireference configurational interaction (CI) calculations have been performed for the H/sub 2/O molecule in a double-zeta basis for four symmetric geometries, for comparison with full CI results. Unlike single-reference results, the energy errors are almost independent of geometry, allowing unbiased treatments of potential energy surfaces. 35 references, 1 figure, 2 tables.

Nanoscale strontium titanate photocatalysts for overall water splitting.

Science.gov (United States)

Townsend, Troy K; Browning, Nigel D; Osterloh, Frank E

2012-08-28

SrTiO(3) (STO) is a large band gap (3.2 eV) semiconductor that catalyzes the overall water splitting reaction under UV light irradiation in the presence of a NiO cocatalyst. As we show here, the reactivity persists in nanoscale particles of the material, although the process is less effective at the nanoscale. To reach these conclusions, Bulk STO, 30 ± 5 nm STO, and 6.5 ± 1 nm STO were synthesized by three different methods, their crystal structures verified with XRD and their morphology observed with HRTEM before and after NiO deposition. In connection with NiO, all samples split water into stoichiometric mixtures of H(2) and O(2), but the activity is decreasing from 28 μmol H(2) g(-1) h(-1) (bulk STO), to 19.4 μmol H(2) g(-1) h(-1) (30 nm STO), and 3.0 μmol H(2) g(-1) h(-1) (6.5 nm STO). The reasons for this decrease are an increase of the water oxidation overpotential for the smaller particles and reduced light absorption due to a quantum size effect. Overall, these findings establish the first nanoscale titanate photocatalyst for overall water splitting.

Extension of PT-symmetric quantum mechanics to quantum field theory with cubic interaction

International Nuclear Information System (INIS)

Bender, Carl M.; Brody, Dorje C.; Jones, Hugh F.

2004-01-01

It has recently been shown that a non-Hermitian Hamiltonian H possessing an unbroken PT symmetry (i) has a real spectrum that is bounded below, and (ii) defines a unitary theory of quantum mechanics with positive norm. The proof of unitarity requires a linear operator C, which was originally defined as a sum over the eigenfunctions of H. However, using this definition to calculate C is cumbersome in quantum mechanics and impossible in quantum field theory. An alternative method is devised here for calculating C directly in terms of the operator dynamical variables of the quantum theory. This method is general and applies to a variety of quantum mechanical systems having several degrees of freedom. More importantly, this method is used to calculate the C operator in quantum field theory. The C operator is a time-independent observable in PT-symmetric quantum field theory

C2-symmetric bisamidines: Chiral Brønsted bases catalysing the Diels-Alder reaction of anthrones

Directory of Open Access Journals (Sweden)

2008-08-01

Full Text Available C2-symmetric bisamidines 8 have been tested as chiral Brønsted bases in the Diels-Alder reaction of anthrones and N-substituted maleimides. High yields of cycloadducts and significant asymmetric inductions up to 76% ee are accessible. The proposed mechanism involves proton transfer between anthrone and bisamidine, association of the resulting ions and finally a cycloaddition step stereoselectively controlled by the chiral ion pair.

Embryo splitting

Directory of Open Access Journals (Sweden)

Karl Illmensee

2010-04-01

Full Text Available Mammalian embryo splitting has successfully been established in farm animals. Embryo splitting is safely and efficiently used for assisted reproduction in several livestock species. In the mouse, efficient embryo splitting as well as single blastomere cloning have been developed in this animal system. In nonhuman primates embryo splitting has resulted in several pregnancies. Human embryo splitting has been reported recently. Microsurgical embryo splitting under Institutional Review Board approval has been carried out to determine its efficiency for blastocyst development. Embryo splitting at the 6–8 cell stage provided a much higher developmental efficiency compared to splitting at the 2–5 cell stage. Embryo splitting may be advantageous for providing additional embryos to be cryopreserved and for patients with low response to hormonal stimulation in assisted reproduction programs. Social and ethical issues concerning embryo splitting are included regarding ethics committee guidelines. Prognostic perspectives are presented for human embryo splitting in reproductive medicine.

The singlet-triplet energy gap in divalent three, five and seven-membered cyclic C2H2M, C4H4M and C6H6M (M = C, Si, Ge, Sn AND Pb

Directory of Open Access Journals (Sweden)

E. Vessally

2009-08-01

Full Text Available Total energy gaps, ∆Et–s, enthalpy gaps, ∆Ht–s, and Gibbs free energy gaps, ∆Gt–s, between singlet (s and triplet (t states were calculated for three, five and seven-membered cyclic C2H2M, C4H4M and C6H6M (M = C, Si, Ge, Sn and Pb at B3LYP/6-311++G**. The singlet-triplet free energy gaps, ∆Gt–s, for C2H2M (M = C, Si, Ge, Sn and Pb are found to be increased in the order: C2H2Si > C2H2C > C2H2Ge > C2H2Sn > C2H2Pb. The ∆Gt–s of C4H4M are found to be increased in the order: C4H4Pb > C4H4Sn > C4H4Ge > C4H4Si > C4H4C. Also, the ∆Gt–s of C6H6M are determined in the order: C6H6Pb > C6H6Ge ≥ C6H6Sn > C6H6Si > C6H6C. The most stable conformers of C2H2M, C4H4M and C6H6M are proposed for both the singlet and triplet states. Nuclear independent chemical shifts (NICS calculations were carried out for determination of aromatic character. The geometrical parameters are calculated and discussed.

Propagation dynamics of off-axis symmetrical and asymmetrical vortices embedded in flat-topped beams

Science.gov (United States)

Zhang, Xu; Wang, Haiyan

2017-11-01

In this paper, propagation dynamics of off-axis symmetrical and asymmetrical optical vortices(OVs) embedded in flat-topped beams have been explored numerically based on rigorous scalar diffraction theory. The distribution properties of phase and intensity play an important role in driving the propagation dynamics of OVs. Numerical results show that the single off-axis vortex moves in a straight line. The displacement of the single off-axis vortex becomes smaller, when either the order of flatness N and the beam size ω0are increased or the off-axis displacement d is decreased. In addition, the phase singularities of high order vortex beams can be split after propagating a certain distance. It is also demonstrated that the movement of OVs are closely related with the spatial symmetrical or asymmetrical distribution of vortex singularities field. Multiple symmetrical and asymmetrical optical vortices(OVs) embedded in flat-topped beams can interact and rotate. The investment of the propagation dynamics of OVs may have many applications in optical micro-manipulation and optical tweezers.

Multipole induced splitting of metal-cage vibrations in crystalline endohedral D2d-M2@C84 dimetallofullerenes.

Science.gov (United States)

Krause, M; Popov, V N; Inakuma, M; Tagmatarchis, N; Shinohara, H; Georgi, P; Dunsch, L; Kuzmany, H

2004-01-22

Metal-carbon cage vibrations of crystalline endohedral D2d-M2@C84 (M=Sc,Y,Dy) dimetallofullerenes were analyzed by temperature dependent Raman scattering and a dynamical force field model. Three groups of metal-carbon cage modes were found at energies of 35-200 cm(-1) and assigned to metal-cage stretching and deformation vibrations. They exhibit a textbook example for the splitting of molecular vibrations in a crystal field. Induced dipole-dipole and quadrupole-quadrupole interactions account quantitatively for the observed mode splitting. Based on the metal-cage vibrational structure it is demonstrated that D2d-Y2@C84 dimetallofullerene retains a monoclinic crystal structure up to 550 K and undergoes a transition from a disordered to an ordered orientational state at a temperature of approximately 150 K.

Dynamics of a split torque helicopter transmission

Science.gov (United States)

Krantz, Timothy L.

1994-06-01

Split torque designs, proposed as alternatives to traditional planetary designs for helicopter main rotor transmissions, can save weight and be more reliable than traditional designs. This report presents the results of an analytical study of the system dynamics and performance of a split torque gearbox that uses a balance beam mechanism for load sharing. The Lagrange method was applied to develop a system of equations of motion. The mathematical model includes time-varying gear mesh stiffness, friction, and manufacturing errors. Cornell's method for calculating the stiffness of spur gear teeth was extended and applied to helical gears. The phenomenon of sidebands spaced at shaft frequencies about gear mesh fundamental frequencies was simulated by modeling total composite gear errors as sinusoid functions. Although the gearbox has symmetric geometry, the loads and motions of the two power paths differ. Friction must be considered to properly evaluate the balance beam mechanism. For the design studied, the balance beam is not an effective device for load sharing unless the coefficient of friction is less than 0.003. The complete system stiffness as represented by the stiffness matrix used in this analysis must be considered to precisely determine the optimal tooth indexing position.

Synthesis of novel symmetrical macrocycle via oxidative homocoupling of bisalkyne

Energy Technology Data Exchange (ETDEWEB)

Kamalulazmy, Nurulain; Hassan, Nurul Izzaty [School of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor Darul Ehsan (Malaysia)

2014-09-03

A novel symmetrical macrocycle has been synthesised via oxidative homocoupling of bisalkyne, diprop-2-ynyl pyridine-2,6-dicarboxylate mediated by copper (I) iodide (CuI) and 4-dimethylaminopyridine (DMAP). The precursor compound was synthesised from 2,6-pyridine dicarbonyl dichloride and propargyl alcohol in the presence of triethylamine. The reaction mixture was stirred overnight and further purified via column chromatograpy with 76% yield. Single crystal for X-ray study was obtained by recrystallization from acetone. Subsequently, a symmetrical macrocycle was synthesised from oxidative homocoupling of precursor compound in open atmosphere. The crude product was purified by column chromatography to furnish macrocycle compound with 5% yield. Both compounds were characterised by IR, {sup 1}H and {sup 13}C NMR and mass spectral techniques. The unusual conformation of the bisalkyne and twisted conformation of designed macrocycle has influence the percentage yield. This has been studied thoroughly by X-ray crystallography and electronic structure calculations.

Substrate-Mediated C-C and C-H Coupling after Dehalogenation.

Science.gov (United States)

Kong, Huihui; Yang, Sha; Gao, Hongying; Timmer, Alexander; Hill, Jonathan P; Díaz Arado, Oscar; Mönig, Harry; Huang, Xinyan; Tang, Qin; Ji, Qingmin; Liu, Wei; Fuchs, Harald

2017-03-15

Intermolecular C-C coupling after cleavage of C-X (mostly, X = Br or I) bonds has been extensively studied for facilitating the synthesis of polymeric nanostructures. However, the accidental appearance of C-H coupling at the terminal carbon atoms would limit the successive extension of covalent polymers. To our knowledge, the selective C-H coupling after dehalogenation has not so far been reported, which may illuminate another interesting field of chemical synthesis on surfaces besides in situ fabrication of polymers, i.e., synthesis of novel organic molecules. By combining STM imaging, XPS analysis, and DFT calculations, we have achieved predominant C-C coupling on Au(111) and more interestingly selective C-H coupling on Ag(111), which in turn leads to selective synthesis of polymeric chains or new organic molecules.

Fabrication of 2D SnS2/g-C3N4 heterojunction with enhanced H2 evolution during photocatalytic water splitting.

Science.gov (United States)

Liu, Enzhou; Chen, Jibing; Ma, Yongning; Feng, Juan; Jia, Jia; Fan, Jun; Hu, Xiaoyun

2018-08-15

In this work, the 2D SnS 2 /g-C 3 N 4 heterojunctions were successfully prepared by heating the homogeneous dispersion of SnS 2 nanosheets and g-C 3 N 4 nanosheets using a microwave muffle. SEM, TEM and HRTEM images indicated that the SnS 2 nanosheets were loaded on the surface of the g-C 3 N 4 nanosheets. The UV-vis spectra show that the absorption intensity of the as-prepared samples was increased and the absorption range was also extended from 420 nm to approximately 600 nm. The H 2 production rate over 5 wt% SnS 2 /g-C 3 N 4 can reach 972.6 μmol·h -1 ·g -1 under visible light irradiation (λ > 420 nm) using TEOA as the sacrifice agent and Pt as the electron trap, which is 2.9 and 25.6 times higher than those of the pristine g-C 3 N 4 and SnS 2 , respectively. According to the obtained PL spectra, photocurrent and EIS spectra, the enhanced performance for H 2 generation over the heterojunctions is primarily ascribed to the rapid charge transfer arising from the suitable band gap positions leading to an improved photocatalytic performance. The recycling experiments indicated that the as-prepared composites exhibit good stability in H 2 production. Additionally, a possible enhanced mechanism for H 2 evolution was deduced based on the results obtained by various characterization techniques. Copyright © 2018 Elsevier Inc. All rights reserved.

Asymmetric valley-resolved beam splitting and incident modes in slanted graphene junctions

International Nuclear Information System (INIS)

Hsieh, S. H.; Chu, C. S.

2016-01-01

Electron injection into a graphene sheet through a slanted armchair graphene nanoribbon (AGNR) is investigated. An incident mode, or subband, in the AGNR is valley-unpolarized. Our attention is on the valley-resolved nature of the injected electron beams and its connection to the incident mode. It is known for a normal injection that an incident mode will split symmetrically into two valley-resolved beams of equal intensity. We show, in contrast, that slanted injections result in asymmetric valley-resolved beam splitting. The most asymmetric beam splitting cases, when one of the valley-resolved beams has basically disappeared, are found and the condition derived. This is shown not due to trigonal warping because it holds even in the low incident energy regime, as long as collimation allows. These most asymmetric beam splitting cases occur at energies within an energy interval near and include the subband edge of an incident mode. The physical picture is best illustrated by a projection of the slanted AGNR subband states onto that of the 2D graphene sheet. It follows that the disappearing of a valley-resolved beam coincides with the situation that the group velocities of the projected states in the corresponding valley are in backward directions

Splitting in Dual-Phase 590 high strength steel plates

International Nuclear Information System (INIS)

Yang Min; Chao, Yuh J.; Li Xiaodong; Tan Jinzhu

2008-01-01

Charpy V-notch impact tests on 5.5 mm thick, hot-rolled Dual-Phase 590 (DP590) steel plate were evaluated at temperatures ranging from 90 deg. C to -120 deg. C. Similar tests on 2.0 mm thick DP590 HDGI steel plate were also conducted at room temperature. Splitting or secondary cracks was observed on the fractured surfaces. The mechanisms of the splitting were then investigated. Fracture surfaces were analyzed by optical microscope (OM) and scanning electron microscope (SEM). Composition of the steel plates was determined by electron probe microanalysis (EPMA). Micro Vickers hardness of the steel plates was also surveyed. Results show that splitting occurred on the main fractured surfaces of hot-rolled steel specimens at various testing temperatures. At temperatures above the ductile-brittle-transition-temperature (DBTT), -95 deg. C, where the fracture is predominantly ductile, the length and amount of splitting decreased with increasing temperature. At temperatures lower than the DBTT, where the fracture is predominantly brittle, both the length and width of the splitting are insignificant. Splitting in HDGI steel plates only appeared in specimens of T-L direction. The analysis revealed that splitting in hot-rolled plate is caused by silicate and carbide inclusions while splitting in HDGI plate results from strip microstructure due to its high content of manganese and low content of silicon. The micro Vickers hardness of either the inclusions or the strip microstructures is higher than that of the respective base steel

Experimental studies of collisions of excited Li(4p) atoms with C2H4, C2H6, C3H8 and theoretical interpretation of the Li-C2H4 system

International Nuclear Information System (INIS)

Semmineh, Natenael; Bililign, Solomon; Hagebaum-Reignier, Denis; Jeung, Gwang-Hi

2009-01-01

Collisions of excited Li(4p) states with C 2 H 4 , C 2 H 6 and C 3 H 8 are studied experimentally using far-wing scattering state spectroscopy techniques. High-level ab initio quantum mechanical studies of the Li-C 2 H 4 system are conducted to explain the results of the experiment for this system. The recent and present works indicate that knowledge of the internal structure of the perturber (C 2 H 4 , C 2 H 6 and C 3 H 8 ) is essential to fully understand the interaction between the metal and the hydrocarbon molecules. The ab initio calculation shows that the Li(4d) (with little probability under the experimental conditions) and the Li(4p) can be formed directly through the laser pumping. It also shows that the Li(4s) and Li(3d) states can be formed through an electronic diabatic coupling involving a radiationless process. However, the Li(3p), Li(3s) and Li(2p) states can only be formed through a secondary diabatic coupling which is a much less probable process than the primary one. The calculation limited to two C 2v sections of the potential energy surfaces (PESs) shows peculiar multi-state crossings that we have never seen in other lithium complexes we studied

Kinetic-energy distribution for symmetric fission of 236U

International Nuclear Information System (INIS)

Brissot, R.; Bocquet, J.P.; Ristori, C.; Crancon, J.; Guet, C.R.; Nifenecker, H.A.; Montoya, M.

1980-01-01

Fission fragment kinetic-energy distributions have been measured at the Grenoble high-flux reactor with the Lohengrin facility. Spurious events were eliminated in the symmetric region by a coherence test based on a time-of-flight measurement of fragment velocities. A Monte-Carlo calculation is then performed to correct the experimental data for neutron evaporation. The difference between the most probable kinetic energy in symmetric fission and the fission in which the heavy fragment is 'magic' (Zsub(H)=50) is found to be approximately =30 MeV. The results suggest that for the symmetric case the total excitation energy available at scission is shared equally among the fragments. (author)

Ferromagnetic behavior in linear charge-transfer complexes. Structural and magnetic characterization of octamethylferrocene salts: (Fe(C sub 5 Me sub 4 H) sub 2 ) sup sm bullet + (A) sup sm bullet minus (A = TCNE, TCNQ)

Energy Technology Data Exchange (ETDEWEB)

Miller, J.S.; Glatzhofer, D.T.; O' Hare, D.M. (E.I. de Pont de Nemours and Co., Inc., Wilmington, DE (USA)); Reiff, W.M. (Northeastern Univ., Boston, MA (USA)); Chakraborty, A.; Epstein, A.J. (Ohio Sate Univ., Columbus (USA))

1989-07-26

The reaction of Fe{sup II}({eta}{sup 5}-C{sub 5}Me{sub 4}H){sub 2} with cyano acceptors A (A = TCNE (tetracyanoethylene), TCNQ (7,7,8,8-tetracyano-p-quanodimethane), n-C{sub 4}(CN){sub 6} (n-hexacyanobutadiene), C{sub 6}(CN){sub 6} (tris(dicyanomethylene)cyclopropane), DDQ (2,3-dichloro-5,6-dicyanobenzoquinone), TCNQF{sub 4} (perfluoro-7,7,8,8-tetracyano-p-quinodimethane) results in formation of 1:1 charge-transfer salts of (Fe{sup III})(C{sub 5}Me{sub 4}H){sub 2}){sup {sm bullet}+}(A){sup {sm bullet}{minus}} composition. The TCNE and TCNQ complexes have been structurally characterized. The high-temperature magnetic susceptibility for polycrystalline samples of these complexes can be fit by the Curie-Qeiss law, {chi} = C(T-{theta}){sup {minus}1}, with {theta} = +0.5 {plus minus} 2.2 K, and {mu}{sub eff} ranges from 2.71 to 3.97 {mu}{sub B}, suggesting that the polycrystalline samples measured had varying degrees of orientation. The 7.0 K EPR spectrum of the radical cation exhibits an axially symmetric powder pattern with g{sub {parallel}} = 4.11 and g{sub {perpendicular}} = 1.42, and the EPR parameters are essentially identical with those reported for ferrocenium and decamethylferrocenium. No EPR spectrum is observed at 78 K. Akin to the (Fe(C{sub 5}Me{sub 5}){sub 2}){sup {sm bullet}+} salts, these salts have {sup 57}Fe Moessbauer spectra consistent with complete charge transfer; however, unlike the case for the former complexes, quadrupole splittings of 0.30 and 0.220 mm/s are observed at 4.8 and 298 K, respectively. The absence of strong interionic magnetic coupling for the (Fe(C{sub 5}Me{sub 4}H){sub 2}){sup {sm bullet}+} salts contrasts with the behavior of the (Fe(C{sub 5}Me{sub 5}){sub 2}){sup {sm bullet}+} salts. 26 refs., 13 figs., 8 tabs.

Solving symmetric-definite quadratic lambda-matrix problems without factorization

International Nuclear Information System (INIS)

Scott, D.S.; Ward, R.C.

1982-01-01

Algorithms are presented for computing some of the eigenvalues and their associated eigenvectors of the quadratic lambda-matrix M lambda 2 C lambda + K. M, C, and K are assumed to have special symmetry-type properties which insure that theory analogous to the standard symmetric eigenproblem exists. The algorithms are based on a generalization of the Rayleigh quotient and the Lanczos method for computing eigenpairs of standard symmetric eigenproblems. Monotone quadratic convergence of the basic method is proved. Test examples are presented

Facade Layout Symmetrization

KAUST Repository

Jiang, Haiyong

2016-04-11

We present an automatic algorithm for symmetrizing facade layouts. Our method symmetrizes a given facade layout while minimally modifying the original layout. Based on the principles of symmetry in urban design, we formulate the problem of facade layout symmetrization as an optimization problem. Our system further enhances the regularity of the final layout by redistributing and aligning boxes in the layout. We demonstrate that the proposed solution can generate symmetric facade layouts efficiently. © 2015 IEEE.

Facade Layout Symmetrization

KAUST Repository

Jiang, Haiyong; Dong, Weiming; Yan, Dongming; Zhang, Xiaopeng

2016-01-01

We present an automatic algorithm for symmetrizing facade layouts. Our method symmetrizes a given facade layout while minimally modifying the original layout. Based on the principles of symmetry in urban design, we formulate the problem of facade layout symmetrization as an optimization problem. Our system further enhances the regularity of the final layout by redistributing and aligning boxes in the layout. We demonstrate that the proposed solution can generate symmetric facade layouts efficiently. © 2015 IEEE.

Symmetric cryptographic protocols

CERN Document Server

Ramkumar, Mahalingam

2014-01-01

This book focuses on protocols and constructions that make good use of symmetric pseudo random functions (PRF) like block ciphers and hash functions - the building blocks for symmetric cryptography. Readers will benefit from detailed discussion of several strategies for utilizing symmetric PRFs. Coverage includes various key distribution strategies for unicast, broadcast and multicast security, and strategies for constructing efficient digests of dynamic databases using binary hash trees.   •        Provides detailed coverage of symmetric key protocols •        Describes various applications of symmetric building blocks •        Includes strategies for constructing compact and efficient digests of dynamic databases

Polymeric thermal analysis of C + H and C + H + Ar ion implanted UHMWPE samples

International Nuclear Information System (INIS)

Kaya, N.; Oztarhan, Ahmet M.; Urkac, E.S.; Ila, D.; Budak, S.; Oks, E.; Nikolaev, A.; Ezdesir, A.; Tihminlioglu, F.; Tek, Z.; Cetiner, S.; Muntele, C.

2007-01-01

Chemical surface characterization of C + H hybrid ion implanted UHMWPE samples were carried out using DSC (differential scanning calorimeter) and TGA (thermal gravimetric analysis) techniques. Samples were implanted with a fluence of 10 17 ion/cm 2 and an extraction voltage of 30 kV. The study of TGA and DSC curves showed that: (1) Polymeric decomposition temperature increased (2) T m , ΔC p and ΔH m values changed while ΔC p and ΔH m increased. T g value could not be measured, because of some experimental limitations. However, the increase in ΔH m values showed that T g values increased (3) the branch density which indicated the increase in number of cross-link (M c ) decreased in ion implanted samples and (4) increase in ΔH m values indicated increase in crystallinity of implanted surface of UHMWPE samples

Computational Study of Pincer Iridium Catalytic Systems: C-H, N-H, and C-C Bond Activation and C-C Coupling Reactions

Science.gov (United States)

Zhou, Tian

Computational chemistry has achieved vast progress in the last decades in the field, which was considered to be only experimental before. DFT (density functional theory) calculations have been proven to be able to be applied to large systems, while maintaining high accuracy. One of the most important achievements of DFT calculations is in exploring the mechanism of bond activation reactions catalyzed by organometallic complexes. In this dissertation, we discuss DFT studies of several catalytic systems explored in the lab of Professor Alan S. Goldman. Headlines in the work are: (1) (R4PCP)Ir alkane dehydrogenation catalysts are highly selective and different from ( R4POCOP)Ir catalysts, predicting different rate-/selectivity-determining steps; (2) The study of the mechanism for double C-H addition/cyclometalation of phenanthrene or biphenyl by (tBu4PCP)Ir(I) and ( iPr4PCP)Ir illustrates that neutral Ir(III) C-H addition products can undergo a very facile second C-H addition, particularly in the case of sterically less-crowded Ir(I) complexes; (3) (iPr4PCP)Ir pure solid phase catalyst is highly effective in producing high yields of alpha-olefin products, since the activation enthalpy for dehydrogenation is higher than that for isomerization via an allyl pathway; higher temperatures favor the dehydrogenation/isomerization ratio; (4) (PCP)Ir(H)2(N2H4) complex follows a hydrogen transfer mechanism to undergo both dehydrogenation to form N 2 and H2, as well as hydrogen transfer followed by N-N bond cleavage to form NH3, N2, and H2; (5) The key for the catalytic effect of solvent molecule in CO insertion reaction for RMn(CO)5 is hydrogen bond assisted interaction. The basicity of the solvent determines the strength of the hydrogen bond interaction during the catalytic path and determines the catalytic power of the solvent; and (6) Dehydrogenative coupling of unactivated C-H bonds (intermolecular vinyl-vinyl, intramolecular vinyl-benzyl) is catalyzed by precursors of the

Experimental and Theoretical Studies of the Factors Affecting the Cycloplatination of the Chiral Ferrocenylaldimine (SC-[(η5-C5H5Fe{(η5-C5H4–C(H=N–CH(Me(C6H5}

Directory of Open Access Journals (Sweden)

Concepción López

2014-11-01

Full Text Available The study of the reactivity of the enantiopure ferrocenyl Schiff base (SC-[FcCH=N–CH(Me(C6H5] (1 (Fc = (η5-C5H5Fe(η5-C5H4 with cis-[PtCl2(dmso2] under different experimental conditions is reported. Four different types of chiral Pt(II have been isolated and characterized. One of them is the enantiomerically pure trans-(SC-[Pt{κ1-N[FcCH=N–CH(Me(C6H5]}Cl2(dmso] (2a in which the imine acts as a neutral N-donor ligand; while the other three are the cycloplatinated complexes: [Pt{κ2-C,N [(C6H4–N=CHFc]}Cl(dmso] (7a and the two diastereomers {(Sp,SC and (Rp,SC} of [Pt{κ2-C,N[(η5-C5H3–CH=N–{CH(Me(C6H5}]Fe(η5-C5H5}Cl(dmso] (8a and 9a, respectively. Isomers 7a-9a, differ in the nature of the metallated carbon atom [CPh (in 7a or CFc (in 8a and 9a] or the planar chirality of the 1,2-disubstituted ferrocenyl unit (8a and 9a. Reactions of 7a–9a with PPh3 gave [Pt{κ2-C,N[(C6H4–N=CHFc]}Cl(PPh3] (in 7b and the diastereomers (Sp,SC and (Rp,SC of [Pt{κ2-C,N[(η5-C5H3–CH=N–{CH(Me(C6H5}] Fe(η5-C5H5}Cl(PPh3] (8b and 9b, respectively. Comparative studies of the electrochemical properties and cytotoxic activities on MCF7 and MDA-MB231 breast cancer cell lines of 2a and cycloplatinated complexes 7b-9b are also reported. Theoretical studies based on DFT calculations have also been carried out in order to rationalize the results obtained from the cycloplatination of 1, the stability of the Pt(II complexes and their electrochemical properties.

Theoretical study of the D-->C emission spectrum of NO(2).

Science.gov (United States)

Schinke, R

2008-09-28

The 3 (2)A(')(D)-->1 (2)A(")(C) emission spectrum of NO(2) has been calculated by means of exact dynamics calculations and an accurate potential energy surface for the C state. The potential energy surface has been obtained by electronic structure calculations employing the internally contracted multireference configuration interaction method plus Davidson correction and the augmented correlation consistent polarized quadruple zeta basis set. The calculated spectrum, based on energies as well as intensities, agrees well with the measured one. Despite the two asymmetric C(s) potential wells of the C potential energy surface, the spectrum is best described by a C(2v) assignment in terms of symmetric stretch, bending, and antisymmetric stretch quantum numbers. The barrier separating the two wells is merely of the order of 500 cm(-1) with the consequence that only the two lowest states, (0,0,0) and (0,0,1), show a tunneling splitting. Essential for the correct assignment of the spectrum is the pronounced negative anharmonicity of the antisymmetric stretch mode. Excitation of the symmetric stretch mode is not directly seen in the main part of the spectrum.

Torsionally mediated spin-rotation hyperfine splittings at moderate to high J values in methanol

Science.gov (United States)

Belov, S. P.; Golubiatnikov, G. Yu.; Lapinov, A. V.; Ilyushin, V. V.; Alekseev, E. A.; Mescheryakov, A. A.; Hougen, J. T.; Xu, Li-Hong

2016-07-01

This paper presents an explanation based on torsionally mediated proton-spin-overall-rotation interaction for the observation of doublet hyperfine splittings in some Lamb-dip sub-millimeter-wave transitions between ground-state torsion-rotation states of E symmetry in methanol. These unexpected doublet splittings, some as large as 70 kHz, were observed for rotational quantum numbers in the range of J = 13 to 34, and K = - 2 to +3. Because they increase nearly linearly with J for a given branch, we confined our search for an explanation to hyperfine operators containing one nuclear-spin angular momentum factor I and one overall-rotation angular momentum factor J (i.e., to spin-rotation operators) and ignored both spin-spin and spin-torsion operators, since they contain no rotational angular momentum operator. Furthermore, since traditional spin-rotation operators did not seem capable of explaining the observed splittings, we constructed totally symmetric "torsionally mediated spin-rotation operators" by multiplying the E-species spin-rotation operator by an E-species torsional-coordinate factor of the form e±niα. The resulting operator is capable of connecting the two components of a degenerate torsion-rotation E state. This has the effect of turning the hyperfine splitting pattern upside down for some nuclear-spin states, which leads to bottom-to-top and top-to-bottom hyperfine selection rules for some transitions, and thus to an explanation for the unexpectedly large observed hyperfine splittings. The constructed operator cannot contribute to hyperfine splittings in the A-species manifold because its matrix elements within the set of torsion-rotation A1 and A2 states are all zero. The theory developed here fits the observed large doublet splittings to a root-mean-square residual of less than 1 kHz and predicts unresolvable splittings for a number of transitions in which no doublet splitting was detected.

The HCClF_2-HCCH Complex: Microwave Spectrum, Structure and C-H\\cdotsπ Interactions

Science.gov (United States)

Peebles, Rebecca A.; Sexton, John M.; Elliott, Ashley A.; Steber, Amanda L.; Peebles, Sean A.; Neill, Justin L.; Muckle, Matt T.; Pate, Brooks H.

2010-06-01

The HCF_3-HCCH complex was recently found to have a weak C-H\\cdotsπ interaction between the fluoroform and acetylene, as well as having a secondary interaction between the fluorine atoms and one of the acetylene hydrogen atoms; however, extensive splittings due to large amplitude motions within the complex have complicated our efforts at making a full assignment of the HCF_3-HCCH spectrum. In an attempt to remove some of the ambiguity in the HCF_3-HCCH study, we have substituted a chlorine atom for one fluorine atom and undertaken an investigation of the HCClF_2-HCCH complex. This eliminates the possibility of internal rotation of the methane subunit, while still maintaining a C-H\\cdotsπ interaction. Using the chirped-pulse Fourier-transform microwave (CP-FTMW) spectrometer at the University of Virginia and the Balle-Flygare FTMW spectrometer at Eastern Illinois University, the spectra of four isotopologues of HCClF_2-HCCH have been assigned, with no indication of internal motions within the complex. The structure has been determined from the experimental moments of inertia, confirming that this dimer has the expected weak C-H\\cdotsπ interaction. In addition, the off-diagonal χab quadrupole coupling constant has been used to determine the angle between the C-Cl bond and the a-axis of the complex. This, and Kraitchman coordinates for the chlorine atom, help confirm the structural details from the inertial fit. The structural results will be compared with other complexes showing C-H\\cdotsπ and C-H\\cdotsO interactions. S. A. Peebles, M. M. Serafin, R. A. Peebles, 61st International Symposium on Molecular Spectroscopy, Talk MH13, June 19, 2006.

Physical aspects of pseudo-Hermitian and PT-symmetric quantum mechanics

International Nuclear Information System (INIS)

Mostafazadeh, Ali; Batal, Ahmet

2004-01-01

For a non-Hermitian Hamiltonian H possessing a real spectrum, we introduce a canonical orthonormal basis in which a previously introduced unitary mapping of H to a Hermitian Hamiltonian h takes a simple form. We use this basis to construct the observables O α of the quantum mechanics based on H. In particular, we introduce pseudo-Hermitian position and momentum operators and a pseudo-Hermitian quantization scheme that relates the latter to the ordinary classical position and momentum observables. These allow us to address the problem of determining the conserved probability density and the underlying classical system for pseudo-Hermitian and in particular PT-symmetric quantum systems. As a concrete example we construct the Hermitian Hamiltonian h, the physical observables O α , the localized states and the conserved probability density for the non-Hermitian PT-symmetric square well. We achieve this by employing an appropriate perturbation scheme. For this system, we conduct a comprehensive study of both the kinematical and dynamical effects of the non-Hermiticity of the Hamiltonian on various physical quantities. In particular, we show that these effects are quantum mechanical in nature and diminish in the classical limit. Our results provide an objective assessment of the physical aspects of PT-symmetric quantum mechanics and clarify its relationship with both conventional quantum mechanics and classical mechanics

Palladium Catalyzed Allylic C-H Alkylation

DEFF Research Database (Denmark)

Engelin, Casper Junker; Fristrup, Peter

2011-01-01

are highlighted with emphasis on those leading to C-C bond formation, but where it was deemed necessary for the general understanding of the process closely related C-H oxidations and aminations are also included. It is found that C-H cleavage is most likely achieved by ligand participation which could involve......-H alkylation reaction which is the topic of the current review. Particular emphasis is put on current mechanistic proposals for the three reaction types comprising the overall transformation: C-H activation, nucleophillic addition, and re-oxidation of the active catalyst. Recent advances in C-H bond activation...... an acetate ion coordinated to Pd. Several of the reported systems rely on benzoquinone for re-oxidation of the active catalyst. The scope for nucleophilic addition in allylic C-H alkylation is currently limited, due to demands on pKa of the nucleophile. This limitation could be due to the pH dependence...

Immanant Conversion on Symmetric Matrices

Directory of Open Access Journals (Sweden)

Purificação Coelho M.

2014-01-01

Full Text Available Letr Σn(C denote the space of all n χ n symmetric matrices over the complex field C. The main objective of this paper is to prove that the maps Φ : Σn(C -> Σn (C satisfying for any fixed irre- ducible characters X, X' -SC the condition dx(A +aB = dχ·(Φ(Α + αΦ(Β for all matrices A,В ε Σ„(С and all scalars a ε C are automatically linear and bijective. As a corollary of the above result we characterize all such maps Φ acting on ΣИ(С.

Study for the charge symmetric systems, 12C+13N and 12C+13C with the orthogonalized coupled-reaction-channel method

International Nuclear Information System (INIS)

Imanishi, B.; Denisov, V.; Motobayashi, T.

1996-10-01

The charge-symmetric scattering systems, 12 C+ 13 N and 12 C+ 13 C have been investigated by using the orthogonalized coupled-reaction-channel (OCRC) method with the basis functions of the elastic, inelastic and transfer channels defined by the single-particle states, 1p1/2, 2s1/2, 1d5/2 and 1d3/2 of the valence nucleon in 13 N or 13 C. The data of the elastic scattering of 13 N on 12 C measured by Lienard et al. have been explained consistently with the data of the elastic and inelastic scattering of the 12 C+ 13 C system. The CRC effects both on the above systems are very strong, although those on the 12 C+ 13 N system are fairly weaker than the 12 C+ 13 C system. The role of the highly excited single-particle states 1d3/2 is particularly important in the formation of a specific CRC scheme, i.e., the formation of the covalent molecules due to the hybridization caused by the mixing of the different parity single-particle states. The fusion cross sections of the 12 C+ 13 C system at energies below the Coulomb barrier are strongly enhanced as a result of the strong CRC effects as compared with those of the 12 C+ 12 C system, while in 12 C+ 13 N system the enhancement of the sub-barrier fusion has not been observed. The above absorption mechanism for the 12 C+ 13 C system explains the lack of the molecular-resonance phenomena observed in the 12 C+ 12 C system. We check the effects of the dipole (E1) transition of the valence nucleon in 13 N (and also in 13 C) due to the core-core Coulomb interaction in the scattering at sub-barrier energies. The effects are not appreciable. (author)

An iteration for indefinite and non-symmetric systems and its application to the Navier-Stokes equations

Energy Technology Data Exchange (ETDEWEB)

Wathen, A. [Oxford Univ. (United Kingdom); Golub, G. [Stanford Univ., CA (United States)

1996-12-31

A simple fixed point linearisation of the Navier-Stokes equations leads to the Oseen problem which after appropriate discretisation yields large sparse linear systems with coefficient matrices of the form (A B{sup T} B -C). Here A is non-symmetric but its symmetric part is positive definite, and C is symmetric and positive semi-definite. Such systems arise in other situations. In this talk we will describe and present some analysis for an iteration based on an indefinite and symmetric preconditioner of the form (D B{sup T} B -C).

Anion binding in the C3v-symmetric cavity of a protonated tripodal amine receptor: potentiometric and single crystal X-ray studies.

Science.gov (United States)

Bose, Purnandhu; Ravikumar, I; Ghosh, Pradyut

2011-11-07

Tris(2-aminoethyl)amine (tren) based pentafluorophenyl-substituted tripodal L, tris[[(2,3,4,5,6-pentafluorobenzyl)amino]ethyl]amine receptor is synthesized in good yield and characterized by single crystal X-ray diffraction analysis. Detailed structural aspects of binding of different anionic guests toward L in its triprotonated form are examined thoroughly. Crystallographic results show binding of fluoride in the C(3v)-symmetric cavity of [H(3)L](3+) where spherical anion fluoride is in tricoordinated geometry via (N-H)(+)···F interaction in the complex [H(3)L(F)]·[F](2)·2H(2)O, (3). In the case of complexes [H(3)L(OTs)]·[OTs](2), (4) and [H(3)L(OTs)]·[NO(3)]·[OTs], (5), tetrahedral p-toluenesulphonate ion is engulfed in the cavity of [H(3)L](3+) via (N-H)(+)···O interactions. Interestingly, complex [(H(3)L)(2)(SiF(6))]·[BF(4)](4)·CH(3)OH·H(2)O, (6) shows encapsulation of octahedral hexafluorosilicate in the dimeric capsular assembly of two [H(3)L](3+) units, via a number of (N-H)(+)···F interactions. The kinetic parameters of L upon binding with different anions are evaluated using a potentiometric study in solution state. The potentiometric titration experiments in a polar protic methanol/water (1:1 v/v) binary solvent system show high affinity of the receptor toward more basic fluoride and acetate anions, with a lesser affinity for other inorganic anions (e.g., chloride, bromide, nitrate, sulfate, dihydrogenphosphate, and p-toluenesulphonate). © 2011 American Chemical Society

Computer Code for Interpreting 13C NMR Relaxation Measurements with Specific Models of Molecular Motion: The Rigid Isotropic and Symmetric Top Rotor Models and the Flexible Symmetric Top Rotor Model

Science.gov (United States)

2017-01-01

top rotor superimposes an effective correlation time, τe, onto a symmetric top rotor to account for internal motion. 2. THEORY The purpose...specifically describe how simple 13C relaxation theory is used to describe quantitatively simple molecular 3 motions. More-detailed accounts ...of nuclear magnetic relaxation can be found in a number of basic textbooks (i.e., Farrar and Becker, 1971; Fukushima and Roeder, 1981; Harris, 1986

Metallogels derived from silver coordination polymers of C3-symmetric tris(pyridylamide) tripodal ligands: synthesis of Ag nanoparticles and catalysis.

Science.gov (United States)

Paul, Mithun; Sarkar, Koushik; Dastidar, Parthasarathi

2015-01-02

By applying a recently developed crystal engineering rationale, four C3 symmetric tris(pyridylamide) ligands namely 1,3,5-tris(nicotinamidomethyl)-2,4,6-triethylbenzene, 1,3,5-tris(isonicotinamidomethyl)-2,4,6-triethylbenzene, 1,3,5-tris(nicotinamidomethyl)-2,4,6-trimethylbenzene, and 1,3,5-tris(isonicotinamidomethyl)-2,4,6-trimethylbenzene, which contain potential hydrogen-bonding sites, were designed and synthesized for generating Ag(I) coordination polymers and coordination-polymer-based gels. The coordination polymers thus obtained were characterized by single-crystal X-ray diffraction. The silver metallogels were characterized by transmission electron microscopy (TEM) and dynamic rheology. Upon exposure to visible light, these silver metallogels produced silver nanoparticles (AgNPs), which were characterized by TEM, powder X-ray diffraction, energy dispersive X-ray and X-ray photoelectron spectroscopy. These NPs were found to be effectively catalyzed the reduction of 4-nitrophenolate to 4-aminophenolate without the use of any exogenous reducing agent. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Recent developments in solar H 2 generation from water splitting

Indian Academy of Sciences (India)

Hydrogen production from water and sunlight through photocatalysis could become one of the channels, in the not-so-distant future, to meet a part of ever growing energy demands. However, accomplishing solar water splitting through semiconductor particulate photocatalysis seems to be the 'Holy Grail' problem of science.

Thermodynamic properties of hydrated cement phases: C-S-H, C-A-S-H and M-S-H

International Nuclear Information System (INIS)

Roosz, Cedric

2016-01-01

Concrete is one of the most widely used building materials in the world. Durability, mechanical and chemical properties have made it a material of choice in storage concepts proposed by the French National Agency for Radioactive Waste Management (Andra), including the achievement of retaining structures, cell plugs, massive supports or conditioning waste. The study of the stability of the constituent phases of cementitious materials is needed in view of the planned quantities and the durability of the structures, and must consider (i) temperature ranges suitable for cement matrices containment in contact with exothermic waste (25-80 deg. C), and (ii) a representative time scale of the lifetime of the storage. The Andra ThermoChimie project therefore aims to develop a consistent thermodynamic database, to model the chemical evolution of cement materials in the environment of radioactive waste. However, in the present state, the database offers only thermodynamic data of cementitious crystalline phases, as well as a limited data set of three different chemical compositions for nano-crystalline C-S-H. This does not allow to reproduce the degradation of cementitious materials, or model the degradation of the new formulations, such as 'Low pH' concretes. The objective is therefore to acquire a thermodynamic complementary data set on phases such as C-S-H (Calcium Silicate Hydrates) C-A-S-H (Calcium Aluminate Silicate Hydrates) and M-S-H (Magnesium Silicate Hydrates), to complete the ThermoChimie database. This study is based on experimental, analytical and digital work, in order to obtain a set of thermodynamic data (Δ f G 0 , Δ f H 0 , Cp(T), S 0 ) sufficiently representative of the chemical variability of these phases. Finally, this set of data allows the development of a thermodynamic predictive model in extended spaces of compositions and temperatures. Development of this predictive model requires (i) The acquisition of thermodynamic properties on

Sunspot splitting triggering an eruptive flare

Science.gov (United States)

Louis, Rohan E.; Puschmann, Klaus G.; Kliem, Bernhard; Balthasar, Horst; Denker, Carsten

2014-02-01

Aims: We investigate how the splitting of the leading sunspot and associated flux emergence and cancellation in active region NOAA 11515 caused an eruptive M5.6 flare on 2012 July 2. Methods: Continuum intensity, line-of-sight magnetogram, and dopplergram data of the Helioseismic and Magnetic Imager were employed to analyse the photospheric evolution. Filtergrams in Hα and He I 10830 Å of the Chromospheric Telescope at the Observatorio del Teide, Tenerife, track the evolution of the flare. The corresponding coronal conditions were derived from 171 Å and 304 Å images of the Atmospheric Imaging Assembly. Local correlation tracking was utilized to determine shear flows. Results: Emerging flux formed a neutral line ahead of the leading sunspot and new satellite spots. The sunspot splitting caused a long-lasting flow towards this neutral line, where a filament formed. Further flux emergence, partly of mixed polarity, as well as episodes of flux cancellation occurred repeatedly at the neutral line. Following a nearby C-class precursor flare with signs of interaction with the filament, the filament erupted nearly simultaneously with the onset of the M5.6 flare and evolved into a coronal mass ejection. The sunspot stretched without forming a light bridge, splitting unusually fast (within about a day, complete ≈6 h after the eruption) in two nearly equal parts. The front part separated strongly from the active region to approach the neighbouring active region where all its coronal magnetic connections were rooted. It also rotated rapidly (by 4.9° h-1) and caused significant shear flows at its edge. Conclusions: The eruption resulted from a complex sequence of processes in the (sub-)photosphere and corona. The persistent flows towards the neutral line likely caused the formation of a flux rope that held the filament. These flows, their associated flux cancellation, the emerging flux, and the precursor flare all contributed to the destabilization of the flux rope. We

Admissible perturbations and false instabilities in PT -symmetric quantum systems

Science.gov (United States)

Znojil, Miloslav

2018-03-01

One of the most characteristic mathematical features of the PT -symmetric quantum mechanics is the explicit Hamiltonian dependence of its physical Hilbert space of states H =H (H ) . Some of the most important physical consequences are discussed, with emphasis on the dynamical regime in which the system is close to phase transition. Consistent perturbation treatment of such a regime is proposed. An illustrative application of the innovated perturbation theory to a non-Hermitian but PT -symmetric user-friendly family of J -parametric "discrete anharmonic" quantum Hamiltonians H =H (λ ⃗) is provided. The models are shown to admit the standard probabilistic interpretation if and only if the parameters remain compatible with the reality of the spectrum, λ ⃗∈D(physical ) . In contradiction to conventional wisdom, the systems are then shown to be stable with respect to admissible perturbations, inside the domain D(physical ), even in the immediate vicinity of the phase-transition boundaries ∂ D(physical ) .

Experimental investigation of slow-positron emission from 4H-SiC and 6H-SiC surfaces

International Nuclear Information System (INIS)

Ling, C.C.; Beling, C.D.; Fung, S.; Weng, H.M.

2002-01-01

Slow-positron emission from the surfaces of as-grown n-type 4H-SiC and 6H-SiC (silicon carbide) with a conversion efficiency of ∼10 -4 has been observed. After 30 min of 1000 deg. C annealing in forming gas, the conversion efficiency of the n-type 6H-SiC sample was observed to be enhanced by 75% to 1.9x10 -4 , but it then dropped to ∼10 -5 upon a further 30 min annealing at 1400 deg. C. The positron work function of the n-type 6H-SiC was found to increase by 29% upon 1000 deg. C annealing. For both p-type 4H-SiC and p-type 6H-SiC materials, the conversion efficiency was of the order of ∼10 -5 , some ten times lower than that for the n-type materials. This was attributed to the band bending at the p-type material surface which caused positrons to drift away from the positron emitting surface. (author)

Electrochemical Cobalt-Catalyzed C-H Activation.

Science.gov (United States)

Sauermann, Nicolas; Meyer, Tjark H; Ackermann, Lutz

2018-06-19

Carbon-heteroatom bonds represent omnipresent structural motifs of the vast majority of functionalized materials and bioactive compounds. C-H activation has emerged as arguably the most efficient strategy to construct C-Het bonds. Despite of major advances, these C-H transformations were largely dominated by precious transition metal catalysts, in combination with stoichiometric, toxic metal oxidants. Herein, we discuss the recent evolution of cobalt-catalyzed C-H activations that enable C-Het formations with electricity as the sole sustainable oxidant until May 2018. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Structural stability of the square flux line lattice in YNi2B2C and LuNi2B2C studied with small angle neutron scattering

DEFF Research Database (Denmark)

Eskildsen, M.R.; Gammel, P.L.; Barber, B.P.

1997-01-01

We have studied the flux line lattice in YNi2B2C and LuNi2B2C, the nonmagnetic end members of the borocarbide superconductors using small angle neutron scattering and transport. For fields, H parallel to c, we find a square symmetric lattice which disorders rapidly above H/H-c2 similar to 0.2, well...... below the ''peak effect'' at H/H-c2 = 0.9. The results for H/H-c2 controlled by the tilt modulus c(44). For H/H-c2 > 0.2, the disordering appears to be associated with the field dependence of the shear modulus, C-66....

Nilpotent orbits in real symmetric pairs and stationary black holes

Energy Technology Data Exchange (ETDEWEB)

Dietrich, Heiko [School of Mathematical Sciences, Monash University, VIC (Australia); De Graaf, Willem A. [Department of Mathematics, University of Trento, Povo (Italy); Ruggeri, Daniele [Universita di Torino, Dipartimento di Fisica (Italy); INFN, Sezione di Torino (Italy); Trigiante, Mario [DISAT, Politecnico di Torino (Italy)

2017-02-15

In the study of stationary solutions in extended supergravities with symmetric scalar manifolds, the nilpotent orbits of a real symmetric pair play an important role. In this paper we discuss two approaches to determine the nilpotent orbits of a real symmetric pair. We apply our methods to an explicit example, and thereby classify the nilpotent orbits of (SL{sub 2}(R)){sup 4} acting on the fourth tensor power of the natural 2-dimensional SL{sub 2}(R)-module. This makes it possible to classify all stationary solutions of the so-called STU-supergravity model. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Nilpotent orbits in real symmetric pairs and stationary black holes

International Nuclear Information System (INIS)

Dietrich, Heiko; De Graaf, Willem A.; Ruggeri, Daniele; Trigiante, Mario

2017-01-01

In the study of stationary solutions in extended supergravities with symmetric scalar manifolds, the nilpotent orbits of a real symmetric pair play an important role. In this paper we discuss two approaches to determine the nilpotent orbits of a real symmetric pair. We apply our methods to an explicit example, and thereby classify the nilpotent orbits of (SL 2 (R)) 4 acting on the fourth tensor power of the natural 2-dimensional SL 2 (R)-module. This makes it possible to classify all stationary solutions of the so-called STU-supergravity model. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Photodissociation of C3H5Br and C4H7Br at 234 nm

International Nuclear Information System (INIS)

Kim, Hyun Kook; Paul, Dababrata; Hong, Ki Ryong; Cho, Ha Na; Kim, Tae Kyu; Lee, Kyoung Seok

2012-01-01

The photodissociation dynamics of cyclopropyl bromide (C-3H 5 Br) and cyclobutyl bromide (C 4 H 7 Br) at 234 nm was investigated. A two-dimensional photofragment ion-imaging technique coupled with a [2+1] resonance enhanced multiphoton ionization scheme was utilized to obtain speed and angular distributions of the nascent Br( 2 P 3/2 ) and Br*( 2 P 1/2 ) atoms. The recoil anisotropies for the Br and Br* channels were measured to be βBr = 0.92 ± 0.03 and βBr* = 1.52 ± 0.04 for C 3 H 5 Br and βBr = 1.10 ± 0.03 and βBr* = 1.49 ± 0.05 for C 4 H 7 Br. The relative quantum yield for Br was found to be ΦBr = 0.13 ± 0.03 and for C 3 H 5 Br and C 4 H 7 Br, respectively. The soft radical limit of the impulsive model adequately modeled the related energy partitioning. The nonadiabatic transition probability from the 3A' and 4A' potential energy surfaces was estimated and discussed

A Paley-Wiener theorem for reductive symmetric spaces

NARCIS (Netherlands)

Ban, E.P. van den; Schlichtkrull, H.

2006-01-01

Let X = G/H be a reductive symmetric space and K a maximal compact subgroup of G. The image under the Fourier transform of the space of K-finite compactly supported smooth functions on X is characterized.

Experimental and theoretical studies of the C{sub 6}H{sub 5} + C{sub 6}H{sub 6} reaction

Energy Technology Data Exchange (ETDEWEB)

Park, J.; Burova, S.; Rodgers, A.S.; Lin, M.C.

1999-11-11

The absolute rate constants for the C{sub 6}H{sub 5} + C{sub 6}H{sub 6} and C{sub 6}D{sub 6} reactions have been measured by cavity ringdown spectrometry at temperatures between 298 and 495 K at a constant 40 Torr Ar pressure. The new results, which reveal no detectable kinetic isotopic effect, can be represented by the Arrhenius equation, {kappa}{sub 1} = 10{sup (11.91{+-}0.13)} exp[{minus}(2,102 {+-} 106)/T] cm{sup 3}/(mol s). Low-temperature data for the addition/stabilization process, C{sub 6}H{sub 5} + C{sub 6}H{sub 6} {r{underscore}arrow} C{sub 12}H{sub 11}, can be correlated with those obtained in a low-pressure, high-temperature Knudsen cell study for the addition/displacement reaction, C{sub 6}H{sub 5} + C{sub 6}H{sub 6} {r{underscore}arrow} C{sub 12}H{sub 10} + H, by the RRKM theory using the molecular and transition-state parameters computed at the B3LYP/6-311G(d,p) level of theory. Combination of these two sets of data gives {kappa}{sub 1} = 10{sup (11.98{+-}0.03)} exp[{minus}(2168 {+-} 34)/T] cm{sup 3}/(mol s) covering the temperature range 298--1,330 K. The RRKM theory also correlates satisfactorily the forward reaction data with the high-temperature shock-tube result for the reverse H-for-C{sub 6}H{sub 5} substitution process with 2.7 and 4.7 kcal/mol barriers for the entrance (C{sub 6}H{sub 5} + C{sub 6}H{sub 6}) and reverse (H + C{sub 12}H{sub 10}) reactions, respectively. For modeling applications, the authors have calculated the forward reaction rate constants for the formation of the two competing products, H + C{sub 12}H{sub 10} and C{sub 12}H{sub 11}, at several pressures covering 300 K {lt} T {lt} 2,500 K.

Numerical investigation on splitting of ferrofluid microdroplets in T-junctions using an asymmetric magnetic field with proposed correlation

Science.gov (United States)

Aboutalebi, Mohammad; Bijarchi, Mohamad Ali; Shafii, Mohammad Behshad; Kazemzadeh Hannani, Siamak

2018-02-01

The studies surrounding the concept of microdroplets have seen a dramatic increase in recent years. Microdroplets have applications in different fields such as chemical synthesis, biology, separation processes and micro-pumps. This study numerically investigates the effect of different parameters such as Capillary number, Length of droplets, and Magnetic Bond number on the splitting process of ferrofluid microdroplets in symmetric T-junctions using an asymmetric magnetic field. The use of said field that is applied asymmetrically to the T-junction center helps us control the splitting of ferrofluid microdroplets. During the process of numerical simulation, a magnetic field with various strengths from a dipole located at a constant distance from the center of the T-junction was applied. The main advantage of this design is its control over the splitting ratio of daughter droplets and reaching various microdroplet sizes in a T-junction by adjusting the magnetic field strength. The results showed that by increasing the strength of the magnetic field, the possibility of asymmetric splitting of microdroplets increases in a way that for high values of field strength, high splitting ratios can be reached. Also, by using the obtained results at various Magnetic Bond numbers and performing curve fitting, a correlation is derived that can be used to accurately predict the borderline between splitting and non-splitting zones of microdroplets flow in micro T-junctions.

Deposition and characterisation of multilayer hard coatings. Ti/TiNδ/TiCxNy/(TiC) a-C:H/(Ti) a-C:H

International Nuclear Information System (INIS)

Burinprakhon, T.

2001-02-01

Multilayer hard coatings containing Ti, TiNδ, TiC x N y , (TiC m ) a-C:H, (TiC n ) a-C:H, and (Ti) a-C:H were deposited on commercially pure titanium substrates by using an asymmetric bipolar pulsed-dc reactive magnetron sputtering of a titanium target, with Ar, Ar+N 2 , Ar+N 2 +CH 4 , and Ar+CH 4 gas mixtures. The microstructures, elemental compositions and bonding states of the interlayers and the coating surfaces were studied by using cross-sectional transmission electron microscopy (XTEM), electron energy loss spectroscopy (EELS), X-ray diffraction (XRD), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). The microstructure development of the multilayer coating was strongly influenced by target poisoning. As a result of the complete poisoning of the titanium target during the deposition of TiNδ and TiC x N y interlayers, the a-C:H interlayers containing graded titanium and nitrogen contents were found to develop successively to the TiC x N y interlayer without the formation of near-stoichiometric TiC. The (TiC m ) a-C:H interlayer consisted of nano-particles of distorted fcc crystal structure embedded in the a-C:H matrix. The (TiC n ) a-C:H and (Ti) a-C:H top layers were found to be a-C:H matrix without nano-particles. In the (Ti) a-C:H top layer there was no measurable amount of Ti observed, regardless of the variation of CH 4 concentration between 37.5 and 60 % flow rate in Ar+-CH4 gas mixture. The top layer (Ti) a-C:H was found to contain approximately 10 atomic % nitrogen, due to N 2 contamination during deposition caused by low conductance of N 2 through the nominally closed valve of the mass flow controller. The change of the CH 4 concentration during deposition of the top layer (Ti) a-C:H, however, showed a strong influence on the hydrogen content. The comparison of the fluorescence background of the Raman spectra revealed that hydrogen-less (Ti) a-C:H was deposited at a CH 4 concentration of less than 50 % flow rate in Ar. The hardness

The Split Nucleus of Comet Wilson (C/1986 P1 = 1987 VII).

Science.gov (United States)

Meech, Karen J.; Knopp, Graham P.; Farnham, Tony L.; Green, Daniel

1995-07-01

We present CCD observations of Comet Wilson (C/1986 P1 = 1987 VII) from 26 nights during the time period 1986 October to 1991 February, which brackets perihelion, During the observing run of 1988 February, the comet was observed to have split into two fragments. Our broadband CCD photometry, along with photometry from the International Cometary Quarterly, shows a steady decline in brightness of Comet Wilson post-perihelion, with an outburst between heliocentric distances r = 2.8 and 3.3 AU during 1987 October and November. By r ≈ 7 AU, the fragment had faded with respect to the parent and was no longer centrally condensed. A brightness limit of mR ≈ 25, when the comet was at r = 12.65 AU, constrains the primary nucleus to have a maximum radius between 5 and 7 km, assuming an albedo of 0.04. The accuracy of direct orbital solutions for the parent body and fragment to determine the time of splitting was limited by the presence of significant nongravitational forces and the limited fragment orbital coverage. We used the relative position of the fragment with respect to the parent to calculate a time of splitting which was consistent with the time of the observed outburst. We discuss the possible causes of the splitting. The coma of Comet Wilson was observed to have a surface-brightness profile which fell off as p-1 (characteristic of a canonical steady-state coma under the influence of radiation pressure) for all of the data with the exception of the data taken during 1987 November when the gradient was p-1.3 . This steeper slope was probably caused by the injection of new material into the coma during the outburst. During 1986 October, there was a break in the surface-brightness profile slope which may be interpreted as the distance at which grains are swept into the tail. The profiles suggested grain velocities of a few x 10 2 to 10 m sec -1 for grains between 1 and a few hundred micrometers. Finson-Probstein dust modeling showed that ejection of grains began

Volume properties and refraction of aqueous solutions of bisadducts of light fullerene C60 and essential amino acids lysine, threonine, and oxyproline (C60(C6H13N2O2)2, C60(C4H8NO3)2, and C60(C5H9NO2)2) at 25°C

Science.gov (United States)

Semenov, K. N.; Ivanova, N. M.; Charykov, N. A.; Keskinov, V. A.; Kalacheva, S. S.; Duryagina, N. N.; Garamova, P. V.; Kulenova, N. A.; Nabieva, A.

2017-02-01

Concentration dependences of the density of aqueous solutions of bisadducts of light fullerene C60 and essential amino acids are studied by pycnometry. Concentration dependences of the average molar volumes and partial volumes of components (H2O and corresponding bisadducts) are calculated for C60(C6H13N2O2)2-H2O, C60(C4H8NO3)2-H2O, and C60(C5H9NO2)2-H2O binary systems at 25°C. Concentration dependences of the indices of refraction of C60(C6H13N2O2)2-H2O, C60(C4H8NO3)2-H2O, and C60(C5H9NO2)2-H2O binary systems are determined at 25°C. The concentration dependences of specific refraction and molar refraction of bisadducts and aqueous solutions of them are calculated.

Algorithms for sparse, symmetric, definite quadratic lambda-matrix eigenproblems

International Nuclear Information System (INIS)

Scott, D.S.; Ward, R.C.

1981-01-01

Methods are presented for computing eigenpairs of the quadratic lambda-matrix, M lambda 2 + C lambda + K, where M, C, and K are large and sparse, and have special symmetry-type properties. These properties are sufficient to insure that all the eigenvalues are real and that theory analogous to the standard symmetric eigenproblem exists. The methods employ some standard techniques such as partial tri-diagonalization via the Lanczos Method and subsequent eigenpair calculation, shift-and- invert strategy and subspace iteration. The methods also employ some new techniques such as Rayleigh-Ritz quadratic roots and the inertia of symmetric, definite, quadratic lambda-matrices

Height in splittings of hyperbolic groups

Indian Academy of Sciences (India)

R. Narasimhan (Krishtel eMaging) 1461 1996 Oct 15 13:05:22

of G. We choose a finite symmetric generating set for H and extend it to a finite ...... [10] Bonahon F, Geodesic currents on negatively curved groups, in: Arboreal ... [14] Canary R D, Epstein D B A and Green P, Notes on notes of Thurston, in: ...

The Approximate Capacity Region of the Symmetric $K$-user Gaussian Interference Channel with Strong Interference

KAUST Repository

Chaaban, Anas

2016-03-01

The symmetric K-user interference channel is studied with the goal of characterizing its capacity region in the strong interference regime within a constant gap. The achievable rate region of a scheme combining rate-splitting at the transmitters and interference alignment and successive decoding/computation at the receivers is derived. Next it is shown that this scheme achieves the so-called greedy-max corner points of the capacity region within a constant gap. By combining this result with previous results by Ordentlich et al. on the sum-capacity of the symmetric interference channel, a constant gap characterization of the capacity region for the strong interference regime is obtained. This leads to the first approximate characterization of the capacity region of the symmetric K-user IC. Furthermore, a new scheme that achieves the sum-capacity of the channel in the strong interference regime within a constant gap is also proposed, and the corresponding gap is calculated. The advantage of the new scheme is that it leads to a characterization within a constant gap without leaving an outage set contrary to the scheme by Ordentlich et al..

The Approximate Capacity Region of the Symmetric $K$-user Gaussian Interference Channel with Strong Interference

KAUST Repository

Chaaban, Anas; Sezgin, Aydin

2016-01-01

The symmetric K-user interference channel is studied with the goal of characterizing its capacity region in the strong interference regime within a constant gap. The achievable rate region of a scheme combining rate-splitting at the transmitters and interference alignment and successive decoding/computation at the receivers is derived. Next it is shown that this scheme achieves the so-called greedy-max corner points of the capacity region within a constant gap. By combining this result with previous results by Ordentlich et al. on the sum-capacity of the symmetric interference channel, a constant gap characterization of the capacity region for the strong interference regime is obtained. This leads to the first approximate characterization of the capacity region of the symmetric K-user IC. Furthermore, a new scheme that achieves the sum-capacity of the channel in the strong interference regime within a constant gap is also proposed, and the corresponding gap is calculated. The advantage of the new scheme is that it leads to a characterization within a constant gap without leaving an outage set contrary to the scheme by Ordentlich et al..

On Symmetric Polynomials

OpenAIRE

Golden, Ryan; Cho, Ilwoo

2015-01-01

In this paper, we study structure theorems of algebras of symmetric functions. Based on a certain relation on elementary symmetric polynomials generating such algebras, we consider perturbation in the algebras. In particular, we understand generators of the algebras as perturbations. From such perturbations, define injective maps on generators, which induce algebra-monomorphisms (or embeddings) on the algebras. They provide inductive structure theorems on algebras of symmetric polynomials. As...

Ferroelectric phase transition in hydrogen-bonded 2-aminopyridine phosphate (NC sub 4 H sub 4 NH sub 2)centre dot H sub 3 PO sub 4

CERN Document Server

Czapla, Z; Waskowska, A

2003-01-01

A new crystal of 2-aminopyridine phosphate (NC sub 4 H sub 4 NH sub 2)centre dot H sub 3 PO sub 4 has been grown and its x-ray structure and physical properties were studied. At room temperature the crystals are monoclinic, space group C2/c. The flat 2-aminopyridine cations are hydrogen bonded to the anionic [PO sub 4 ] groups. The interesting feature of the crystal structure is the three-dimensional network of hydrogen bonds including, among others, two strong, symmetrical O centre dot centre dot centre dot H, H centre dot centre dot centre dot O interactions with disordered proton locations. Symmetrically related PO sub 4 anions linked through these protons form infinite (PO sub 4) subinfinity chains along the crystal a-axis. The anomalies in the temperature dependence of the electric permittivity showed that the crystal undergoes ferroelectric phase transition at T sub c = 103.5 K. The spontaneous polarization takes place along the crystal a-axis, being parallel to the chains of the hydrogen-bonded PO sub ...

Prevalence of Split Nerve Fiber Layer Bundles in Healthy People Imaged with Spectral Domain Optical Coherence Tomography

Directory of Open Access Journals (Sweden)

Sirel Gür Güngör

2016-12-01

Full Text Available Objectives: The presence of retinal nerve fiber layer (RNFL split bundles was recently described in normal eyes scanned using scanning laser polarimetry and by histologic studies. Split bundles may resemble RNFL loss in healthy eyes. The aim of our study was to determine the prevalence of nerve fiber layer split bundles in healthy people. Materials and Methods: We imaged 718 eyes of 359 healthy persons with the spectral domain optical coherence tomography in this cross-sectional study. All eyes had intraocular pressure of 21 mmHg or less, normal appearance of the optic nerve head, and normal visual fields (Humphrey Field Analyzer 24-2 full threshold program. In our study, a bundle was defined as ‘split’ when there is localized defect not resembling a wedge defect in the RNFL deviation map with a symmetrically divided RNFL appearance on the RNFL thickness map. The classification was performed by two independent observers who used an identical set of reference examples to standardize the classification. Results: Inter-observer consensus was reached in all cases. Bilateral superior split bundles were seen in 19 cases (5.29% and unilateral superior split was observed in 15 cases (4.16%. In 325 cases (90.52% there was no split bundle. Conclusion: Split nerve fiber layer bundles, in contrast to single nerve fiber layer bundles, are not common findings in healthy eyes. In eyes with normal optic disc appearance, especially when a superior RNFL defect is observed in RNFL deviation map, the RNLF thickness map and graphs should also be examined for split nerve fiber layer bundles.

Fourier inversion on a reductive symmetric space

NARCIS (Netherlands)

Ban, E.P. van den

1999-01-01

Let X be a semisimple symmetric space. In previous papers, [8] and [9], we have dened an explicit Fourier transform for X and shown that this transform is injective on the space C 1 c (X) ofcompactly supported smooth functions on X. In the present paper, which is a continuation of these papers, we

A control-oriented simulation model of a power-split hybrid electric vehicle

International Nuclear Information System (INIS)

Cipek, Mihael; Pavković, Danijel; Petrić, Joško

2013-01-01

Highlights: ► A simulation model of a two mode power-split hybrid electric vehicle (HEV) is proposed. ► Modeling the energy losses in the HEV transmission components are presented. ► The control optimization model implementation aspects are discussed. -- Abstract: A simulation model of a two mode power-split hybrid electric vehicle (HEV) is proposed in this paper for the purpose of HEV dynamics analysis and control system design. The bond graph methodology is used to model dominant dynamic effects of the mechanical part of the HEV transmission. Simple quasi-static battery model, the environment model, the tire and the power losses model of a vehicle are included, as well. A low-level electric generator speed control loop is designed, which includes a PI controller tuned according to the symmetrical optimum tuning procedure. Finally, off-line optimization by conjugate gradient-based BPTT-like optimal control algorithm, which is based on the presented mathematical model, is also given in the paper.

Direct measurements of rate constants for the reactions of CH3 radicals with C2H6, C2H4, and C2H2 at high temperatures.

Science.gov (United States)

Peukert, S L; Labbe, N J; Sivaramakrishnan, R; Michael, J V

2013-10-10

The shock tube technique has been used to study the reactions CH3 + C2H6 → C2H4 + CH4 + H (1), CH3 + C2H4 → Products + H (2), and CH3 + C2H2 → Products + H (3). Biacetyl, (CH3CO)2, was used as a clean high temperature thermal source for CH3-radicals for all the three reactions studied in this work. For reaction 1, the experiments span a T-range of 1153 K ≤ T ≤ 1297 K, at P ~ 0.4 bar. The experiments on reaction 2 cover a T-range of 1176 K ≤ T ≤ 1366 K, at P ~ 1.0 bar, and those on reaction 3 a T-range of 1127 K ≤ T ≤ 1346 K, at P ~ 1.0 bar. Reflected shock tube experiments performed on reactions 1-3, monitored the formation of H-atoms with H-atom Atomic Resonance Absorption Spectrometric (ARAS). Fits to the H-atom temporal profiles using an assembled kinetics model were used to make determinations for k1, k2, and k3. In the case of C2H6, the measurements of [H]-atoms were used to derive direct high-temperature rate constants, k1, that can be represented by the Arrhenius equation k1(T) = 5.41 × 10(-12) exp(-6043 K/T) cm(3) molecules(-1) s(-1) (1153 K ≤ T ≤ 1297 K) for the only bimolecular process that occurs, H-atom abstraction. TST calculations based on ab initio properties calculated at the CCSD(T)/CBS//M06-2X/cc-pVTZ level of theory show excellent agreement, within ±20%, of the measured rate constants. For the reaction of CH3 with C2H4, the present rate constant results, k2', refer to the sum of rate constants, k(2b) + k(2c), from two competing processes, addition-elimination, and the direct abstraction CH3 + C2H4 → C3H6 + H (2b) and CH3 + C2H4 → C2H2 + H + CH4 (2c). Experimental rate constants for k2' can be represented by the Arrhenius equation k2'(T) = 2.18 × 10(-10) exp(-11830 K/T) cm(3) molecules(-1) s(-1) (1176 K ≤ T ≤ 1366 K). The present results are in excellent agreement with recent theoretical predictions. The present study provides the only direct measurement for the high-temperature rate constants for these channels

SplitDist—Calculating Split-Distances for Sets of Trees

DEFF Research Database (Denmark)

Mailund, T

2004-01-01

We present a tool for comparing a set of input trees, calculating for each pair of trees the split-distances, i.e., the number of splits in one tree not present in the other.......We present a tool for comparing a set of input trees, calculating for each pair of trees the split-distances, i.e., the number of splits in one tree not present in the other....

Symmetrization of Facade Layouts

KAUST Repository

Jiang, Haiyong; Yan, Dong-Ming; Dong, Weiming; Wu, Fuzhang; Nan, Liangliang; Zhang, Xiaopeng

2016-01-01

We present an automatic approach for symmetrizing urban facade layouts. Our method can generate a symmetric layout through minimally modifying the original input layout. Based on the principles of symmetry in urban design, we formulate facade layout symmetrization as an optimization problem. Our method further enhances the regularity of the final layout by redistributing and aligning elements in the layout. We demonstrate that the proposed solution can effectively generate symmetric facade layouts.

Symmetrization of Facade Layouts

KAUST Repository

Jiang, Haiyong

2016-02-26

We present an automatic approach for symmetrizing urban facade layouts. Our method can generate a symmetric layout through minimally modifying the original input layout. Based on the principles of symmetry in urban design, we formulate facade layout symmetrization as an optimization problem. Our method further enhances the regularity of the final layout by redistributing and aligning elements in the layout. We demonstrate that the proposed solution can effectively generate symmetric facade layouts.

Non-flipping 13C spins near an NV center in diamond: hyperfine and spatial characteristics by density functional theory simulation of the C510[NV]H252 cluster

Science.gov (United States)

Nizovtsev, A. P.; Kilin, S. Ya; Pushkarchuk, A. L.; Pushkarchuk, V. A.; Kuten, S. A.; Zhikol, O. A.; Schmitt, S.; Unden, T.; Jelezko, F.

2018-02-01

Single NV centers in diamond coupled by hyperfine interaction (hfi) to neighboring 13C nuclear spins are now widely used in emerging quantum technologies as elements of quantum memory adjusted to a nitrogen-vacancy (NV) center electron spin qubit. For nuclear spins with low flip-flop rate, single shot readout was demonstrated under ambient conditions. Here we report on a systematic search for such stable NV-13C systems using density functional theory to simulate the hfi and spatial characteristics of all possible NV-13C complexes in the H-terminated cluster C510[NV]-H252 hosting the NV center. Along with the expected stable ‘NV-axial-13C’ systems wherein the 13C nuclear spin is located on the NV axis, we found for the first time new families of positions for the 13C nuclear spin exhibiting negligible hfi-induced flipping rates due to near-symmetric local spin density distribution. Spatially, these positions are located in the diamond bilayer passing through the vacancy of the NV center and being perpendicular to the NV axis. Analysis of available publications showed that, apparently, some of the predicted non-axial near-stable NV-13C systems have already been observed experimentally. A special experiment performed on one of these systems confirmed the prediction made.

Symmetry-adapted HAM/3 method and its application to some symmetric molecules

Directory of Open Access Journals (Sweden)

Narita Susumu

2004-01-01

Full Text Available The semiempirical HAM/3 method developed by Lindholm and coworkers about two decades ago has been known to have a deficiency that splits energies for the degenerate energy states. We have recently proposed a group-theoretical approach to remedy the internally broken symmetry of the HAM/3 Hamiltonians. In this paper, we present some results of its application to various small molecules with symmetry Td, C3v, and D3h. The proposed scheme gives correct degeneracy for these molecules.

Symmetry-adapted HAM/3 method and its application to some symmetric molecules

OpenAIRE

Narita, Susumu; Shibuya, Tai-ichi; Fujiwara, Fred Y.; Takahata, Yuji

2004-01-01

The semiempirical HAM/3 method developed by Lindholm and coworkers about two decades ago has been known to have a deficiency that splits energies for the degenerate energy states. We have recently proposed a group-theoretical approach to remedy the internally broken symmetry of the HAM/3 Hamiltonians. In this paper, we present some results of its application to various small molecules with symmetry Td, C3v, and D3h. The proposed scheme gives correct degeneracy for these molecules. O método...

Helically symmetric experiment, (HSX) goals, design and status

International Nuclear Information System (INIS)

Anderson, F.S.B.; Almagri, A.F.; Anderson, D.T.; Matthews, P.G.; Talmadge, J.N.; Shohet, J.L.

1995-01-01

HSX is a quasi-helically symmetric (QHS) stellarator currently under construction at the Torsatron-Stellarator Laboratory of the University of Wisconsin-Madison. This device is unique in its magnetic design in that the magnetic field spectrum possesses only a single dominant (helical) component. This design avoids the large direct orbit losses and the low-collisionality neoclassical losses associated with conventional stellarators. The restoration of symmetry to the confining magnetic field makes the neoclassical confinement in this device analogous to an axisymmetric q=1/3 tokamak. The HSX device has been designed with a clear set of primary physics goals: demonstrate the feasibility of construction of a QHS device, examine single particle confinement of injected ions with regard to magnetic field symmetry breaking, compare density and temperature profiles in this helically symmetric system to those for axisymmetric tokamaks and conventional stellarators, examine electric fields and plasma rotation with edge biasing in relation to L-H transitions in symmetric versus non-symmetric stellarator systems, investigate QHS effects on 1/v regime electron confinement, and examine how greatly-reduced neoclassical electron thermal conductivity compares to the experimental χ e profile. 3 refs., 4 figs., 1 tab

Characterization of the human pH- and PKA-activated ClC-2G(2 alpha) Cl- channel.

Science.gov (United States)

Sherry, A M; Stroffekova, K; Knapp, L M; Kupert, E Y; Cuppoletti, J; Malinowska, D H

1997-08-01

A ClC-2G(2 alpha) Cl- channel was identified to be present in human lung and stomach, and a partial cDNA for this Cl- channel was cloned from a human fetal lung library. A full-length expressible human ClC-2G(2 alpha) cDNA was constructed by ligation of mutagenized expressible rabbit ClC-2G(2 alpha) cDNA with the human lung ClC-2G(2 alpha) cDNA, expressed in oocytes, and characterized at the single-channel level. Adenosine 3',5'-cyclic monophosphate-dependent protein kinase (PKA) treatment increased the probability of opening of the channel (Po). After PKA activation, the channel exhibited a linear (r = 0.99) current-voltage curve with a slope conductance of 22.1 +/- 0.8 pS in symmetric 800 mM tetraethylammonium chloride (TEACl; pH 7.4). Under fivefold gradient conditions of TEACl, a reversal potential of +21.5 +/- 2.8 mV was measured demonstrating anion-to-cation discrimination. As previously demonstrated for the rabbit ClC-2G(2 alpha) Cl- channel, the human analog, hClC-2G(2 alpha), was active at pH 7.4 as well as when the pH of the extracellular face of the channel (trans side of the bilayer; pHtrans) was asymmetrically reduced to pH 3.0. The extent of PKA activation was dependent on pHtrans. With PKA treatment, Po increased fourfold with a pHtrans of 7.4 and eightfold with a pHtrans of 3.0. Effects of sequential PKA addition followed by pHtrans reduction on the same channel suggested that the PKA- and pH-dependent increases in channel Po were separable and cumulative. Northern analysis showed ClC-2G(2 alpha) mRNA to be present in human adult and fetal lung and adult stomach, and quantitative reverse transcriptase-polymerase chain reaction showed this channel to be present in the adult human lung and stomach at about one-half the level found in fetal lung. The findings of the present study suggest that the ClC-2G(2 alpha) Cl- channel may play an important role in Cl- transport in the fetal and adult human lung.

Torsionally mediated spin-rotation hyperfine splittings at moderate to high J values in methanol

Energy Technology Data Exchange (ETDEWEB)

Belov, S. P.; Golubiatnikov, G. Yu.; Lapinov, A. V. [Institute of Applied Physics of the Russian Academy of Sciences, 46 Ulyanov Street, 603950 Nizhny Novgorod (Russian Federation); Ilyushin, V. V.; Mescheryakov, A. A. [Institute of Radio Astronomy of National Academy of Sciences of Ukraine, Chervonopraporna 4, 61002 Kharkov (Ukraine); Alekseev, E. A. [Institute of Radio Astronomy of National Academy of Sciences of Ukraine, Chervonopraporna 4, 61002 Kharkov (Ukraine); Quantum Radiophysics Department of V. N. Karazin Kharkiv National University, Svobody Square 4, 61022 Kharkov (Ukraine); Hougen, J. T., E-mail: jon.hougen@nist.gov [Sensor Science Division, National Institute of Standards and Technology, Gaithersburg, Maryland 20899-8441 (United States); Xu, Li-Hong [Department of Physics and Centre for Laser, Atomic, and Molecular Sciences, University of New Brunswick, Saint John, New Brunswick E2L 4L5 (Canada)

2016-07-14

This paper presents an explanation based on torsionally mediated proton-spin–overall-rotation interaction for the observation of doublet hyperfine splittings in some Lamb-dip sub-millimeter-wave transitions between ground-state torsion-rotation states of E symmetry in methanol. These unexpected doublet splittings, some as large as 70 kHz, were observed for rotational quantum numbers in the range of J = 13 to 34, and K = − 2 to +3. Because they increase nearly linearly with J for a given branch, we confined our search for an explanation to hyperfine operators containing one nuclear-spin angular momentum factor I and one overall-rotation angular momentum factor J (i.e., to spin-rotation operators) and ignored both spin-spin and spin-torsion operators, since they contain no rotational angular momentum operator. Furthermore, since traditional spin-rotation operators did not seem capable of explaining the observed splittings, we constructed totally symmetric “torsionally mediated spin-rotation operators” by multiplying the E-species spin-rotation operator by an E-species torsional-coordinate factor of the form e{sup ±niα}. The resulting operator is capable of connecting the two components of a degenerate torsion-rotation E state. This has the effect of turning the hyperfine splitting pattern upside down for some nuclear-spin states, which leads to bottom-to-top and top-to-bottom hyperfine selection rules for some transitions, and thus to an explanation for the unexpectedly large observed hyperfine splittings. The constructed operator cannot contribute to hyperfine splittings in the A-species manifold because its matrix elements within the set of torsion-rotation A{sub 1} and A{sub 2} states are all zero. The theory developed here fits the observed large doublet splittings to a root-mean-square residual of less than 1 kHz and predicts unresolvable splittings for a number of transitions in which no doublet splitting was detected.

Uniqueness of flat spherically symmetric spacelike hypersurfaces admitted by spherically symmetric static spacetimes

Science.gov (United States)

Beig, Robert; Siddiqui, Azad A.

2007-11-01

It is known that spherically symmetric static spacetimes admit a foliation by flat hypersurfaces. Such foliations have explicitly been constructed for some spacetimes, using different approaches, but none of them have proved or even discussed the uniqueness of these foliations. The issue of uniqueness becomes more important due to suitability of flat foliations for studying black hole physics. Here, flat spherically symmetric spacelike hypersurfaces are obtained by a direct method. It is found that spherically symmetric static spacetimes admit flat spherically symmetric hypersurfaces, and that these hypersurfaces are unique up to translation under the timelike Killing vector. This result guarantees the uniqueness of flat spherically symmetric foliations for such spacetimes.

Rings of continuous functions, symmetric products, and Frobenius algebras

International Nuclear Information System (INIS)

Buchstaber, Viktor M; Rees, E G

2004-01-01

A constructive proof is given for the classical theorem of Gel'fand and Kolmogorov (1939) characterising the image of the evaluation map from a compact Hausdorff space X into the linear space C(X)* dual to the ring C(X) of continuous functions on X. Our approach to the proof enabled us to obtain a more general result characterising the image of the evaluation map from the symmetric products Sym n (X) into C(X)*. A similar result holds if X=C m and leads to explicit equations for symmetric products of affine algebraic varieties as algebraic subvarieties in the linear space dual to the polynomial ring. This leads to a better understanding of the algebra of multisymmetric polynomials. The proof of all these results is based on a formula used by Frobenius in 1896 in defining higher characters of finite groups. This formula had no further applications for a long time; however, it has appeared in several independent contexts during the last fifteen years. It was used by A. Wiles and R.L. Taylor in studying representations and by H.-J. Hoehnke and K.W. Johnson and later by J. McKay in studying finite groups. It plays an important role in our work concerning multivalued groups. Several properties of this remarkable formula are described. It is also used to prove a theorem on the structure constants of Frobenius algebras, which have recently attracted attention due to constructions taken from topological field theory and singularity theory. This theorem develops a result of Hoehnke published in 1958. As a corollary, a direct self-contained proof is obtained for the fact that the 1-, 2-, and 3-characters of the regular representation determine a finite group up to isomorphism. This result was first published by Hoehnke and Johnson in 1992

Sub-Doppler slit jet infrared spectroscopy of astrochemically relevant cations: Symmetric (ν1) and antisymmetric (ν6) NH stretching modes in ND2H2+

Science.gov (United States)

Chang, Chih-Hsuan; Nesbitt, David J.

2018-01-01

Sub-Doppler infrared rovibrational transitions in the symmetric (v1) and antisymmetric (v6) NH stretch modes of the isotopomerically substituted ND2H2+ ammonium cation are reported for the first time in a slit jet discharge supersonic expansion spectrometer. The partially H/D substituted cation is generated by selective isotopic exchange of ND3 with H2O to form NHD2, followed by protonation with H3+ formed in the NHD2/H2/Ne slit-jet discharge expansion environment. Rotational assignment for ND2H2+ is confirmed rigorously by four line ground state combination differences, which agree to be within the sub-Doppler precision in the slit jet (˜9 MHz). Observation of both b-type (ν1) and c-type (ν6) bands enables high precision determination of the ground and vibrationally excited state rotational constants. From an asymmetric top Watson Hamiltonian analysis, the ground state constants are found to be A″ = 4.856 75(4) cm-1, B″ = 3.968 29(4) cm-1, and C″ = 3.446 67(6) cm-1, with band origins at 3297.5440(1) and 3337.9050(1) cm-1 for the v1 and v6 modes, respectively. This work permits prediction of precision microwave/mm-wave transitions, which should be invaluable in facilitating ongoing spectroscopic searches for partially deuterated ammonium cations in interstellar clouds and star-forming regions of the interstellar medium.

Vapor pressure and specific electrical conductivity in the solid and molten H2O-CsH2PO4-CsPO3 system—a novel electrolyte for water electrolysis at ~ 225–400 °C

DEFF Research Database (Denmark)

Nikiforov, Aleksey Valerievich; Berg, Rolf W.; Bjerrum, Niels J.

2018-01-01

Cesium dihydrogen phosphate, CsH2PO4 (CDP) was studied for water electrolysis at ~ 225–400 °C. In the presence of sufficient humidity, CDP is structurally disordered and super-protonic conducting with conductivities reaching 0.2–0.25 S cm−1, when determined in suitable H-shaped sealed conductivity...... on internal reference gases. Pressures up to ~ 49 bar were estimated, much higher than previously expected. Conductivities were given as polynomials and plotted in solid and liquid states. Water splitting electrolysis 2H2O → 2H2 + O2 was demonstrated by Raman at ~ 355 °C under a water pressure of ~ 23 bar...... in a quartz cell with platinum electrodes, showing molten CDP to have significant potential for water electrolysis....

Electrodeposition of Ni-Mo alloy coatings for water splitting reaction

Science.gov (United States)

Shetty, Akshatha R.; Hegde, Ampar Chitharanjan

2018-04-01

The present study reports the development of Ni-Mo alloy coatings for water splitting applications, using a citrate bath the inducing effect of Mo (reluctant metal) on electrodeposition, its relationship with their electrocatalytic efficiency were studied. The alkaline water splitting efficiency of Ni-Mo alloy coatings, for both hydrogen evolution reaction (HER) and oxygen evolution reaction were tested using cyclic voltammetry (CV) and chronopotentiometry (CP) techniques. Moreover, the practical utility of these electrode materials were evaluated by measuring the amount of H2 and O2 gas evolved. The variation in electrocatalytic activity with composition, structure, and morphology of the coatings were examined using XRD, SEM, and EDS analyses. The experimental results showed that Ni-Mo alloy coating is the best electrode material for alkaline HER and OER reactions, at lower and higher deposition current densities (c. d.'s) respectively. This behavior is attributed by decreased Mo and increased Ni content of the alloy coating and the number of electroactive centers.

Normalizations of Eisenstein integrals for reductive symmetric spaces

NARCIS (Netherlands)

van den Ban, E.P.; Kuit, Job

2017-01-01

We construct minimal Eisenstein integrals for a reductive symmetric space G/H as matrix coefficients of the minimal principal series of G. The Eisenstein integrals thus obtained include those from the \\sigma-minimal principal series. In addition, we obtain related Eisenstein integrals, but with

Splitting strings on integrable backgrounds

Energy Technology Data Exchange (ETDEWEB)

Vicedo, Benoit

2011-05-15

We use integrability to construct the general classical splitting string solution on R x S{sup 3}. Namely, given any incoming string solution satisfying a necessary self-intersection property at some given instant in time, we use the integrability of the worldsheet {sigma}-model to construct the pair of outgoing strings resulting from a split. The solution for each outgoing string is expressed recursively through a sequence of dressing transformations, the parameters of which are determined by the solutions to Birkhoff factorization problems in an appropriate real form of the loop group of SL{sub 2}(C). (orig.)

Bandgap measurements and the peculiar splitting of E2H phonon modes of InxAl1-xN nanowires grown by plasma assisted molecular beam epitaxy

KAUST Repository

Tangi, Malleswararao; Mishra, Pawan; Janjua, Bilal; Ng, Tien Khee; Anjum, Dalaver H.; Prabaswara, Aditya; Yang, Yang; Albadri, Abdulrahman M.; Alyamani, Ahmed Y.; El-Desouki, Munir M.; Ooi, Boon S.

2016-01-01

SE. The micro-Raman spectra in the NWs with x = 0.5 showed two-mode behavior for A1(LO) phonons and single mode behavior for E2 H phonons. As for x = 0.17, i.e., high Al content, we observed a peculiar E2 H phonon mode splitting. Further, we observe

An Integrated Photoelectrochemical-Chemical Loop for Solar-Driven Overall Splitting of Hydrogen Sulfide

DEFF Research Database (Denmark)

Zong, Xu; Han, Jingfeng; Seger, Brian

2014-01-01

Abundant and toxic hydrogen sulfide (H2S) from industry and nature has been traditionally considered a liability. However, it represents a potential resource if valuable H-2 and elemental sulfur can be simultaneously extracted through a H2S splitting reaction. Herein a photochemical-chemical loop...... simulated solar light. This new conceptual design will not only provide a possible route for using solar energy to convert H2S into valuable resources, but also sheds light on some challenging photochemical reactions such as CH4 activation and CO2 reduction.......Abundant and toxic hydrogen sulfide (H2S) from industry and nature has been traditionally considered a liability. However, it represents a potential resource if valuable H-2 and elemental sulfur can be simultaneously extracted through a H2S splitting reaction. Herein a photochemical-chemical loop...... linked by redox couples such as Fe2+/Fe3+ and I-/I-3(-) for photoelectrochemical H-2 production and H2S chemical absorption redox reactions are reported. Using functionalized Si as photoelectrodes, H2S was successfully split into elemental sulfur and H-2 with high stability and selectivity under...

Directing-Group-mediated C-H-Alkynylations.

Science.gov (United States)

Caspers, Lucien D; Nachtsheim, Boris J

2018-05-18

C-C triple bonds are amongst the most versatile functional groups in synthetic chemistry. Complementary to the Sonogashira coupling the direct metal-catalyzed alkynylation of C-H bonds has emerged as a highly promising approach in recent years. To guarantee a high regioselectivity suitable directing groups (DGs) are necessary to guide the transition metal (TM) into the right place. In this Focus Review we present the current developments in DG-mediated C(sp 2 )-H and C(sp 3 )-H modifications with terminal alkynes under oxidative conditions and with electrophilic alkynylation reagents. We will discuss further modifications of the alkyne, in particular subsequent cyclizations to carbo- and heterocycles and modifications of the DG in the presence of the alkyne. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Superconductivity induced by flexural modes in non-σh-symmetric Dirac-like two-dimensional materials: A theoretical study for silicene and germanene

Science.gov (United States)

Fischetti, Massimo V.; Polley, Arup

2018-04-01

In two-dimensional crystals that lack symmetry under reflections on the horizontal plane of the lattice (non-σh-symmetric), electrons can couple to flexural modes (ZA phonons) at first order. We show that in materials of this type that also exhibit a Dirac-like electron dispersion, the strong coupling can result in electron pairing mediated by these phonons, as long as the flexural modes are not damped or suppressed by additional interactions with a supporting substrate or gate insulator. We consider several models: The weak-coupling limit, which is applicable only in the case of gapped and parabolic materials, like stanene and HfSe2, thanks to the weak coupling; the full gap-equation, solved using the constant-gap approximation and considering statically screened interactions; its extensions to energy-dependent gap and to dynamic screening. We argue that in the case of silicene and germanene superconductivity mediated by this process can exhibit a critical temperature of a few degrees K, or even a few tens of degrees K when accounting for the effect of a high-dielectric-constant environment. We conclude that the electron/flexural-modes coupling should be included in studies of possible superconductivity in non-σh-symmetric two-dimensional crystals, even if alternative forms of coupling are considered.

Symmetric q-Bessel functions

Directory of Open Access Journals (Sweden)

Giuseppe Dattoli

1996-05-01

Full Text Available q analog of bessel functions, symmetric under the interchange of q and q^ −1 are introduced. The definition is based on the generating function realized as product of symmetric q-exponential functions with appropriate arguments. Symmetric q-Bessel function are shown to satisfy various identities as well as second-order q-differential equations, which in the limit q → 1 reproduce those obeyed by the usual cylindrical Bessel functions. A brief discussion on the possible algebraic setting for symmetric q-Bessel functions is also provided.

Efficient Visible-Light-Driven Z-Scheme Overall Water Splitting Using a MgTa2O(6-x)N(y)/TaON Heterostructure Photocatalyst for H2 Evolution.

Science.gov (United States)

Chen, Shanshan; Qi, Yu; Hisatomi, Takashi; Ding, Qian; Asai, Tomohiro; Li, Zheng; Ma, Su Su Khine; Zhang, Fuxiang; Domen, Kazunari; Li, Can

2015-07-13

An (oxy)nitride-based heterostructure for powdered Z-scheme overall water splitting is presented. Compared with the single MgTa2O(6-x)N(y) or TaON photocatalyst, a MgTa2O(6-x)N(y)/TaON heterostructure fabricated by a simple one-pot nitridation route was demonstrated to effectively suppress the recombination of carriers by efficient spatial charge separation and decreased defect density. By employing Pt-loaded MgTa2O(6-x)N(y)/TaON as a H2-evolving photocatalyst, a Z-scheme overall water splitting system with an apparent quantum efficiency (AQE) of 6.8% at 420 nm was constructed (PtO(x)-WO3 and IO3(-)/I(-) pairs were used as an O2-evolving photocatalyst and a redox mediator, respectively), the activity of which is circa 7 or 360 times of that using Pt-TaON or Pt-MgTa2O(6-x)N)y) as a H2-evolving photocatalyst, respectively. To the best of our knowledge, this is the highest AQE among the powdered Z-scheme overall water splitting systems ever reported. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermal stability of nanocomposite CrC/a-C:H thin films

International Nuclear Information System (INIS)

Gassner, G.; Mayrhofer, P.H.; Patscheider, J.; Mitterer, C.

2007-01-01

The thermal stability of low-friction Me-C/a-C:H coatings is important for their potential applications in the tool and automotive industry. Recently we showed that CrC x /a-C:H coatings prepared by unbalanced magnetron sputtering of a Cr target in Ar + CH 4 glow discharges exhibit a nanocomposite structure where metastable fcc CrC nanocrystals are encapsulated by an a-C:H phase. Here, we present the structural evolution of these nanocomposite CrC/a-C:H coatings during annealing. High-temperature X-ray diffraction in vacuum and differential scanning calorimetry (DSC) combined with thermo-gravimetric analysis in Ar atmosphere indicate decomposition of the formed metastable fcc CrC phase and subsequent formation of Cr 3 C 2 and Cr 7 C 3 and structural transformation of the a-C:H matrix phase towards higher sp 2 bonding contents at temperatures above 450 deg. C. Combined DSC and mass spectrometer analysis as well as elemental profiling after annealing in vacuum by elastic recoil detection analysis relate this transformation to the loss of bonded hydrogen at temperatures above 200 deg. C. Due to these structural changes the coefficient of friction depends on the annealing temperature of the nanocomposite a-C:H coatings and shows a minimum of ∼ 0.13 for T = 200 deg. C. The more complex tribochemical reactions, influenced by the hydrogen loss from the coating during in-situ high temperatures ball-on disc tests, result in coefficient of friction values below 0.05 for T < 120 deg. C

Nido-Carborane building-block reagents. 2. Bulky-substituent (alkyl)2C2B4H6 derivatives and (C6H5)2C2B4H6: synthesis and properties

International Nuclear Information System (INIS)

Boyter, H.A. Jr.; Grimes, R.N.

1988-01-01

The preparation and chemistry of nido-2,3-R 2 C 2 C 2 B 4 H 6 carboranes in which R is n-butyl, isopentyl, n-hexyl, and phenyl was investigated in order to further assess the steric and electronic influence of the R groups on the properties of the nido-C 2 B 4 cage, especially with respect to metal complexation at the C 2 B 3 face and metal-promoted oxidative fusion. The three dialkyl derivatives were prepared from the corresponding dialkylacetylenes via reaction with B 5 H 9 and triethylamine, but the diphenyl compound could not be prepared in this manner and was obtained instead in a thermal reaction of B 5 H 9 with diphenylacetylene in the absence of amine. All four carboranes are readily bridge-deprotonated by NaH in THF, and the anions of the dialkyl species, on treatment with FeCl 2 and air oxidation, generate the respective R 4 C 4 B 8 H 8 carborane fusion products were R = n-C 4 H 9 , i-C 5 H 11 or n-C 6 H 13 . The diphenylcarborane anion Ph 2 C 2 B 4 H 5 - did not form detectable metal complexes with Fe 2+ , Co 2+ , or Ni 2+ , and no evidence of a Ph 4 C 4 B 8 H 8 fusion product has been found. Treatment of Ph 2 C 2 B 4 H 6 with Cr(CO) 6 did not lead to metal coordination of the phenyl rings, unlike (PhCH 2 ) 2 C 2 B 4 H 6 , which had previously been shown to form mono- and bis(tricarbonylchromium) complexes. However, the reaction of Ph 2 C 2 B 4 H 5 - , CoCl 2 , and (PhPCH 2 ) 2 did give 1,1-(Ph 2 PCH 2 ) 2 -1-Cl-1,2,3-Co(Ph 2 C 2 B 4 H 4 ), the only case in which metal complexation of the diphenylcarborane was observed. 14 references, 3 figures, 3 tables

Differential cross sections for the one electron two center symmetric systems

International Nuclear Information System (INIS)

Maidagan, J.M.; Piacentini, R.D.; Rivarola, R.D.; Universidad Autonoma de Madrid

1982-01-01

We use the two-state atomic expansion with variable nuclear charge to study charge-exchange differential cross sections for symmetrical one-electron systems at intermediate energy. The nonclassical small angle diffraction scattering is discussed. Our results are compared with data for H + -H collisions. (orig.)

Differential cross sections for the one electron two center symmetric systems

Energy Technology Data Exchange (ETDEWEB)

Maidagan, J.M.; Piacentini, R.D. (Universidad Nacional de Rosario (Argentina). Dept. de Fisica); Rivarola, R.D. (Bordeaux-1 Univ., 33 - Talence (France). Lab. d' Astrophysique; Universidad Autonoma de Madrid (Spain). Dept. de Quimica Fisica y Quimica Cuantica)

1982-03-01

We use the two-state atomic expansion with variable nuclear charge to study charge-exchange differential cross sections for symmetrical one-electron systems at intermediate energy. The nonclassical small angle diffraction scattering is discussed. Our results are compared with data for H/sup +/-H collisions.

Measurement of the C / H ratio using neutrons; Mesure du rapport C / H au moyen des neutrons

Energy Technology Data Exchange (ETDEWEB)

Martinelli, P [Commissariat a l' Energie Atomique, Saclay (France).Centre d' Etudes Nucleaires; Ricci, H [Universite de Lima (Peru)

1960-07-01

A probe made up of a Ra ({alpha}, n) Be neutron source and a proportional counter filled with boron trifluoride has been used to measure the C/H ratio in hydrocarbons. The intensity of the thermal neutron flux in the neighbourhood of the detector increases with the concentration of the hydrocarbon hydrogen surrounding it. By measuring the density it is possible to deduce the C/H ratio. It is thus possible to evaluate the C/H ratio with a precision equal to that given by the {beta}-ray transmission method. The errors arising from the chemical nature of the hydrocarbon can be reduced to a minimum. This method has the advantage of allowing the measurement of the C/H ratio of hydrocarbons contained in recipients or thick steel tubing by means an independent portable apparatus. (author) [French] Une sonde constituee d'une source de neutrons Ra ({alpha}, n) Be et d'un compteur proportionnel a remplissage de trifluorure de bore a ete utilisee pour mesurer le rapport C/H dans les hydrocarbures. Le flux des neutrons thermiques au voisinage du detecteur est d'autant plus intense que la concentration en hydrogene de l'hydrocarbure qui entoure la sonde est plus elevee. Une mesure de densite permet d'en deduire le rapport C/H. On peut ainsi evaluer le rapport C/H avec une precision aussi bonne que celle que l'on obtient par transmission de rayons {beta}. Les erreurs provenant de la nature chimique de l'hydrocarbure peuvent etre minimisees. Cette methode presente l'avantage de permettre la mesure du rapport C/H d'hydrocarbures contenus dans des recipients ou des canalisations epaisses en acier a l'aide d'un appareil exterieur transportable. (auteur)

Electrooxidative Ruthenium-Catalyzed C-H/O-H Annulation by Weak O-Coordination.

Science.gov (United States)

Qiu, Youai; Tian, Cong; Massignan, Leonardo; Rogge, Torben; Ackermann, Lutz

2018-05-14

Electrocatalysis has been identified as a powerful strategy for organometallic catalysis, and yet electrocatalytic C-H activation is restricted to strongly N-coordinating directing groups. The first example of electrocatalytic C-H activation by weak O-coordination is presented, in which a versatile ruthenium(II) carboxylate catalyst enables electrooxidative C-H/O-H functionalization for alkyne annulations in the absence of metal oxidants; thereby exploiting sustainable electricity as the sole oxidant. Mechanistic insights provide strong support for a facile organometallic C-H ruthenation and an effective electrochemical reoxidation of the key ruthenium(0) intermediate. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Fast Homoepitaxial Growth of 4H-SiC Films on 4° off-Axis Substrates in a SiH4-C2H4-H2 System

International Nuclear Information System (INIS)

Liu Bin; Sun Guo-Sheng; Liu Xing-Fang; Zhang Feng; Dong Lin; Zheng Liu; Yan Guo-Guo; Liu Sheng-Bei; Zhao Wan-Shun; Wang Lei; Zeng Yi-Ping; Wang Zhan-Guo; Li Xi-Guang; Yang Fei

2013-01-01

Homoepitaxial growth of 4H-SiC epilayers is conducted in a SiH 4 -C 2 H 4 -H 2 system by low pressure hot-wall vertical chemical vapor deposition (CVD). Thick epilayers of 45 μm are achieved at a high growth rate up to 26 μm/h under an optimized growth condition, and are characterized by using a Normaski optical microscope, a scanning electronic microscope (SEM), an atomic force microscope (AFM) and an x-ray diffractometer (XRD), indicating good crystalline quality with mirror-like smooth surfaces and an rms roughness of 0.9 nm in a 5 μm × 5μm area. The dependence of the 4H-SiC growth rate on growth conditions on 4° off-axis 4H-SiC substrates and its mechanism are investigated. It is found that the H 2 flow rate could influence the surface roughness, while good surface morphologies without Si droplets and epitaxial defects such as triangular defects could be obtained by increasing temperature

Rhodium-Catalyzed C-C Bond Formation via Heteroatom-Directed C-H Bond Activation

Energy Technology Data Exchange (ETDEWEB)

Colby, Denise; Bergman, Robert; Ellman, Jonathan

2010-05-13

Once considered the 'holy grail' of organometallic chemistry, synthetically useful reactions employing C-H bond activation have increasingly been developed and applied to natural product and drug synthesis over the past decade. The ubiquity and relative low cost of hydrocarbons makes C-H bond functionalization an attractive alternative to classical C-C bond forming reactions such as cross-coupling, which require organohalides and organometallic reagents. In addition to providing an atom economical alternative to standard cross - coupling strategies, C-H bond functionalization also reduces the production of toxic by-products, thereby contributing to the growing field of reactions with decreased environmental impact. In the area of C-C bond forming reactions that proceed via a C-H activation mechanism, rhodium catalysts stand out for their functional group tolerance and wide range of synthetic utility. Over the course of the last decade, many Rh-catalyzed methods for heteroatom-directed C-H bond functionalization have been reported and will be the focus of this review. Material appearing in the literature prior to 2001 has been reviewed previously and will only be introduced as background when necessary. The synthesis of complex molecules from relatively simple precursors has long been a goal for many organic chemists. The ability to selectively functionalize a molecule with minimal pre-activation can streamline syntheses and expand the opportunities to explore the utility of complex molecules in areas ranging from the pharmaceutical industry to materials science. Indeed, the issue of selectivity is paramount in the development of all C-H bond functionalization methods. Several groups have developed elegant approaches towards achieving selectivity in molecules that possess many sterically and electronically similar C-H bonds. Many of these approaches are discussed in detail in the accompanying articles in this special issue of Chemical Reviews. One approach

Hydrogen production via thermochemical water-splitting by lithium redox reaction

International Nuclear Information System (INIS)

Nakamura, Naoya; Miyaoka, Hiroki; Ichikawa, Takayuki; Kojima, Yoshitsugu

2013-01-01

Highlights: •Hydrogen production via water-splitting by lithium redox reactions possibly proceeds below 800 °C. •Entropy control by using nonequilibrium technique successfully reduces the reaction temperature. •The operating temperature should be further reduced by optimizing the nonequilibrium condition to control the cycle. -- Abstracts: Hydrogen production via thermochemical water-splitting by lithium redox reactions was investigated as energy conversion technique. The reaction system consists of three reactions, which are hydrogen generation by the reaction of lithium and lithium hydroxide, metal separation by thermolysis of lithium oxide, and oxygen generation by hydrolysis of lithium peroxide. The hydrogen generation reaction completed at 500 °C. The metal separation reaction is thermodynamically difficult because it requires about 3400 °C in equilibrium condition. However, it was indicated from experimental results that the reaction temperature was drastically reduced to 800 °C by using nonequilibrium technique. The hydrolysis reaction was exothermic reaction, and completed by heating up to 300 °C. Therefore, it was expected that the water-splitting by lithium redox reactions was possibly operated below 800 °C under nonequilibrium condition

Spherically symmetric models with pressure: separating expansion from contraction and generalizing TOV condition

CERN Document Server

Mimoso, José Pedro; Mena, Filipe C

2010-01-01

We investigate spherically symmetric perfect fluid spacetimes and discuss the existence and stability of a dividing shell separating expanding and collapsing regions. We perform a 3+1 splitting and obtain gauge invariant conditions relating the intrinsic spatial curvature of the shells to the ADM mass and to a function of the pressure which we introduce and that generalises the Tolman-Oppenheimer-Volkoff equilibrium condition. We analyse the particular cases of the Lema\\^itre-Tolman-Bondi dust models with a cosmological constant as an example of a $\\Lambda$-CDM model and its generalization to contain a central perfect fluid core. These models provide simple, but physically interesting illustrations of our results.

Synthesis of new trihalo methylated and non-symmetrical substituted 2-(1H-pyrazolyl)-5-(1H-pyrazolylcarbonyl)pyridines

International Nuclear Information System (INIS)

Bonacorso, Helio G.; Paim, Gisele R.; Guerra, Carolina Z.; Sehnem, Ronan C.; Cechinel, Cleber A.; Porte, Liliane M. F.; Martins, Marcos A. P.; Zanatta, Nilo

2009-01-01

This paper describes the synthesis of a new series of 2-[3-alkyl(aryl/heteroaryl)-5-trifluoro(chloro)methyl-5-hydroxy-4,5-dihydro -1H-pyrazol-1-yl]-5- [3-alkyl(aryl/heteroaryl)-5-trifluoro(chloro)methyl-5-hydroxy= -4,5-dihydro-1H-pyrazol-1-yl-1-carbonyl] pyridines by the cyclocondensation reaction of 4-alkoxy-4-alkyl(aryl/heteroaryl)-1,1,1- trifluoro(chloro) -3-alken- 2-ones [CX 3 C(O)CH=CR 1 OR, where R = Me, Et; R 1 = H, Me, Ph, 4-MeOPh, 4-NO 2 Ph, 4,4'-Biphenyl, 1-Naphthyl, Fur-2-yl, Thien-2-yl and X = F, Cl] with 6-hydrazinonicotinic hydrazide hydrate. Yields of 62 to 97% were obtained when the reactions were performed in ethanol as solvent at 78 deg C for 4 hours. In a subsequent step, the dehydration reactions of 2-(5-hydroxy-1H-pyrazol-1-yl)-5-(5-hydroxy-1H?pyrazol-1-yl-1-carbonyl) pyridines were carried out in pyridine/benzene in the presence of thionyl chloride and led to the isolation of a series of 2- [3-alkyl(aryl/heteroaryl)-5-trifluoro(chloro)methyl-1H-pyrazol-1-yl]-5- [3-alkyl(aryl/heteroaryl)-5 -trifluoro(chloro)methyl-1H-pyrazol-1-yl-1-carbonyl]pyridi= nes, in 64 to 86% yields. (author)

Synthesis, characterization, vibrational spectroscopy, and factor group analysis of partially metal-doped phosphate materials

Science.gov (United States)

Sronsri, Chuchai; Boonchom, Banjong

2018-04-01

A simple precipitating method was used to synthesize effectively a partially metal-doped phosphate hydrate (Mn0.9Mg0.1HPO4·3H2O), whereas the thermal decomposition process of the above hydrate precursor was used to obtain Mn1.8Mg0.2P2O7 and LiMn0.9Mg0.1PO4 compounds under different conditions. To separate the overlapping thermal decomposition peak, a deconvolution technique was used, and the separated peak was applied to calculate the water content. The factor group splitting analysis was used to exemplify their vibrational spectra obtained from normal vibrations of HPO42-, H2O, P2O74- and PO43- functional groups. Further, the deconvoluted bending mode of water was clearly observed. Mn0.9Mg0.1HPO4·3H2O was observed in the orthorhombic crystal system with the space group of Pbca (D2h15). The formula units per unit cell were found to be eight (Z = 8), and the site symmetric type of HPO42- was observed as Cs. For the HPO42- unit, the correlation filed splitting analysis of type C3v - Cs - D2h15 was calculated and had 96 internal modes, whereas H2O in the above hydrate was symbolized as C2v - Cs - D2h15 and had 24 modes. The symbol C2v - Cs - C2h3 was used for the correlation filed splitting analysis of P2O74- in Mn1.8Mg0.2P2O7 (monoclinic, C2/m (C2h3), Z = 2, and 42 modes). Finally, the symbol Td - Cs - D2h16 was used for the correlation filed splitting analysis of PO43- in LiMn0.9Mg0.1PO4 (orthorhombic, Pnma (D2h16), Z = 4, and 36 modes).

Presheaves of symmetric tensor categories and nets of C*-algebras

OpenAIRE

Vasselli, Ezio

2012-01-01

Motivated by algebraic quantum field theory, we study presheaves of symmetric tensor categories defined over the base of a space, intended as a spacetime. Any section of a presheaf (that is, any "superselection sector", in the applications that we have in mind) defines a holonomy representation whose triviality is measured by Cheeger-Chern-Simons characteristic classes, and a non-abelian unitary cocycle defining a Lie group gerbe. We show that, given an embedding in a presheaf of full subcate...

Relationship between interlayer hydration and photocatalytic water splitting of A'1-xNaxCa2Ta3O10.nH2O (A'=K and Li)

International Nuclear Information System (INIS)

Mitsuyama, Tomohiro; Tsutsumi, Akiko; Sato, Sakiko; Ikeue, Keita; Machida, Masato

2008-01-01

Partial replacement of alkaline metals in anhydrous KCa 2 Ta 3 O 10 and LiCa 2 Ta 3 O 10 was studied to control interlayer hydration and photocatalytic activity for water splitting under UV irradiation. A' 1-x Na x Ca 2 Ta 3 O 10 .nH 2 O (A'=K and Li) samples were synthesized by ion exchange of CsCa 2 Ta 3 O 10 in mixed molten nitrates at 400 deg. C. In K 1-x Na x Ca 2 Ta 3 O 10 .nH 2 O, two phases with the orthorhombic (C222) and tetragonal (I4/mmm) structures were formed at x≤0.7 and x≥0.5, respectively. Upon replacement by Na + having a larger enthalpy of hydration (ΔH h 0 ), the interlayer hydration occurred at x≥0.3 and the hydration number (n) was increased monotonically with an increase of x. Li 1-x Na x Ca 2 Ta 3 O 10 .nH 2 O showed a similar hydration behavior, but the phase was changed from I4/mmm (x 1-x Na x Ca 2 Ta 3 O 10 .nH 2 O exhibited the activity increasing in consistent with n, whereas Li 1-x Na x Ca 2 Ta 3 O 10 .nH 2 O exhibited the activity maximum at x=0.77, where the rates of H 2 /O 2 evolution were nearly doubled compared with those for end-member compositions (x=0 and 1). - Graphical abstract: The partial substitution of Na in the interlayer of anhydrous-layered perovskite has been found as useful structural modification toward highly active hydrated photocatalysts

Higgs, Binos and Gluinos: Split Susy within Reach

Energy Technology Data Exchange (ETDEWEB)

Alves, Daniele S.M.; Izaguirre, Eder; /SLAC /Stanford U., Phys. Dept.; Wacker, Jay G.; /SLAC /Stanford U., ITP

2012-09-14

Recent results from the LHC for the Higgs boson with mass between 142 GeV {approx}< m{sub h{sup 0}} {approx}< 147 GeV points to PeV-scale Split Supersymmetry. This article explores the consequences of a Higgs mass in this range and possible discovery modes for Split Susy. Moderate lifetime gluinos, with decay lengths in the 25 {micro}m to 10 yr range, are its imminent smoking gun signature. The 7TeV LHC will be sensitive to the moderately lived gluinos and trilepton signatures from direct electroweakino production. Moreover, the dark matter abundance may be obtained from annihilation through an s-channel Higgs resonance, with the LSP almost purely bino and mass m{sub {chi}{sub 1}{sup 0}} {approx_equal} 70 GeV. The Higgs resonance region of Split Susy has visible signatures in dark matter direct and indirect detection and electric dipole moment experiments. If the anomalies go away, the majority of Split Susy parameter space will be excluded.

A bonding study of c-C5H8 adsorption on Pt(111)

International Nuclear Information System (INIS)

Simonetti, S.; Jasen, P.; Gonzalez, E.; Juan, A.; Brizuela, G.

2006-01-01

The chemisorption of cyclopentane (c-C 5 H 8 ) on Pt(111) has been studied using a qualitative band-structure calculations in the framework of tight-binding implementation with the YAeHMOP package. We modeled the metal surface by a two-dimensional slab of finite thickness with an overlayer of c-C 5 H 8 , in a (3x3) di-σ geometry. The c-C 5 H 8 molecule is attached to the surface with its C?C atoms bonded mainly with two Pt atoms while the opposite CH 2 bends towards the surface. The Pt?Pt bonds in the underlying surface and the C?C bonds of c-C 5 H 8 are weakened upon the chemisorption. A noticeable Pt-H and Pt-C interactions has been observed. We found that of Pt 5d z 2 band plays an important role in the bonding between c-C 5 H 8 and the surface, as do the Pt 6s and 6p z bands. The HOMO-LUMO bands of c-C 5 H 8 are very dispersed, indicative of a strong interaction with the metal surface

MOF-derived Co-doped nickel selenide/C electrocatalysts supported on Ni foam for overall water splitting

KAUST Repository

Ming, Fangwang; Liang, Hanfeng; Shi, Huanhuan; Xu, Xun; Mei, Gui; Wang, Zhoucheng

2016-01-01

It is of prime importance to develop dual-functional electrocatalysts with good activity for overall water splitting, which remains a great challenge. Herein, we report the synthesis of a Co-doped nickel selenide (a mixture of NiSe and NiSe)/C hybrid nanostructure supported on Ni foam using a metal-organic framework as the precursor. The resulting catalyst exhibits excellent catalytic activity toward the oxygen evolution reaction (OER), which only requires an overpotential of 275 mV to drive a current density of 30 mA cm. This overpotential is much lower than those reported for precious metal free OER catalysts. The hybrid is also capable of catalyzing the hydrogen evolution reaction (HER) efficiently. A current density of -10 mA cm can be achieved at 90 mV. In addition, such a hybrid nanostructure can achieve 10 and 30 mA cm at potentials of 1.6 and 1.71 V, respectively, along with good durability when functioning as both the cathode and the anode for overall water splitting in basic media.

MOF-derived Co-doped nickel selenide/C electrocatalysts supported on Ni foam for overall water splitting

KAUST Repository

Ming, Fangwang

2016-09-01

It is of prime importance to develop dual-functional electrocatalysts with good activity for overall water splitting, which remains a great challenge. Herein, we report the synthesis of a Co-doped nickel selenide (a mixture of NiSe and NiSe)/C hybrid nanostructure supported on Ni foam using a metal-organic framework as the precursor. The resulting catalyst exhibits excellent catalytic activity toward the oxygen evolution reaction (OER), which only requires an overpotential of 275 mV to drive a current density of 30 mA cm. This overpotential is much lower than those reported for precious metal free OER catalysts. The hybrid is also capable of catalyzing the hydrogen evolution reaction (HER) efficiently. A current density of -10 mA cm can be achieved at 90 mV. In addition, such a hybrid nanostructure can achieve 10 and 30 mA cm at potentials of 1.6 and 1.71 V, respectively, along with good durability when functioning as both the cathode and the anode for overall water splitting in basic media.

Quantum fluctuations of D5d polarons on C60 molecules

International Nuclear Information System (INIS)

Wang Chui-Lin; Wang Wenzheng; Liu Yuliang; Su Zhaobin; Yu Lu.

1994-06-01

The dynamic Jahn-Teller splitting of the six equivalent D 5d polarons due to quantum fluctuations is studied in the framework of the Bogoliubov-de Gennes formalism. The tunneling induced level splittings are determined to be 2 T 1u + 2 T 2u and 1 A g + 1 H g for C 1- 60 and C -2 60 , respectively, which should give rise to observable effects in experiments. (author). 17 refs, 2 tabs

Pd-Catalyzed Consecutive C-H Arylation Triggered Cyclotrimerization: Synthesis of Star-shaped Benzotristhiazoles and Benzotrisoxazoles.

Science.gov (United States)

Xu, Zhanqiang; Oniwa, Kazuaki; Kikuchi, Hiromasa; Bao, Ming; Yamamoto, Yoshinori; Jin, Tienan; Terada, Masahiro

2018-05-18

Star-shaped π-extended molecules comprising discotic aromatic cores and peripheral π-conjugated arms have attracted significant attention as diverse optoelectronic materials in terms of their large π-surface, tunable self-assembly, enhanced charge transport and fluorescence, and liquid crystallinity. Although many efforts have been made in construction of various aromatic discotic cores, a new class of C3-symmetric star-shaped discotic π-molecules consisting of electron-deficient benzotristhiazole and benzotrisoxazole cores remains unexplored owing to the unachievable synthetic approaches, which are expected to exhibit distinct optoelectronic properties. Herein, we report a novel and highly efficient Pd-catalyzed cyclotrimerization of the functionalized thiazoles or oxazoles for the construction of a new class of discotic molecules of benzotristhiazole and benzotrisoxazole central cores with star-shaped π-conjugated arms. The combination of Pd2(dba)3/XPhos catalyst systems with the 4-bromo-substituted thiazole enables the formation of a sufficiently stable thiazole-Pd species that participates in the subsequent C-H arylations consecutively to form the corresponding cyclic trimer products. This new class of star-shaped discotic π-extended products showed tunable energy levels and high fluorescence quantum yields that make them promising candidates in optoelectronic application. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Particulate Photocatalyst Sheets Based on Carbon Conductor Layer for Efficient Z-Scheme Pure-Water Splitting at Ambient Pressure.

Science.gov (United States)

Wang, Qian; Hisatomi, Takashi; Suzuki, Yohichi; Pan, Zhenhua; Seo, Jeongsuk; Katayama, Masao; Minegishi, Tsutomu; Nishiyama, Hiroshi; Takata, Tsuyoshi; Seki, Kazuhiko; Kudo, Akihiko; Yamada, Taro; Domen, Kazunari

2017-02-01

Development of sunlight-driven water splitting systems with high efficiency, scalability, and cost-competitiveness is a central issue for mass production of solar hydrogen as a renewable and storable energy carrier. Photocatalyst sheets comprising a particulate hydrogen evolution photocatalyst (HEP) and an oxygen evolution photocatalyst (OEP) embedded in a conductive thin film can realize efficient and scalable solar hydrogen production using Z-scheme water splitting. However, the use of expensive precious metal thin films that also promote reverse reactions is a major obstacle to developing a cost-effective process at ambient pressure. In this study, we present a standalone particulate photocatalyst sheet based on an earth-abundant, relatively inert, and conductive carbon film for efficient Z-scheme water splitting at ambient pressure. A SrTiO 3 :La,Rh/C/BiVO 4 :Mo sheet is shown to achieve unassisted pure-water (pH 6.8) splitting with a solar-to-hydrogen energy conversion efficiency (STH) of 1.2% at 331 K and 10 kPa, while retaining 80% of this efficiency at 91 kPa. The STH value of 1.0% is the highest among Z-scheme pure water splitting operating at ambient pressure. The working mechanism of the photocatalyst sheet is discussed on the basis of band diagram simulation. In addition, the photocatalyst sheet split pure water more efficiently than conventional powder suspension systems and photoelectrochemical parallel cells because H + and OH - concentration overpotentials and an IR drop between the HEP and OEP were effectively suppressed. The proposed carbon-based photocatalyst sheet, which can be used at ambient pressure, is an important alternative to (photo)electrochemical systems for practical solar hydrogen production.

Recent Developments in C-H Activation for Materials Science in the Center for Selective C-H Activation.

Science.gov (United States)

Zhang, Junxiang; Kang, Lauren J; Parker, Timothy C; Blakey, Simon B; Luscombe, Christine K; Marder, Seth R

2018-04-16

Abstract : Organic electronics is a rapidly growing field driven in large part by the synthesis of ∏-conjugated molecules and polymers. Traditional aryl cross-coupling reactions such as the Stille and Suzuki have been used extensively in the synthesis of ∏-conjugated molecules and polymers, but the synthesis of intermediates necessary for traditional cross-couplings can include multiple steps with toxic and hazardous reagents. Direct arylation through C-H bond activation has the potential to reduce the number of steps and hazards while being more atom-economical. Within the Center for Selective C-H Functionalization (CCHF), we have been developing C-H activation methodology for the synthesis of ∏-conjugated materials of interest, including direct arylation of difficult-to-functionalize electron acceptor intermediates and living polymerization of ∏-conjugated polymers through C-H activation.

Unfolding the Quantum Nature of Proton Bound Symmetric Dimers of (MeOH)2H+ and (Me2O)2H+: a Theoretical Study

Science.gov (United States)

Tan, Jake Acedera; Kuo, Jer-Lai

2014-06-01

A proton under a tug of war between two competing Lewis bases is a common motif in biological systems and proton transfer processes. Over the past decades, model compounds for such motifs can be prepared by delicate stoichiometric control of salt solutions. Unfortunately, condensed phase studies, which aims to identify the key vibrational signatures are complicated to analyze. As a result, gas-phase studies do provide promising insights on the behavior of the shared proton. This study attempts to understand the quantum nature of the shared proton under theoretical paradigms. Proton bound symmetric dimers of (MeOH)2H+ and (Me2O)2H+ are chosen as the model compounds. The simulation is performed using Density Functional Theory (DFT) at the B3LYP level with 6-311+G(d,p) as the basis set. It was found out that stretching mode of shared proton couples with several other normal modes and its corresponding oscillator strength do distribute to other normal modes. J.R. Roscioli, L.R. McCunn and M.A. Johnson. Science 2007, 316, 249 T.E. DeCoursey. Physiol. Rev., 2003, 83, 475 E.S. Stoyanov. Psys. Chem. Phys., 2000,2,1137

Mixed-strain housing for female C57BL/6, DBA/2, and BALB/c mice: validating a split-plot design that promotes refinement and reduction.

Science.gov (United States)

Walker, Michael; Fureix, Carole; Palme, Rupert; Newman, Jonathan A; Ahloy Dallaire, Jamie; Mason, Georgia

2016-01-27

Inefficient experimental designs are common in animal-based biomedical research, wasting resources and potentially leading to unreplicable results. Here we illustrate the intrinsic statistical power of split-plot designs, wherein three or more sub-units (e.g. individual subjects) differing in a variable of interest (e.g. genotype) share an experimental unit (e.g. a cage or litter) to which a treatment is applied (e.g. a drug, diet, or cage manipulation). We also empirically validate one example of such a design, mixing different mouse strains -- C57BL/6, DBA/2, and BALB/c -- within cages varying in degree of enrichment. As well as boosting statistical power, no other manipulations are needed for individual identification if co-housed strains are differentially pigmented, so also sparing mice from stressful marking procedures. The validation involved housing 240 females from weaning to 5 months of age in single- or mixed- strain trios, in cages allocated to enriched or standard treatments. Mice were screened for a range of 26 commonly-measured behavioural, physiological and haematological variables. Living in mixed-strain trios did not compromise mouse welfare (assessed via corticosterone metabolite output, stereotypic behaviour, signs of aggression, and other variables). It also did not alter the direction or magnitude of any strain- or enrichment-typical difference across the 26 measured variables, or increase variance in the data: indeed variance was significantly decreased by mixed- strain housing. Furthermore, using Monte Carlo simulations to quantify the statistical power benefits of this approach over a conventional design demonstrated that for our effect sizes, the split- plot design would require significantly fewer mice (under half in most cases) to achieve a power of 80%. Mixed-strain housing allows several strains to be tested at once, and potentially refines traditional marking practices for research mice. Furthermore, it dramatically illustrates the

Hydrogenation and Deuteration of C{sub 2}H{sub 2} and C{sub 2}H{sub 4} on Cold Grains: A Clue to the Formation Mechanism of C{sub 2}H{sub 6} with Astronomical Interest

Energy Technology Data Exchange (ETDEWEB)

Kobayashi, Hitomi; Kawakita, Hideyo [Koyama Astronomical Observatory, Kyoto Sangyo University Motoyama, Kamigamo, Kita-ku, Kyoto 603-8555 (Japan); Hidaka, Hiroshi; Hama, Tetsuya; Watanabe, Naoki [Institute of Low Temperature Science, Hokkaido University N19-W8, Kita-ku, Sapporo, Hokkaido 060-0819 (Japan); Lamberts, Thanja; Kästner, Johannes, E-mail: h_kobayashi@kyoto-nijikoubou.com [Institute for Theoretical Chemistry, University of Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart (Germany)

2017-03-10

We quantitatively investigated the hydrogen addition reactions of acetylene (C{sub 2}H{sub 2}) and ethylene (C{sub 2}H{sub 4}) on amorphous solid water (ASW) at 10 and 20 K relevant to the formation of ethane (C{sub 2}H{sub 6}) on interstellar icy grains. We found that the ASW surface enhances the reaction rates for C{sub 2}H{sub 2} and C{sub 2}H{sub 4} by approximately a factor of 2 compared to those on the pure-solid C{sub 2}H{sub 2} and C{sub 2}H{sub 4} at 10 K, probably due to an increase in the sticking coefficient and adsorption energy of the H atoms on ASW. In contrast to the previous proposal that the hydrogenation rate of C{sub 2}H{sub 4} is orders of magnitude larger than that of C{sub 2}H{sub 2}, the present results show that the difference in hydrogenation rates of C{sub 2}H{sub 2} and C{sub 2}H{sub 4} is only within a factor of 3 on both the surfaces of pure solids and ASW. In addition, we found the small kinetic isotope effect for hydrogenation/deuteration of C{sub 2}H{sub 2} and C{sub 2}H{sub 4} at 10 K, despite the requirement of quantum tunneling. At 20 K, the reaction rate of deuteration becomes even larger than that of hydrogenation. These unusual isotope effects might originate from a slightly larger number density of D atoms than H atoms on ASW at 20 K. The hydrogenation of C{sub 2}H{sub 2} is four times faster than CO hydrogenation and can produce C{sub 2}H{sub 6} efficiently through C{sub 2}H{sub 4} even in the environment of a dark molecular cloud.

Symmetric vectors and algebraic classification

International Nuclear Information System (INIS)

Leibowitz, E.

1980-01-01

The concept of symmetric vector field in Riemannian manifolds, which arises in the study of relativistic cosmological models, is analyzed. Symmetric vectors are tied up with the algebraic properties of the manifold curvature. A procedure for generating a congruence of symmetric fields out of a given pair is outlined. The case of a three-dimensional manifold of constant curvature (''isotropic universe'') is studied in detail, with all its symmetric vector fields being explicitly constructed

Densities, viscosities, and refractive indexes for {C2H5CO2(CH2)2CH3+C6H13OH+C6H6} at T=308.15 K

International Nuclear Information System (INIS)

Casas, Herminio; Garcia-Garabal, Sandra; Segade, Luisa; Cabeza, Oscar.; Franjo, Carlos; Jimenez, Eulogio

2003-01-01

In this work we present densities, kinematic viscosities, and refractive indexes of the ternary system {C 2 H 5 CO 2 (CH 2 ) 2 CH 3 +C 6 H 13 OH+C 6 H 6 } and the corresponding binary mixtures {C 2 H 5 CO 2 (CH 2 ) 2 CH 3 +C 6 H 6 }, {C 2 H 5 CO 2 (CH 2 ) 2 CH 3 +C 6 H 13 OH}, and {C 6 H 13 OH+C 6 H 6 }. All data have been measured at T=308.15 K and atmospheric pressure over the whole composition range. The excess molar volumes, dynamic viscosity deviations, and changes of the refractive index on mixing were calculated from experimental measurements. The results for binary mixtures were fitted to a polynomial relationship to estimate the coefficients and standard deviations. The Cibulka equation has been used to correlate the experimental values of ternary mixtures. Also, the experimental values obtained for the ternary mixture were used to test the empirical methods of Kohler, Jacob and Fitzner, Colinet, Tsao and Smith, Toop, Scatchard et al., and Hillert. These methods predict excess properties of the ternary mixtures from those of the involved binary mixtures. The results obtained for dynamic viscosities of the binary mixtures were used to test the semi-empirical relations of Grunberg-Nissan, McAllister, Auslaender, and Teja-Rice. Finally, the experimental refractive indexes were compared with the predicted results for the Lorentz-Lorenz, Gladstone-Dale, Wiener, Heller, and Arago-Biot equations. In all cases, we give the standard deviation between the experimental data and that calculated with the above named relations

Solution Structure of a Novel C2-Symmetrical Bifunctional Bicyclic Inhibitor Based on SFTI-1

International Nuclear Information System (INIS)

Jaulent, Agnes M.; Brauer, Arnd B. E.; Matthews, Stephen J.; Leatherbarrow, Robin J.

2005-01-01

A novel bifunctional bicyclic inhibitor has been created that combines features both from the Bowman-Birk inhibitor (BBI) proteins, which have two distinct inhibitory sites, and from sunflower trypsin inhibitor-1 (SFTI-1), which has a compact bicyclic structure. The inhibitor was designed by fusing together a pair of reactive loops based on a sequence derived from SFTI-1 to create a backbone-cyclized disulfide-bridged 16-mer peptide. This peptide has two symmetrically spaced trypsin binding sites. Its synthesis and biological activity have been reported in a previous communication [Jaulent and Leatherbarrow, 2004, PEDS 17, 681]. In the present study we have examined the three-dimensional structure of the molecule. We find that the new inhibitor, which has a symmetrical 8-mer half-cystine CTKSIPP'I' motif repeated through a C 2 symmetry axis also shows a complete symmetry in its three-dimensional structure. Each of the two loops adopts the expected canonical conformation common to all BBIs as well as SFTI-1. We also find that the inhibitor displays a strong and unique structural identity, with a notable lack of minor conformational isomers that characterise most reactive site loop mimics examined to date as well as SFTI-1. This suggests that the presence of the additional cyclic loop acts to restrict conformational mobility and that the deliberate introduction of cyclic symmetry may offer a general route to locking the conformation of β-hairpin structures

Topology on the spectrum of the algebra of entire symmetric functions of bounded type on the complex $L_\\infty$

Directory of Open Access Journals (Sweden)

T. V. Vasylyshyn

2017-07-01

Full Text Available It is known that the so-called elementary symmetric polynomials $R_n(x = \\int_{[0,1]}(x(t^n\\,dt$ form an algebraic basis in the algebra of all symmetric continuous polynomials on the complex Banach space $L_\\infty,$ which is dense in the Fr\\'{e}chet algebra $H_{bs}(L_\\infty$ of all entire symmetric functions of bounded  type on $L_\\infty.$ Consequently, every continuous homomorphism $\\varphi: H_{bs}(L_\\infty \\to \\mathbb{C}$ is uniquely determined by the sequence $\\{\\varphi(R_n\\}_{n=1}^\\infty.$ By the continuity of the homomorphism $\\varphi,$ the sequence $\\{\\sqrt[n]{|\\varphi(R_n|}\\}_{n=1}^\\infty$ is bounded. On the other hand, for every sequence $\\{\\xi_n\\}_{n=1}^\\infty \\subset \\mathbb{C},$ such that the sequence $\\{\\sqrt[n]{|\\xi_n|}\\}_{n=1}^\\infty$ is bounded,  there exists  $x_\\xi \\in L_\\infty$ such that $R_n(x_\\xi = \\xi_n$ for every $n \\in \\mathbb{N}.$ Therefore, for the point-evaluation functional $\\delta_{x_\\xi}$ we have $\\delta_{x_\\xi}(R_n = \\xi_n$ for every $n \\in \\mathbb{N}.$ Thus, every continuous complex-valued homomorphism of $H_{bs}(L_\\infty$ is a point-evaluation functional at some point of $L_\\infty.$ Note that such a point is not unique. We can consider an equivalence relation on $L_\\infty,$ defined by $x\\sim y \\Leftrightarrow \\delta_x = \\delta_y.$ The spectrum (the set of all continuous complex-valued homomorphisms $M_{bs}$ of the algebra $H_{bs}(L_\\infty$ is one-to-one with the quotient set $L_\\infty/_\\sim.$ Consequently, $M_{bs}$ can be endowed with the quotient topology. On the other hand, it is naturally to identify $M_{bs}$ with the set of all sequences $\\{\\xi_n\\}_{n=1}^\\infty \\subset \\mathbb{C}$ such that the sequence $\\{\\sqrt[n]{|\\xi_n|}\\}_{n=1}^\\infty$ is bounded.We show that the quotient topology is Hausdorffand that $M_{bs}$ with the operation of coordinate-wise addition of sequences forms an abelian topological group.

Representations of locally symmetric spaces

International Nuclear Information System (INIS)

Rahman, M.S.

1995-09-01

Locally symmetric spaces in reference to globally and Hermitian symmetric Riemannian spaces are studied. Some relations between locally and globally symmetric spaces are exhibited. A lucid account of results on relevant spaces, motivated by fundamental problems, are formulated as theorems and propositions. (author). 10 refs

Ultra-wideband circular-polarization converter with micro-split Jerusalem-cross metasurfaces

Science.gov (United States)

Gao, Xi; Yu, Xing-Yang; Cao, Wei-Ping; Jiang, Yan-Nan; Yu, Xin-Hua

2016-12-01

An ultrathin micro-split Jerusalem-cross metasurface is proposed in this paper, which can efficiently convert the linear polarization of electromagnetic (EM) wave into the circular polarization in ultra-wideband. By symmetrically employing two micro-splits on the horizontal arm (in the x direction) of the Jerusalem-cross structure, the bandwidth of the proposed device is significantly extended. Both simulated and experimental results show that the proposed metasurface is able to convert linearly polarized waves into circularly polarized waves in a frequency range from 12.4 GHz to 21 GHz, with an axis ratio better than 1 dB. The simulated results also show that such a broadband and high-performance are maintained over a wide range of incident angle. The presented polarization converter can be used in a number of areas, such as spectroscopy and wireless communications. Project supported by the National Natural Science Foundation of China (Grant Nos. 61461016 and 61661012), the Natural Science Foundation of Guangxi Zhuang Autonomous Region, China (Grant Nos. 2014GXNSFAA118366, 2014GXNSFAA118283, and 2015jjBB7002), and the Innovation Project of Graduate Education of Guilin University of Electronic Technology, China (Grant No. 2016YJCX82).

Stress analysis and optimization of Nd:YAG pulsed laser processing of notches for fracture splitting of a C70S6 connecting rod

International Nuclear Information System (INIS)

Kou, Shuqing; Gao, Yan; Zhao, Yong; Lin, Baojun

2017-01-01

The pulsed laser pre-processing of a notch as the fracture initiation source for the splitting process is the key mechanism of an advanced fracture splitting technology for C70S6 connecting rods. This study investigated the stress field of Nd:YAG pulsed laser grooving, which affects the rapid fracture initiation at the notch root and the controlled crack extension in the critical fracture splitting quality, to improve manufacturing quality. Thermal elastic-plastic incremental theory was applied to build the finite element analysis model of the stress field of pulsed laser grooving for fracture splitting based on the Rotary-Gauss body heat source. The corresponding numerical simulation of the stress field was conducted. The changes and distributions of the stress during pulsed laser grooving were examined, the influence rule of the primary technological parameters on the residual stress was analyzed, and the analysis results were validated by the corresponding cutting experiment. Results showed that the residual stress distribution was concentrated in the Heat-affected zone (HAZ) near the fracture splitting notch, which would cause micro-cracks in the HAZ. The stress state of the notch root in the fracture initiation direction was tensile stress, which was beneficial to the fracture initiation and the crack rapid extension in the subsequent fracture splitting process. However, the uneven distribution of the stress could lead to fracture splitting defects, and thus the residual stress should be lowered to a reasonable range. Decreasing the laser pulse power, increasing the processing speed, and lowering the pulse width can lower the residual stress. Along with the actual production, the reasonable main technological parameters were obtained.

Stress analysis and optimization of Nd:YAG pulsed laser processing of notches for fracture splitting of a C70S6 connecting rod

Energy Technology Data Exchange (ETDEWEB)

Kou, Shuqing; Gao, Yan; Zhao, Yong; Lin, Baojun [Jilin University, Changchun (China)

2017-05-15

The pulsed laser pre-processing of a notch as the fracture initiation source for the splitting process is the key mechanism of an advanced fracture splitting technology for C70S6 connecting rods. This study investigated the stress field of Nd:YAG pulsed laser grooving, which affects the rapid fracture initiation at the notch root and the controlled crack extension in the critical fracture splitting quality, to improve manufacturing quality. Thermal elastic-plastic incremental theory was applied to build the finite element analysis model of the stress field of pulsed laser grooving for fracture splitting based on the Rotary-Gauss body heat source. The corresponding numerical simulation of the stress field was conducted. The changes and distributions of the stress during pulsed laser grooving were examined, the influence rule of the primary technological parameters on the residual stress was analyzed, and the analysis results were validated by the corresponding cutting experiment. Results showed that the residual stress distribution was concentrated in the Heat-affected zone (HAZ) near the fracture splitting notch, which would cause micro-cracks in the HAZ. The stress state of the notch root in the fracture initiation direction was tensile stress, which was beneficial to the fracture initiation and the crack rapid extension in the subsequent fracture splitting process. However, the uneven distribution of the stress could lead to fracture splitting defects, and thus the residual stress should be lowered to a reasonable range. Decreasing the laser pulse power, increasing the processing speed, and lowering the pulse width can lower the residual stress. Along with the actual production, the reasonable main technological parameters were obtained.

Cuspidal discrete series for semisimple symmetric spaces

DEFF Research Database (Denmark)

Andersen, Nils Byrial; Flensted-Jensen, Mogens; Schlichtkrull, Henrik

2012-01-01

We propose a notion of cusp forms on semisimple symmetric spaces. We then study the real hyperbolic spaces in detail, and show that there exists both cuspidal and non-cuspidal discrete series. In particular, we show that all the spherical discrete series are non-cuspidal. (C) 2012 Elsevier Inc. All...

Algebraic techniques for diagonalization of a split quaternion matrix in split quaternionic mechanics

International Nuclear Information System (INIS)

Jiang, Tongsong; Jiang, Ziwu; Zhang, Zhaozhong

2015-01-01

In the study of the relation between complexified classical and non-Hermitian quantum mechanics, physicists found that there are links to quaternionic and split quaternionic mechanics, and this leads to the possibility of employing algebraic techniques of split quaternions to tackle some problems in complexified classical and quantum mechanics. This paper, by means of real representation of a split quaternion matrix, studies the problem of diagonalization of a split quaternion matrix and gives algebraic techniques for diagonalization of split quaternion matrices in split quaternionic mechanics

Rietveld refinement of the structures of 1.0 C-S-H and 1.5 C-S-H

KAUST Repository

Battocchio, Francesco

2012-11-01

Low-Q region Rietveld analyses were performed on C-S-H synchrotron XRD patterns, using the software MAUD. Two different crystal structures of tobermorite 11 Å were used as a starting model: monoclinic ordered Merlino tobermorite, and orthorhombic disordered Hamid tobermorite. Structural modifications were required to adapt the structures to the chemical composition and the different interlayer spacing of the C-S-H samples. Refinement of atomic positions was done by using special constraints called fragments that maintain interatomic distances and orientations within atomic polyhedra. Anisotropic crystallite size refinement showed that C-S-H has a nanocrystalline disordered structure with a preferred direction of elongation of the nanocrystallites in the plane of the Ca interlayer. The quality of the fit showed that the monoclinic structure gives a more adequate representation of C-S-H, whereas the disordered orthorhombic structure can be considered a more realistic model if the lack of long-range order of the silica chain along the c-direction is assumed. © 2012 Elsevier Ltd. All rights reserved.

Introducing inducible fluorescent split cholesterol oxidase to mammalian cells.

Science.gov (United States)

Chernov, Konstantin G; Neuvonen, Maarit; Brock, Ivonne; Ikonen, Elina; Verkhusha, Vladislav V

2017-05-26

Cholesterol oxidase (COase) is a bacterial enzyme catalyzing the first step in the biodegradation of cholesterol. COase is an important biotechnological tool for clinical diagnostics and production of steroid drugs and insecticides. It is also used for tracking intracellular cholesterol; however, its utility is limited by the lack of an efficient temporal control of its activity. To overcome this we have developed a regulatable fragment complementation system for COase cloned from Chromobacterium sp. The enzyme was split into two moieties that were fused to FKBP (FK506-binding protein) and FRB (rapamycin-binding domain) pair and split GFP fragments. The addition of rapamycin reconstituted a fluorescent enzyme, termed split GFP-COase, the fluorescence level of which correlated with its oxidation activity. A rapid decrease of cellular cholesterol induced by intracellular expression of the split GFP-COase promoted the dissociation of a cholesterol biosensor D4H from the plasma membrane. The process was reversible as upon rapamycin removal, the split GFP-COase fluorescence was lost, and cellular cholesterol levels returned to normal. These data demonstrate that the split GFP-COase provides a novel tool to manipulate cholesterol in mammalian cells. © 2017 by The American Society for Biochemistry and Molecular Biology, Inc.

Tunable Robust pacs-MOFs: a Platform for Systematic Enhancement of the C2H2 Uptake and C2H2/C2H4 Separation Performance.

Science.gov (United States)

Chen, Di-Ming; Sun, Chun-Xiao; Zhang, Nan-Nan; Si, Huan-Huan; Liu, Chun-Sen; Du, Miao

2018-03-05

As a modulatable class of porous crystalline materials, metal-organic frameworks (MOFs) have gained intensive research attention in the domain of gas storage and separation. In this study, we report on the synthesis and gas adsorption properties of two robust MOFs with the general formula [Co 3 (μ 3 -OH)(cpt) 3 Co 3 (μ 3 -OH)(L) 3 (H 2 O) 9 ](NO 3 ) 4 (guests) n [L = 3-amino-1,2,4-triazole (1) and 3,5-diamino-1,2,4-triazole (2); Hcpt = 4-(4-carboxyphenyl)-1,2,4-triazole], which show the same pacs topology. Both MOFs are isostructural to each other and show MIL-88-type frameworks whose pore spaces are partitioned by different functionlized trinuclear 1,2,4-triazolate-based clusters. The similar framework components with different amounts of functional groups make them an ideal platform to permit a systematic gas sorption/separation study to evaluate the effects of distinctive parameters on the C 2 H 2 uptake and separation performance. Because of the presence of additional amido groups, the MOF 2 equipped with a datz-based cluster (Hdatz = 3,5-diamino-1,2,4-triazole) shows a much improved C 2 H 2 uptake capacity and separation performance over that of the MOF 1 equipped with atz-based clusters (Hatz = 3-amino-1,2,4-triazole), although the surface area of the MOF 1 is almost twice than that of the MOF 2. Moreover, the high density of open metal sites, abundant free amido groups, and charged framework give the MOF 2 an excellent C 2 H 2 separation performance, with ideal adsorbed solution theory selectivity values reaching up to 11.5 and 13 for C 2 H 2 /C 2 H 4 (1:99) and C 2 H 2 /CO 2 (50:50) at 298 K and 1 bar, showing potential for use in natural gas purification.

The principal series for a reductive symmetric space, II. Eisenstein integrals.

NARCIS (Netherlands)

Ban, E.P. van den

1991-01-01

In this paper we develop a theory of Eisenstein integrals related to the principal series for a reductive symmetric space G=H: Here G is a real reductive group of Harish-Chandra's class, ? an involution of G and H an open subgroup of the group G ? of xed points for ?: The group G itself is a

Double Z-scheme ZnO/ZnS/g-C3N4 ternary structure for efficient photocatalytic H2 production

Science.gov (United States)

Dong, Zhifang; Wu, Yan; Thirugnanam, Natarajan; Li, Gonglin

2018-02-01

In the present work, a novel ZnO/ZnS/g-C3N4 ternary nanocomposite with double Z-scheme heterojunction has been designed via a two-step facile chemical conversion route. The spherical ZnS nanoparticles were uniformly loaded onto ZnO nanoflowers surface. And then the ZnO/ZnS nanocomposite was further hybridized with g-C3N4 nanosheets. Ternary ZnO/ZnS/g-C3N4 nanocomposite displays the largest specific surface area (about 76.2 m2/g), which provides plentiful activated sites for photocatalytic reaction. Furthermore, the ternary material exhibits the highest methylene blue photodegradation rate of about 0.0218 min-1 and the optimum photocatalytic H2 production (1205 μmol/g) over water splitting at 4 h under solar light irradiation. Moreover, it showed the highest photocurrent effect and the minimum charge-transfer resistance. These results implied that the higher photoactivity of ZnO/ZnS/g-C3N4 nanocomposite could be attributed to the multi-steps charge transfer and effective electron-hole separation in the double Z-scheme system.

Bandgap engineering and charge separation in two-dimensional GaS-based van der Waals heterostructures for photocatalytic water splitting

Science.gov (United States)

Wang, Biao; Kuang, Anlong; Luo, Xukai; Wang, Guangzhao; Yuan, Hongkuan; Chen, Hong

2018-05-01

Two-dimensional (2D) gallium sulfide (GaS), hexagonal boron nitride (h-BN) and graphitic carbon nitride (g-C3N4) have been fabricated and expected to be promising photocatalysts under ultraviolet irradiation. Here, we employ hybrid density functional calculations to explore the potential of the 2D GaS-based heterojunctions GaS/h-BN (g-C3N4) for the design of efficient water redox photocatalysts. Both heterostructures can be formed via van der Waals (vdW) interaction and are direct bandgap semiconductors, whose bandgaps are reduced comparing with isolated GaS, h-BN or g-C3N4 monolayers and whose bandedges straddle water redox potentials. Furthermore, the optical absorption of GaS/h-BN (g-C3N4) heterostructures is observably enhanced in the ultraviolet-visible (UV-vis) light range. The electron-hole pairs in GaS/h-BN (g-C3N4) heterostructures are completely separated from different layers. In addition, the in-plane biaxial strain can effectively modulate the electronic properties of GaS/h-BN (g-C3N4) heterostructures. Thus the GaS/h-BN (g-C3N4) heterostructures are anticipated to be promising candidates for photocatalytic water splitting to produce hydrogen.

Continuous symmetric reductions of the Adler-Bobenko-Suris equations

International Nuclear Information System (INIS)

Tsoubelis, D; Xenitidis, P

2009-01-01

Continuously symmetric solutions of the Adler-Bobenko-Suris class of discrete integrable equations are presented. Initially defined by their invariance under the action of both of the extended three-point generalized symmetries admitted by the corresponding equations, these solutions are shown to be determined by an integrable system of partial differential equations. The connection of this system to the Nijhoff-Hone-Joshi 'generating partial differential equations' is established and an auto-Baecklund transformation and a Lax pair for it are constructed. Applied to the H1 and Q1 δ=0 members of the Adler-Bobenko-Suris family, the method of continuously symmetric reductions yields explicit solutions determined by the Painleve trancendents

Disease: H01579 [KEGG MEDICUS

Lifescience Database Archive (English)

Full Text Available H01579 Congenital symmetric circumferential skin creases; Kunze-Riehm syndrome; Michelin tire baby... syndrome Congenital symmetric circumferential skin creases, also known as Michelin tire baby

The influence of split doses of γ-radiation on human erythrocytes

International Nuclear Information System (INIS)

Koziczak, R.; Gonciarz, M.; Krokosz, A.; Szweda-Lewandowska, Z.

2003-01-01

Human erythrocyte suspensions in an isotonic Na-phosphate buffer, pH 7.4, of hematocrit of 2% were exposed under air to gamma radiation at a dose rate of 2.2 kGy. Erythrocytes were irradiated with single doses, and identical doses split into two fractions with an interval time of 3.5 h between following exposures. The obtained results indicated that the irradiation of enucleated human erythrocytes with split doses caused a reduction of hemolysis (2.4 times), a decrease in the level of damage to membrane lipids and the contents of MetHb, compared with identical single doses. However, the splitting of radiation doses did not change the level of damage to the membrane proteins, as was estimated with a maleimide spin label. The obtained results suggest that a decrease in the level of damage to lipids was related to a decrease in hemolysis. (author)

Solar energy conversion by photocatalytic overall water splitting

KAUST Repository

Takanabe, Kazuhiro

2015-01-01

to reduce capital cost. Overall water splitting (OWS) by powder-form photocatalysts directly produces H2 as a chemical energy in a single reactor, which does not require any complicated parabolic mirrors and electronic devices. Because of its simplicity

Polarization Insensitivity in Double-Split Ring and Triple-Split Ring Terahertz Resonators

International Nuclear Information System (INIS)

Wu Qian-Nan; Lan Feng; Tang Xiao-Pin; Yang Zi-Qiang

2015-01-01

A modified double-split ring resonator and a modified triple-split ring resonator, which offer polarization-insensitive performance, are investigated, designed and fabricated. By displacing the two gaps of the conventional double-split ring resonator away from the center, the second resonant frequency for the 0° polarized wave and the resonant frequency for the 90° polarized wave become increasingly close to each other until they are finally identical. Theoretical and experimental results show that the modified double-split ring resonator and the modified triple-split ring resonator are insensitive to different polarized waves and show strong resonant frequency dips near 433 and 444 GHz, respectively. The results of this work suggest new opportunities for the investigation and design of polarization-dependent terahertz devices based on split ring resonators. (paper)

Protein trans-splicing of multiple atypical split inteins engineered from natural inteins.

Directory of Open Access Journals (Sweden)

Ying Lin

Full Text Available Protein trans-splicing by split inteins has many uses in protein production and research. Splicing proteins with synthetic peptides, which employs atypical split inteins, is particularly useful for site-specific protein modifications and labeling, because the synthetic peptide can be made to contain a variety of unnatural amino acids and chemical modifications. For this purpose, atypical split inteins need to be engineered to have a small N-intein or C-intein fragment that can be more easily included in a synthetic peptide that also contains a small extein to be trans-spliced onto target proteins. Here we have successfully engineered multiple atypical split inteins capable of protein trans-splicing, by modifying and testing more than a dozen natural inteins. These included both S1 split inteins having a very small (11-12 aa N-intein fragment and S11 split inteins having a very small (6 aa C-intein fragment. Four of the new S1 and S11 split inteins showed high efficiencies (85-100% of protein trans-splicing both in E. coli cells and in vitro. Under in vitro conditions, they exhibited reaction rate constants ranging from ~1.7 × 10(-4 s(-1 to ~3.8 × 10(-4 s(-1, which are comparable to or higher than those of previously reported atypical split inteins. These findings should facilitate a more general use of trans-splicing between proteins and synthetic peptides, by expanding the availability of different atypical split inteins. They also have implications on understanding the structure-function relationship of atypical split inteins, particularly in terms of intein fragment complementation.

Dual formulation of covariant nonlinear duality-symmetric action of kappa-symmetric D3-brane

Science.gov (United States)

Vanichchapongjaroen, Pichet

2018-02-01

We study the construction of covariant nonlinear duality-symmetric actions in dual formulation. Essentially, the construction is the PST-covariantisation and nonlinearisation of Zwanziger action. The covariantisation made use of three auxiliary scalar fields. Apart from these, the construction proceed in a similar way to that of the standard formulation. For example, the theories can be extended to include interactions with external fields, and that the theories possess two local PST symmetries. We then explicitly demonstrate the construction of covariant nonlinear duality-symmetric actions in dual formulation of DBI theory, and D3-brane. For each of these theories, the twisted selfduality condition obtained from duality-symmetric actions are explicitly shown to match with the duality relation between field strength and its dual from the one-potential actions. Their on-shell actions between the duality-symmetric and the one-potential versions are also shown to match. We also explicitly prove kappa-symmetry of the covariant nonlinear duality-symmetric D3-brane action in dual formulation.

Thermoelectric properties of the 3C, 2H, 4H, and 6H polytypes of the wide-band-gap semiconductors SiC, GaN, and ZnO

Directory of Open Access Journals (Sweden)

Zheng Huang

2015-09-01

Full Text Available We have investigated the thermoelectric properties of the 3C, 2H, 4H, and 6H polytypes of the wide-band-gap(n-type semiconductors SiC, GaN, and ZnO based on first-principles calculations and Boltzmann transport theory. Our results show that the thermoelectric performance increases from 3C to 6H, 4H, and 2H structures with an increase of hexagonality for SiC. However, for GaN and ZnO, their power factors show a very weak dependence on the polytype. Detailed analysis of the thermoelectric properties with respect to temperature and carrier concentration of 4H-SiC, 2H-GaN, and 2H-ZnO shows that the figure of merit of these three compounds increases with temperature, indicating the promising potential applications of these thermoelectric materials at high temperature. The significant difference of the polytype-dependent thermoelectric properties among SiC, GaN, and ZnO might be related to the competition between covalency and ionicity in these semiconductors. Our calculations may provide a new way to enhance the thermoelectric properties of wide-band-gap semiconductors through atomic structure design, especially hexagonality design for SiC.

Um estudo teórico de propriedades moleculares em complexos de hidrogênio trimoleculares C2H4···2HF, C2H2···2HF e C3h6···2HF A theoretical study of molecular properties of C2H4···2HF, C2H2···2HF AND C3H6···2HF trimolecular hydrogen-bonded complexes

Directory of Open Access Journals (Sweden)

Boaz G. Oliveira

2008-01-01

Full Text Available We present a theoretical study of molecular properties in C2H4···2HF, C2H2···2HF and C3H6···2HF trimolecular hydrogen-bonded complexes. From B3LYP/6-311++G(d,p calculations, the most important structural deformations are related to the C=C (C2H4, C≡C (C2H2, C-C (C3H6 and HF bond lengths. According to the Bader's atoms in molecules and CHELPG calculations, it was identified a tertiary interaction between the fluorine atom of the second hydrofluoric acid molecule and hydrogen atoms of the ethylene and acetylene within the C2H4···2HF and C2H2···2HF complexes, respectively. Additionally, the evaluation of the infrared spectrum characterized the new vibrational modes and bathochromic effect of the HF molecules.

The symmetric extendibility of quantum states

International Nuclear Information System (INIS)

Nowakowski, Marcin L

2016-01-01

Studies on the symmetric extendibility of quantum states have become particularly important in the context of the analysis of one-way quantum measures of entanglement, and the distillability and security of quantum protocols. In this paper we analyze composite systems containing a symmetric extendible part, with particular attention devoted to the one-way security of such systems. Further, we introduce a new one-way entanglement monotone based on the best symmetric approximation of a quantum state and the extendible number of a quantum state. We underpin these results with geometric observations about the structures of multi-party settings which posses substantial symmetric extendible components in their subspaces. The impossibility of reducing the maximal symmetric extendibility by means of the one-way local operations and classical communication method is pointed out on multiple copies. Finally, we state a conjecture linking symmetric extendibility with the one-way distillability and security of all quantum states, analyzing the behavior of a private key in the neighborhood of symmetric extendible states. (paper)

A stable and high-order accurate discontinuous Galerkin based splitting method for the incompressible Navier-Stokes equations

Science.gov (United States)

Piatkowski, Marian; Müthing, Steffen; Bastian, Peter

2018-03-01

In this paper we consider discontinuous Galerkin (DG) methods for the incompressible Navier-Stokes equations in the framework of projection methods. In particular we employ symmetric interior penalty DG methods within the second-order rotational incremental pressure correction scheme. The major focus of the paper is threefold: i) We propose a modified upwind scheme based on the Vijayasundaram numerical flux that has favourable properties in the context of DG. ii) We present a novel postprocessing technique in the Helmholtz projection step based on H (div) reconstruction of the pressure correction that is computed locally, is a projection in the discrete setting and ensures that the projected velocity satisfies the discrete continuity equation exactly. As a consequence it also provides local mass conservation of the projected velocity. iii) Numerical results demonstrate the properties of the scheme for different polynomial degrees applied to two-dimensional problems with known solution as well as large-scale three-dimensional problems. In particular we address second-order convergence in time of the splitting scheme as well as its long-time stability.

Advanced TiC/a-C : H nanocomposite coatings deposited by magnetron sputtering

NARCIS (Netherlands)

Pei, Y.T.; Galvan, D.; Hosson, J.Th.M. De; Strondl, C.

2006-01-01

TiC/a-C:H nanocomposite coatings have been deposited by magnetron Sputtering. They consist of 2-5 nm TiC nanocrystallites embedded in the amorphous hydrocarbon (a-C:H) matrix. A transition from a Columnar to a glassy microstructure has been observed in the nanocomposite coatings with increasing

Carbonyl Activation by Borane Lewis Acid Complexation: Transition States of H2 Splitting at the Activated Carbonyl Carbon Atom in a Lewis Basic Solvent and the Proton-Transfer Dynamics of the Boroalkoxide Intermediate.

Science.gov (United States)

Heshmat, Mojgan; Privalov, Timofei

2017-07-06

By using transition-state (TS) calculations, we examined how Lewis acid (LA) complexation activates carbonyl compounds in the context of hydrogenation of carbonyl compounds by H 2 in Lewis basic (ethereal) solvents containing borane LAs of the type (C 6 F 5 ) 3 B. According to our calculations, LA complexation does not activate a ketone sufficiently enough for the direct addition of H 2 to the O=C unsaturated bond; but, calculations indicate a possibly facile heterolytic cleavage of H 2 at the activated and thus sufficiently Lewis acidic carbonyl carbon atom with the assistance of the Lewis basic solvent (i.e., 1,4-dioxane or THF). For the solvent-assisted H 2 splitting at the carbonyl carbon atom of (C 6 F 5 ) 3 B adducts with different ketones, a number of TSs are computed and the obtained results are related to insights from experiment. By using the Born-Oppenheimer molecular dynamics with the DFT for electronic structure calculations, the evolution of the (C 6 F 5 ) 3 B-alkoxide ionic intermediate and the proton transfer to the alkoxide oxygen atom were investigated. The results indicate a plausible hydrogenation mechanism with a LA, that is, (C 6 F 5 ) 3 B, as a catalyst, namely, 1) the step of H 2 cleavage that involves a Lewis basic solvent molecule plus the carbonyl carbon atom of thermodynamically stable and experimentally identifiable (C 6 F 5 ) 3 B-ketone adducts in which (C 6 F 5 ) 3 B is the "Lewis acid promoter", 2) the transfer of the solvent-bound proton to the oxygen atom of the (C 6 F 5 ) 3 B-alkoxide intermediate giving the (C 6 F 5 ) 3 B-alcohol adduct, and 3) the S N 2-style displacement of the alcohol by a ketone or a Lewis basic solvent molecule. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Role of Met80 and Tyr67 in the low-pH conformational equilibria of cytochrome c.

Science.gov (United States)

Battistuzzi, Gianantonio; Bortolotti, Carlo Augusto; Bellei, Marzia; Di Rocco, Giulia; Salewski, Johannes; Hildebrandt, Peter; Sola, Marco

2012-07-31

The low-pH conformational equilibria of ferric yeast iso-1 cytochrome c (ycc) and its M80A, M80A/Y67H, and M80A/Y67A variants were studied from pH 7 to 2 at low ionic strength through electronic absorption, magnetic circular dichroism, and resonance Raman spectroscopies. For wild-type ycc, the protein structure, axial heme ligands, and spin state of the iron atom convert from the native folded His/Met low-spin (LS) form to a molten globule His/H(2)O high-spin (HS) form and a totally unfolded bis-aquo HS state, in a single cooperative transition with an apparent pK(a) of ~3.0. An analogous cooperative transition occurs for the M80A and M80A/Y67H variants. This is preceded by protonation of heme propionate-7, with a pK(a) of ~4.2, and by an equilibrium between a His/OH(-)-ligated LS and a His/H(2)O-ligated HS conformer, with a pK(a) of ~5.9. In the M80A/Y67A variant, the cooperative low-pH transition is split into two distinct processes because of an increased stability of the molten globule state that is formed at higher pH values than the other species. These data show that removal of the axial methionine ligand does not significantly alter the mechanism of acidic unfolding and the ranges of stability of low-pH conformers. Instead, removal of a hydrogen bonding partner at position 67 increases the stability of the molten globule and renders cytochrome c more susceptible to acid unfolding. This underlines the key role played by Tyr67 in stabilizing the three-dimensional structure of cytochrome c by means of the hydrogen bonding network connecting the Ω loops formed by residues 71-85 and 40-57.

Mixed-strain housing for female C57BL/6, DBA/2, and BALB/c mice: validating a split-plot design that promotes refinement and reduction

Directory of Open Access Journals (Sweden)

Michael Walker

2016-01-01

Full Text Available Abstract Background Inefficient experimental designs are common in animal-based biomedical research, wasting resources and potentially leading to unreplicable results. Here we illustrate the intrinsic statistical power of split-plot designs, wherein three or more sub-units (e.g. individual subjects differing in a variable of interest (e.g. genotype share an experimental unit (e.g. a cage or litter to which a treatment is applied (e.g. a drug, diet, or cage manipulation. We also empirically validate one example of such a design, mixing different mouse strains -- C57BL/6, DBA/2, and BALB/c -- within cages varying in degree of enrichment. As well as boosting statistical power, no other manipulations are needed for individual identification if co-housed strains are differentially pigmented, so also sparing mice from stressful marking procedures. Methods The validation involved housing 240 females from weaning to 5 months of age in single- or mixed- strain trios, in cages allocated to enriched or standard treatments. Mice were screened for a range of 26 commonly-measured behavioural, physiological and haematological variables. Results Living in mixed-strain trios did not compromise mouse welfare (assessed via corticosterone metabolite output, stereotypic behaviour, signs of aggression, and other variables. It also did not alter the direction or magnitude of any strain- or enrichment-typical difference across the 26 measured variables, or increase variance in the data: indeed variance was significantly decreased by mixed- strain housing. Furthermore, using Monte Carlo simulations to quantify the statistical power benefits of this approach over a conventional design demonstrated that for our effect sizes, the split- plot design would require significantly fewer mice (under half in most cases to achieve a power of 80 %. Conclusions Mixed-strain housing allows several strains to be tested at once, and potentially refines traditional marking practices

Bad splits in bilateral sagittal split osteotomy: systematic review of fracture patterns.

Science.gov (United States)

Steenen, S A; Becking, A G

2016-07-01

An unfavourable and unanticipated pattern of the mandibular sagittal split osteotomy is generally referred to as a 'bad split'. Few restorative techniques to manage the situation have been described. In this article, a classification of reported bad split pattern types is proposed and appropriate salvage procedures to manage the different types of undesired fracture are presented. A systematic review was undertaken, yielding a total of 33 studies published between 1971 and 2015. These reported a total of 458 cases of bad splits among 19,527 sagittal ramus osteotomies in 10,271 patients. The total reported incidence of bad split was 2.3% of sagittal splits. The most frequently encountered were buccal plate fractures of the proximal segment (types 1A-F) and lingual fractures of the distal segment (types 2A and 2B). Coronoid fractures (type 3) and condylar neck fractures (type 4) have seldom been reported. The various types of bad split may require different salvage approaches. Copyright © 2016 International Association of Oral and Maxillofacial Surgeons. Published by Elsevier Ltd. All rights reserved.

Symmetric Tensor Decomposition

DEFF Research Database (Denmark)

Brachat, Jerome; Comon, Pierre; Mourrain, Bernard

2010-01-01

We present an algorithm for decomposing a symmetric tensor, of dimension n and order d, as a sum of rank-1 symmetric tensors, extending the algorithm of Sylvester devised in 1886 for binary forms. We recall the correspondence between the decomposition of a homogeneous polynomial in n variables...... of polynomial equations of small degree in non-generic cases. We propose a new algorithm for symmetric tensor decomposition, based on this characterization and on linear algebra computations with Hankel matrices. The impact of this contribution is two-fold. First it permits an efficient computation...... of the decomposition of any tensor of sub-generic rank, as opposed to widely used iterative algorithms with unproved global convergence (e.g. Alternate Least Squares or gradient descents). Second, it gives tools for understanding uniqueness conditions and for detecting the rank....

Deprotonation of g-C₃N₄ with Na ions for efficient nonsacrificial water splitting under visible light

DEFF Research Database (Denmark)

Guo, Feng; Chen, Jingling; Zhang, Minwei

2016-01-01

Developing a photocatalyst with the necessary characteristics of being cheap, efficient and robust for visible-light-driven water splitting remains a serious challenge within the photocatalysis field. Herein, an effective strategy, deprotonating g-C3N4 with Na ions from low-cost precursors...

Superfield Lax formalism of supersymmetric sigma model on symmetric spaces

International Nuclear Information System (INIS)

Saleem, U.; Hassan, M.

2006-01-01

We present a superfield Lax formalism of the superspace sigma model based on the target space G/H and show that a one-parameter family of flat superfield connections exists if the target space G/H is a symmetric space. The formalism has been related to the existence of an infinite family of local and non-local superfield conserved quantities. A few examples have been given to illustrate the results. (orig.)

Extensions of pseudo-Perron-Frobenius splitting related to generalized inverse AT,S(2

Directory of Open Access Journals (Sweden)

Huang Shaowu

2018-02-01

Full Text Available We in this paper define the outer-Perron-Frobenius splitting, which is an extension of the pseudo- Perron-Frobenius splitting defined in [A.N. Sushama, K. Premakumari, K.C. Sivakumar, Extensions of Perron-Frobenius splittings and relationships with nonnegative Moore-Penrose inverse, Linear and Multilinear Algebra 63 (2015 1-11]. We present some criteria for the convergence of the outer-Perron-Frobenius splitting. The findings of this paper generalize some known results in the literatures.

Catalyst- and Reagent-free Electrochemical Azole C-H Amination.

Science.gov (United States)

Qiu, Youai; Struwe, Julia; Meyer, Tjark H; Oliveira, Joao Carlos Agostinho Carlos Agostinho; Ackermann, Lutz

2018-06-14

Catalyst-, and chemical oxidant-free electrochemical azole C-H aminations were accomplished via cross-dehydrogenative C-H/N-H functionalization. The catalyst-free electrochemical C-H amination proved feasible on azoles with high levels of efficacy and selectivity, avoiding the use of stoichiometric oxidants under ambient conditions. Likewise, the C(sp3)-H nitrogenation proved viable under otherwise identical conditions. The dehydrogenative C-H amination featured ample scope, including cyclic and acyclic aliphatic amines as well as anilines, and employed sustainable electricity as the sole oxidant. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Spin photocurrent spectra induced by Rashba- and Dresselhaus-type circular photogalvanic effect at inter-band excitation in InGaAs/GaAs/AlGaAs step quantum wells.

Science.gov (United States)

Yu, Jinling; Cheng, Shuying; Lai, Yunfeng; Zheng, Qiao; Chen, Yonghai

2014-03-19

: Spin photocurrent spectra induced by Rashba- and Dresselhaus-type circular photogalvanic effect (CPGE) at inter-band excitation have been experimentally investigated in InGaAs/GaAs/AlGaAs step quantum wells (QWs) at room temperature. The Rashba- and Dresselhaus-induced CPGE spectra are quite similar with each other during the spectral region corresponding to the transition of the excitonic state 1H1E (the first valence subband of heavy hole to the first conduction subband of electrons). The ratio of Rashba- and Dresselhaus-induced CPGE current for the transition 1H1E is estimated to be 8.8±0.1, much larger than that obtained in symmetric QWs (4.95). Compared to symmetric QWs, the reduced well width enhances the Dresselhaus-type spin splitting, but the Rashba-type spin splitting increases more rapidly in the step QWs. Since the degree of the segregation effect of indium atoms and the intensity of build-in field in the step QWs are comparable to those in symmetric QWs, as proved by reflectance difference and photoreflectance spectra, respectively, the larger Rashba-type spin splitting is mainly induced by the additional interface introduced by step structures.

Photocatalytic H 2 production from water splitting under visible light irradiation using Eosin Y-sensitized mesoporous-assembled Pt/TiO 2 nanocrystal photocatalyst

Science.gov (United States)

Sreethawong, Thammanoon; Junbua, Chompoonuch; Chavadej, Sumaeth

Sensitized photocatalytic production of hydrogen from water splitting is investigated under visible light irradiation over mesoporous-assembled titanium dioxide (TiO 2) nanocrystal photocatalysts, without and with Pt loading. The photocatalysts are synthesized by a sol-gel process with the aid of a structure-directing surfactant and are characterized by N 2 adsorption-desorption analysis, X-ray diffraction, UV-vis spectroscopy, scanning electron microscopy, transmission electron microscopy and energy-dispersive X-ray analysis. The dependence of hydrogen production on the type of TiO 2 photocatalyst (synthesized mesoporous-assembled and commercial non-mesoporous-assembled TiO 2 without and with Pt loading), the calcination temperature of the synthesized photocatalyst, the sensitizer (Eosin Y) concentration, the electron donor (diethanolamine) concentration, the photocatalyst dosage and the initial solution pH is systematically studied. The results show that in the presence of the Eosin Y sensitizer, the Pt-loaded mesoporous-assembled TiO 2 synthesized by a single-step sol-gel process and calcined at 500 °C exhibits the highest photocatalytic activity for hydrogen production from a 30 vol.% diethanolamine aqueous solution with dissolved 2 mM Eosin Y. Moreover, the optimum photocatalyst dosage and initial solution pH for the maximum photocatalytic activity for hydrogen production are 3.33 g dm -3 and 11.5, respectively.

Classically integrable boundary conditions for symmetric-space sigma models

International Nuclear Information System (INIS)

MacKay, N.J.; Young, C.A.S.

2004-01-01

We investigate boundary conditions for the non-linear sigma model on the compact symmetric space G/H. The Poisson brackets and the classical local conserved charges necessary for integrability are preserved by boundary conditions which correspond to involutions which commute with the involution defining H. Applied to SO(3)/SO(2), the non-linear sigma model on S 2 , these yield the great circles as boundary submanifolds. Applied to GxG/G, they reproduce known results for the principal chiral model

Ir-catalyzed C-H silylations of phenyldeazapurines

Czech Academy of Sciences Publication Activity Database

Sabat, Nazarii; Poštová Slavětínská, Lenka; Hocek, Michal

2015-01-01

Roč. 56, č. 49 (2015), s. 6860-6862 ISSN 0040-4039 Institutional support: RVO:61388963 Keywords : C-H silylation * deazapurines * iridium catalysis * C-H activations Subject RIV: CC - Organic Chemistry Impact factor: 2.347, year: 2015

Potency of whole virus particle and split virion vaccines using dissolving microneedle against challenges of H1N1 and H5N1 influenza viruses in mice.

Science.gov (United States)

Nakatsukasa, Akihiro; Kuruma, Koji; Okamatsu, Masatoshi; Hiono, Takahiro; Suzuki, Mizuho; Matsuno, Keita; Kida, Hiroshi; Oyamada, Takayoshi; Sakoda, Yoshihiro

2017-05-15

Transdermal vaccination using a microneedle (MN) confers enhanced immunity compared with subcutaneous (SC) vaccination. Here we developed a novel dissolving MN patch for the influenza vaccine. The potencies of split virion and whole virus particle (WVP) vaccines prepared from A/Puerto Rico/8/1934 (H1N1) and A/duck/Hokkaido/Vac-3/2007 (H5N1), respectively, were evaluated. MN vaccination induced higher neutralizing antibody responses than SC vaccination in mice. Moreover, MN vaccination with a lower dose of antigens conferred protective immunity against lethal challenges of influenza viruses than SC vaccination in mice. These results suggest that the WVP vaccines administered using MN are an effective combination for influenza vaccine to be further validated in humans. Copyright © 2017 Elsevier Ltd. All rights reserved.

Market Structure and Stock Splits

OpenAIRE

David Michayluk; Paul Kofman

2001-01-01

Enhanced liquidity is one possible motivation for stock splits but empirical research frequently documents declines in liquidity following stock splits. Despite almost thirty years of inquiry, little is known about all the changes in a stock's trading activity following a stock split. We examine how liquidity measures change around more than 2,500 stock splits and find a pervasive decline in most measures. Large stock splits exhibit a more severe liquidity decline than small stock splits, esp...

Hydrogen behaviour study in plasma facing a-C:H and a-SiC:H hydrogenated amorphous materials for fusion reactors

International Nuclear Information System (INIS)

Barbier, Gauzelin

1997-01-01

Plasma facing components of controlled fusion test devices (tokamaks) are submitted to several constraints (irradiation, high temperatures). The erosion (physical sputtering and chemical erosion) and the hydrogen recycling (retention and desorption) of these materials influence many plasma parameters and thus affect drastically the tokamak running. Firstly, we will describe the different plasma-material interactions. It will be pointed out, how erosion and hydrogen recycling are strongly related to both chemical and physical properties of the material. In order to reduce this interactions, we have selected two amorphous hydrogenated materials (a-C:H and a-SiC:H), which are known for their good thermal and chemical qualities. Some samples have been then implanted with lithium ions at different fluences. Our materials have been then irradiated with deuterium ions at low energy. From our results, it is shown that both the lithium implantation and the use of an a-SiC:H substrate can be benefit in enhancing the hydrogen retention. These results were completed with thermal desorption studies of these materials. It was evidenced that the hydrogen fixation was more efficient in a -SiC:H than in a-C:H substrate. Results in good agreement with those described above have been obtained by exposing a-C:H and a-SiC:H samples to the scrape off layer of the tokamak of Varennes (TdeV, Canada). A modeling of hydrogen diffusion under irradiation has been also proposed. (author)

General allylic C-H alkylation with tertiary nucleophiles.

Science.gov (United States)

Howell, Jennifer M; Liu, Wei; Young, Andrew J; White, M Christina

2014-04-16

A general method for intermolecular allylic C-H alkylation of terminal olefins with tertiary nucleophiles has been accomplished employing palladium(II)/bis(sulfoxide) catalysis. Allylic C-H alkylation furnishes products in good yields (avg. 64%) with excellent regio- and stereoselectivity (>20:1 linear:branched, >20:1 E:Z). For the first time, the olefin scope encompasses unactivated aliphatic olefins as well as activated aromatic/heteroaromatic olefins and 1,4-dienes. The ease of appending allyl moieties onto complex scaffolds is leveraged to enable this mild and selective allylic C-H alkylation to rapidly diversify phenolic natural products. The tertiary nucleophile scope is broad and includes latent functionality for further elaboration (e.g., aliphatic alcohols, α,β-unsaturated esters). The opportunities to effect synthetic streamlining with such general C-H reactivity are illustrated in an allylic C-H alkylation/Diels-Alder reaction cascade: a reactive diene is generated via intermolecular allylic C-H alkylation and approximated to a dienophile contained within the tertiary nucleophile to furnish a common tricyclic core found in the class I galbulimima alkaloids.

Long-pulsed dye laser versus intense pulsed light for photodamaged skin: A randomized split-face trial with blinded response evaluation

DEFF Research Database (Denmark)

Jorgensen, G.F.; Hedelund, L.; Haedersdal, M.

2008-01-01

Objective: In a randomized controlled split-face trial to evaluate efficacy and adverse effects from rejuvenation with long-pulsed dye laser (LPDL) versus intense pulsed light (IPL). Materials and Methods: Twenty female volunteers with Fitzpatrick skin types I-III, classes I-II rhytids......, and symmetrical split-face photodamage were included in the study. Subjects received a series of three treatments at 3-week intervals with half-face LPDL (V-beam Perfecta, 595 nm, Candela Laser Corporation) and half-face IPL (Ellipse Flex, Danish Dermatologic Development); the interventions being randomly...... assigned to left and right sides. Primary end-points were telangiectasias, irregular pigmentation and preferred treatment. Secondary end-points were skin texture, rhytids, pain, and adverse effects. Efficacy was evaluated by patient self-assessments and by blinded clinical on-site and photographic...

A FORMAÇÃO DE LIGAÇÕES DE HIDROGÊNIO π‧‧‧H, F‧‧‧H E C‧‧‧H NOS COMPLEXOS C2H2‧‧‧(HF, C2H2‧‧‧2(HF E C2H2‧‧‧3(HF

Directory of Open Access Journals (Sweden)

Boaz G. Oliveira

2016-04-01

Full Text Available In this work, a theoretical study on the basis of structural, vibrational, electronic and topological parameters of the C2H2‧‧‧(HF, C2H2‧‧‧2(HF and C2H2‧‧‧3(HF complexes concerning the formation of π‧‧‧H, F‧‧‧H and C‧‧‧H hydrogen bonds is presented. The main difference among these complexes is not properly the interaction strength, but the hydrogen bond type whose benchmark is ruled justly by the structure. Meanwhile, the occurrence of π‧‧‧H hydrogen bonds was unveiled in both C2H2‧‧‧(HF dimer and C2H2‧‧‧3(HF tetramer, although in latter, this interaction is stronger than C‧‧‧H of the C2H2‧‧‧2(HF trimer. However, the F‧‧‧H hydrogen bonds within the subunits of hydrofluoric acid are the strongest ones, reaching a partial covalent limit, and thereby contribute decisively to the stabilization of the tetramer structure. In line with this, the largest red-shifts were observed on the hydrofluoric acid trimer of the C2H2‧‧‧3(HF complex.

Crystalline diuranium phosphinidiide and μ-phosphido complexes with symmetric and asymmetric UPU cores

Energy Technology Data Exchange (ETDEWEB)

Rookes, Thomas M.; Gardner, Benedict M.; Gregson, Matthew; Tuna, Floriana; Wooles, Ashley J.; Liddle, Stephen T. [School of Chemistry, The University of Manchester, Manchester (United Kingdom); Balazs, Gabor; Scheer, Manfred [Institute of Inorganic Chemistry, University of Regensburg (Germany)

2017-08-21

Reaction of [U(Tren{sup TIPS})(PH{sub 2})] (1, Tren{sup TIPS}=N(CH{sub 2}CH{sub 2}NSiPr{sup i}{sub 3}){sub 3}) with C{sub 6}H{sub 5}CH{sub 2}K and [U(Tren{sup TIPS})(THF)][BPh{sub 4}] (2) afforded a rare diuranium parent phosphinidiide complex [{U(Tren"T"I"P"S)}{sub 2}(μ-PH)] (3). Treatment of 3 with C{sub 6}H{sub 5}CH{sub 2}K and two equivalents of benzo-15-crown-5 ether (B15C5) gave the diuranium μ-phosphido complex [{U(Tren"T"I"P"S)}{sub 2}(μ-P)][K(B15C5){sub 2}] (4). Alternatively, reaction of [U(Tren{sup TIPS})(PH)][Na(12C4){sub 2}] (5, 12C4=12-crown-4 ether) with [U{N(CH_2CH_2NSiMe_2Bu"t)_2CH_2CH_2NSi(Me)(CH_2)(Bu"t)}] (6) produced the diuranium μ-phosphido complex [{U(Tren"T"I"P"S)}(μ-P){U(Tren"D"M"B"S)}][Na(12C4){sub 2}] [7, Tren{sup DMBS}=N(CH{sub 2}CH{sub 2}NSiMe{sub 2}Bu{sup t}){sub 3}]. Compounds 4 and 7 are unprecedented examples of uranium phosphido complexes outside of matrix isolation studies, and they rapidly decompose in solution underscoring the paucity of uranium phosphido complexes. Interestingly, 4 and 7 feature symmetric and asymmetric UPU cores, respectively, reflecting their differing steric profiles. (copyright 2017 The Authors. Published by Wiley-VCH Verlag GmbH and Co. KGaA.)

One-loop calculations of photon splitting in relativistic quantum plasma by Green's function technique

International Nuclear Information System (INIS)

De la Incera, V.; Ferrer, E.; Shalad, A.Y.

1987-01-01

A homogeneous and isotropic plasma made up of electrons and positrons is examined. The coefficients of the covariant expansion of the three-photon vertex are calculated in the one-loop approximation of the Green's function technique, together with the probability amplitudes of various processes involving three photons that produce information on the probability of the polarization states of the incoming and outgoing photons in the splitting process. The calculation results are used to verify the consequences of all exact symmetries which must be done for the vertex tensor. The case of a charge-symmetric plasma is considered together with the special case of photon collinearity

The Features of Moessbauer Spectra of Hemoglobins: Approximation by Superposition of Quadrupole Doublets or by Quadrupole Splitting Distribution?

International Nuclear Information System (INIS)

Oshtrakh, M. I.; Semionkin, V. A.

2004-01-01

Moessbauer spectra of hemoglobins have some features in the range of liquid nitrogen temperature: a non-Lorentzian asymmetric line shape for oxyhemoglobins and symmetric Lorentzian line shape for deoxyhemoglobins. A comparison of the approximation of the hemoglobin Moessbauer spectra by a superposition of two quadrupole doublets and by a distribution of the quadrupole splitting demonstrates that a superposition of two quadrupole doublets is more reliable and may reflect the non-equivalent iron electronic structure and the stereochemistry in the α- and β-subunits of hemoglobin tetramers.

Novel microwave-assisted synthesis of porous g-C3N4/SnO2 nanocomposite for solar water-splitting

Science.gov (United States)

Seza, A.; Soleimani, F.; Naseri, N.; Soltaninejad, M.; Montazeri, S. M.; Sadrnezhaad, S. K.; Mohammadi, M. R.; Moghadam, H. Asgari; Forouzandeh, M.; Amin, M. H.

2018-05-01

Highly porous nanocomposites of graphitic-carbon nitride and tin oxide (g-C3N4/SnO2) were prepared through simple pyrolysis of urea molecules under microwave irradiation. The initial amount of tin was varied in order to investigate the effect of SnO2 content on preparation and properties of the composites. The synthesized nanocomposites were well-characterized by XRD, FE-SEM, HR-TEM, BET, FTIR, XPS, DRS, and PL. A homogeneous distribution of SnO2 nanoparticles with the size of less than 10 nm on the porous C3N4 sheets could be obtained, suggesting that in-situ synthesis of SnO2 nanoparticles was responsible for the formation of g-C3N4. The process likely occurred by the aid of the large amounts of OH groups formed on the surfaces of SnO2 nanoparticles during the polycondensation reactions of tin derivatives which could facilitate the pyrolysis of urea to carbon nitride. The porous nanocomposite prepared with initial tin amount of 0.175 g had high specific surface area of 195 m2 g-1 which showed high efficiency photoelectrochemical water-splitting ability. A maximum photocurrent density of 33 μA cm-2 was achieved at an applied potential of 0.5 V when testing this nanocomposite as photo-anode in water-splitting reactions under simulated visible light irradiation, introducing it as a promising visible light photoactive material.

The I{sub c}(H)-T{sub c}(H) phase boundary of superconducting Nb thin films with periodic and quasiperiodic antidot arrays

Energy Technology Data Exchange (ETDEWEB)

Bothner, D.; Kemmler, M.; Cozma, R.; Kleiner, R.; Koelle, D. [Physikalisches Institut and Center for Collective Quantum Phenomena, Universitaet Tuebingen (Germany); Misko, V.; Peeters, F. [Departement Fysica, Universiteit Antwerpen (Belgium); Nori, F. [Advanced Science Institute, RIKEN (Japan)

2011-07-01

The magnetic field dependent critical current I{sub c}(H) of superconducting thin films with artificial defects strongly depends on the symmetry of the defect arrangement. Likewise the critical temperature T{sub c}(H) of superconducting wire networks is heavily influenced by the symmetry of the system. Here we present experimental data on the I{sub c}(H)-T{sub c}(H) phase boundary of Nb thin films with artificial defect lattices of different symmetries. For this purpose we fabricated 60 nm thick Nb films with antidots in periodic (triangular) and five different quasiperiodic arrangements. The parameters of the antidot arrays were varied to investigate the influence of antidot diameter and array density. Experiments were performed with high temperature stability ({delta}T<1 mK) at 0.5{<=}T/T{sub c}{<=}1. From the I-V-characteristics at variable H and T we extract I{sub c}(H) and T{sub c}(H) for different voltage and resistance criteria. The experimental data for the critical current density are compared with results from numerical molecular dynamics simulations.

Extensions of the Hardy-Littlewood inequalities for Schwarz symmetrization

Directory of Open Access Journals (Sweden)

H. Hajaiej

2004-01-01

Full Text Available For a class of functions H:(0,∞×ℝ+2→ℝ, including discontinuous functions of Carathéodory type, we establish that ∫ℝNH(|x|,u(x,v(xdx≤∫ℝNH(|x|,u*(x,v*(xdx, where u*(x and v*(x denote the Schwarz symmetrizations of nonnegative functions u and v.

Theoretical study of the changes in the vibrational characteristics arising from the hydrogen bonding between Vitamin C ( L-ascorbic acid) and H 2O

Science.gov (United States)

Dimitrova, Yordanka

2006-02-01

The vibrational characteristics (vibrational frequencies, infrared intensities and Raman activities) for the hydrogen-bonded system of Vitamin C ( L-ascorbic acid) with five water molecules have been predicted using ab initio SCF/6-31G(d, p) calculations and DFT (BLYP) calculations with 6-31G(d, p) and 6-31++G(d, p) basis sets. The changes in the vibrational characteristics from free monomers to a complex have been calculated. The ab initio and BLYP calculations show that the complexation between Vitamin C and five water molecules leads to large red shifts of the stretching vibrations for the monomer bonds involved in the hydrogen bonding and very strong increase in their IR intensity. The predicted frequency shifts for the stretching vibrations from Vitamin C taking part in the hydrogen bonding are up to -508 cm -1. The magnitude of the wavenumber shifts is indicative of relatively strong OH···H hydrogen-bonded interactions. In the same time the IR intensity and Raman activity of these vibrations increase upon complexation. The IR intensity increases dramatically (up to 12 times) and Raman activity increases up to three times. The ab initio and BLYP calculations show, that the symmetric OH vibrations of water molecules are more sensitive to the complexation. The hydrogen bonding leads to very large red shifts of these vibrations and very strong increase in their IR intensity. The asymmetric OH stretching vibrations of water, free from hydrogen bonding are less sensitive to the complexation than the hydrogen-bonded symmetric O sbnd H stretching vibrations. The increases of the IR intensities for these vibrations are lower and red shifts are negligible.

Symmetric extendibility of quantum states

OpenAIRE

Nowakowski, Marcin L.

2015-01-01

Studies on symmetric extendibility of quantum states become especially important in a context of analysis of one-way quantum measures of entanglement, distilabillity and security of quantum protocols. In this paper we analyse composite systems containing a symmetric extendible part with a particular attention devoted to one-way security of such systems. Further, we introduce a new one-way monotone based on the best symmetric approximation of quantum state. We underpin those results with geome...

Photodissociation of C{sub 3}H{sub 5}Br and C{sub 4}H{sub 7}Br at 234 nm

Energy Technology Data Exchange (ETDEWEB)

Kim, Hyun Kook; Paul, Dababrata; Hong, Ki Ryong; Cho, Ha Na; Kim, Tae Kyu [Pusan National University, Busan (Korea, Republic of); Lee, Kyoung Seok [Korea Research Institute of Standards and Science, Daejeon (Korea, Republic of)

2012-01-15

The photodissociation dynamics of cyclopropyl bromide (C-3H{sub 5}Br) and cyclobutyl bromide (C{sub 4}H{sub 7}Br) at 234 nm was investigated. A two-dimensional photofragment ion-imaging technique coupled with a [2+1] resonance enhanced multiphoton ionization scheme was utilized to obtain speed and angular distributions of the nascent Br({sup 2}P{sub 3/2}) and Br*({sup 2}P{sub 1/2}) atoms. The recoil anisotropies for the Br and Br* channels were measured to be βBr = 0.92 ± 0.03 and βBr* = 1.52 ± 0.04 for C{sub 3}H{sub 5}Br and βBr = 1.10 ± 0.03 and βBr* = 1.49 ± 0.05 for C{sub 4}H{sub 7}Br. The relative quantum yield for Br was found to be ΦBr = 0.13 ± 0.03 and for C{sub 3}H{sub 5}Br and C{sub 4}H{sub 7}Br, respectively. The soft radical limit of the impulsive model adequately modeled the related energy partitioning. The nonadiabatic transition probability from the 3A' and 4A' potential energy surfaces was estimated and discussed.

Symmetric eikonal expansion

International Nuclear Information System (INIS)

Matsuki, Takayuki

1976-01-01

Symmetric eikonal expansion for the scattering amplitude is formulated for nonrelativistic and relativistic potential scatterings and also for the quantum field theory. The first approximations coincide with those of Levy and Sucher. The obtained scattering amplitudes are time reversal invariant for all cases and are crossing symmetric for the quantum field theory in each order of approximation. The improved eikonal phase introduced by Levy and Sucher is also derived from the different approximation scheme from the above. (auth.)

On symmetric structures of order two

Directory of Open Access Journals (Sweden)

Michel Bousquet

2008-04-01

Full Text Available Let (ω n 0 < n be the sequence known as Integer Sequence A047749 http://www.research.att.com/ njas/sequences/A047749 In this paper, we show that the integer ω n enumerates various kinds of symmetric structures of order two. We first consider ternary trees having a reflexive symmetry and we relate all symmetric combinatorial objects by means of bijection. We then generalize the symmetric structures and correspondences to an infinite family of symmetric objects.

Recent Advances in Bismuth-Based Nanomaterials for Photoelectrochemical Water Splitting.

Science.gov (United States)

Bhat, Swetha S M; Jang, Ho Won

2017-08-10

In recent years, bismuth-based nanomaterials have drawn considerable interest as potential candidates for photoelectrochemical (PEC) water splitting owing to their narrow band gaps, nontoxicity, and low costs. The unique electronic structure of bismuth-based materials with a well-dispersed valence band comprising Bi 6s and O 2p orbitals offers a suitable band gap to harvest visible light. This Review presents significant advancements in exploiting bismuth-based nanomaterials for solar water splitting. An overview of the different strategies employed and the new ideas adopted to improve the PEC performance of bismuth-based nanomaterials are discussed. Morphology control, the construction of heterojunctions, doping, and co-catalyst loading are several approaches that are implemented to improve the efficiency of solar water splitting. Key issues are identified and guidelines are suggested to rationalize the design of efficient bismuth-based materials for sunlight-driven water splitting. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

The osmotic stress response of split influenza vaccine particles in an acidic environment.

Science.gov (United States)

Choi, Hyo-Jick; Kim, Min-Chul; Kang, Sang-Moo; Montemagno, Carlo D

2014-12-01

Oral influenza vaccine provides an efficient means of preventing seasonal and pandemic disease. In this work, the stability of envelope-type split influenza vaccine particles in acidic environments has been investigated. Owing to the fact that hyper-osmotic stress can significantly affect lipid assembly of vaccine, osmotic stress-induced morphological change of split vaccine particles, in conjunction with structural change of antigenic proteins, was investigated by the use of stopped-flow light scattering (SFLS), intrinsic fluorescence, transmission electron microscopy (TEM), and hemagglutination assay. Split vaccine particles were found to exhibit a step-wise morphological change in response to osmotic stress due to double-layered wall structure. The presence of hyper-osmotic stress in acidic medium (0.3 osmolarity, pH 2.0) induced a significant level of membrane perturbation as measured by SFLS and TEM, imposing more damage to antigenic proteins on vaccine envelope than can be caused by pH-induced conformational change at acidic iso-osmotic condition. Further supports were provided by the intrinsic fluorescence and hemagglutinin activity measurements. Thus, hyper-osmotic stress becomes an important factor for determining stability of split vaccine particles in acidic medium. These results are useful in better understanding the destabilizing mechanism of split influenza vaccine particles in gastric environment and in designing oral influenza vaccine formulations.

Skyrmions and vector mesons: a symmetric approach

International Nuclear Information System (INIS)

Caldi, D.G.

1984-01-01

We propose an extension of the effective, low-energy chiral Lagrangian known as the Skyrme model, to one formulated by a non-linear sigma model generalized to include vector mesons in a symmetric way. The model is based on chiral SU(6) x SU(6) symmetry spontaneously broken to static SU(6). The rho and other vector mesons are dormant Goldstone bosons since they are in the same SU(6) multiplet as the pion and other pseudoscalars. Hence the manifold of our generalized non-linear sigma model is the coset space (SU(6) x SU(6))/Su(6). Relativistic effects, via a spin-dependent mass term, break the static SU(6) and give the vectors a mass. The model can then be fully relativistic and covariant. The lowest-lying Skyrmion in this model is the whole baryonic 56-plet, which splits into the octet and decuplet in the presence of relativistic SU(6)-breaking. Due to the built-in SU(6) and the presence of vector mesons, the model is expected to have better phenomenological results, as well as providing a conceptually more unified picture of mesons and baryons. 29 references

Conformation-induced remote meta-C-H activation of amines

Science.gov (United States)

Tang, Ri-Yuan; Li, Gang; Yu, Jin-Quan

2014-03-01

Achieving site selectivity in carbon-hydrogen (C-H) functionalization reactions is a long-standing challenge in organic chemistry. The small differences in intrinsic reactivity of C-H bonds in any given organic molecule can lead to the activation of undesired C-H bonds by a non-selective catalyst. One solution to this problem is to distinguish C-H bonds on the basis of their location in the molecule relative to a specific functional group. In this context, the activation of C-H bonds five or six bonds away from a functional group by cyclometallation has been extensively studied. However, the directed activation of C-H bonds that are distal to (more than six bonds away) functional groups has remained challenging, especially when the target C-H bond is geometrically inaccessible to directed metallation owing to the ring strain encountered in cyclometallation. Here we report a recyclable template that directs the olefination and acetoxylation of distal meta-C-H bonds--as far as 11 bonds away--of anilines and benzylic amines. This template is able to direct the meta-selective C-H functionalization of bicyclic heterocycles via a highly strained, tricyclic-cyclophane-like palladated intermediate. X-ray and nuclear magnetic resonance studies reveal that the conformational biases induced by a single fluorine substitution in the template can be enhanced by using a ligand to switch from ortho- to meta-selectivity.

A General Catalyst for Site-Selective C(sp(3))-H Bond Amination of Activated Secondary over Tertiary Alkyl C(sp(3))-H Bonds.

Science.gov (United States)

Scamp, Ryan J; Jirak, James G; Dolan, Nicholas S; Guzei, Ilia A; Schomaker, Jennifer M

2016-06-17

The discovery of transition metal complexes capable of promoting general, catalyst-controlled and selective carbon-hydrogen (C-H) bond amination of activated secondary C-H bonds over tertiary alkyl C(sp(3))-H bonds is challenging, as substrate control often dominates when reactive nitrene intermediates are involved. In this letter, we report the design of a new silver complex, [(Py5Me2)AgOTf]2, that displays general and good-to-excellent selectivity for nitrene insertion into propargylic, benzylic, and allylic C-H bonds over tertiary alkyl C(sp(3))-H bonds.

Complex {PT}-symmetric extensions of the nonlinear ultra-short light pulse model

Science.gov (United States)

Yan, Zhenya

2012-11-01

The short pulse equation u_{xt}=u+\\frac{1}{2}(u^2u_x)_x is PT symmetric, which arises in nonlinear optics for the ultra-short pulse case. We present a family of new complex PT-symmetric extensions of the short pulse equation, i[(iu_x)^{\\sigma }]_t=au+bu^m+ic[u^n(iu_x)^{\\epsilon }]_x \\,\\, (\\sigma ,\\, \\epsilon ,\\,a,\\,b,\\,c,\\,m,\\,n \\in {R}), based on the complex PT-symmetric extension principle. Some properties of these equations with some chosen parameters are studied including the Hamiltonian structures and exact solutions such as solitary wave solutions, doubly periodic wave solutions and compacton solutions. Our results may be useful to understand complex PT-symmetric nonlinear physical models. This article is part of a special issue of Journal of Physics A: Mathematical and Theoretical devoted to ‘Quantum physics with non-Hermitian operators’.

Spectra of PT -symmetric Hamiltonians on tobogganic contours

Indian Academy of Sciences (India)

The term PT -symmetric quantum mechanics, although defined to be of a much broader use, was coined in tight connection with C. Bender's analysis of one- ... on the other hand, the other members of the family were strange Hamiltonians with imaginary potentials which do not appear physical at all. The aim of the.

Analysis of mobile fronthaul bandwidth and wireless transmission performance in split-PHY processing architecture.

Science.gov (United States)

Miyamoto, Kenji; Kuwano, Shigeru; Terada, Jun; Otaka, Akihiro

2016-01-25

We analyze the mobile fronthaul (MFH) bandwidth and the wireless transmission performance in the split-PHY processing (SPP) architecture, which redefines the functional split of centralized/cloud RAN (C-RAN) while preserving high wireless coordinated multi-point (CoMP) transmission/reception performance. The SPP architecture splits the base stations (BS) functions between wireless channel coding/decoding and wireless modulation/demodulation, and employs its own CoMP joint transmission and reception schemes. Simulation results show that the SPP architecture reduces the MFH bandwidth by up to 97% from conventional C-RAN while matching the wireless bit error rate (BER) performance of conventional C-RAN in uplink joint reception with only 2-dB signal to noise ratio (SNR) penalty.

Facile synthesis of flake-like TiO{sub 2}/C nano-composites for photocatalytic H{sub 2} evolution under visible-light irradiation

Energy Technology Data Exchange (ETDEWEB)

Yan, Baolin; Zhou, Juan; Liang, Xiaoyu; Song, Kainan; Su, Xintai, E-mail: suxintai827@163.com

2017-01-15

Highlights: • TiO{sub 2}/C nano-flakes were prepared by a facile phase-transfer strategy combined with salt-template calcination method. • The sub–10 nm of TiO{sub 2} NPs were uniformly dispersed on the carbon flakes. • The TiO{sub 2}/C nano-flakes showed a superior visible-light photocatalytic activity for H{sub 2} production. - Abstract: The production of H{sub 2} by photocatalytic water splitting has become a promising approach for clean, economical, and renewable evolution of H{sub 2} by using solar energy. In spite of tremendous efforts, the present challenge for materials scientists is to build a highly active photocatalytic system with high efficiency and low cost. Here we report a facile method for the preparation of TiO{sub 2}/C nano-flakes, which was used as an efficient visible-light photocatalyst for H{sub 2} evolution. This composite material was prepared by using a phase-transfer strategy combined with salt-template calcination treatment. The results showed that anatase TiO{sub 2} nanoparticles with the diameter of ∼10 nm were uniformly dispersed on the carbon nano-flakes. In addition, the samples prepared at 600 °C (denoted as T600) endowed a larger surface area of 196 m{sup 2} g{sup −1} and higher light absorption, resulting in enhanced photocatalytic activity. Further, the T600 product reached a high H{sub 2} production rate of 57.2 μmol h{sup −1} under visible-light irradiation. This unusual photocatalytic activity arose from the positive synergetic effect between the TiO{sub 2} and carbon in this hybrid catalyst. This work highlights the potential of TiO{sub 2}/C nano-flakes in the field of photocatalytic H{sub 2} evolution under visible-light irradiation.

Experimental ion mobility measurements in Xe-C2H6

Science.gov (United States)

Perdigoto, J. M. C.; Cortez, A. F. V.; Veenhof, R.; Neves, P. N. B.; Santos, F. P.; Borges, F. I. G. M.; Conde, C. A. N.

2017-10-01

In this paper we present the results of the ion mobility measurements made in gaseous mixtures of xenon (Xe) with ethane (C2H6) for pressures ranging from 6 to 10 Torr (8-10.6 mbar) and for low reduced electric fields in the 10 Td to 25 Td range (2.4-6.1 kVṡcm-1ṡ bar-1), at room temperature. The time of arrival spectra revealed two peaks throughout the entire range studied which were attributed to ion species with 3-carbons (C3H5+, C3H6+ C3H8+ and C3H9+) and with 4-carbons (C4H7+, C4H9+ and C4H10+). Besides these, and for Xe concentrations above 70%, a bump starts to appear at the right side of the main peak for reduced electric fields higher than 20 Td, which was attributed to the resonant charge transfer of C2H6+ to C2H6 that affects the mobility of its ion products (C3H8+ and C3H9+). The time of arrival spectra for Xe concentrations of 20%, 50%, 70% and 90% are presented, together with the reduced mobilities as a function of the Xe concentration calculated from the peaks observed for the low reduced electric fields and pressures studied.

Effect of H/C ratio on coal ignition

Energy Technology Data Exchange (ETDEWEB)

Furimsky, E.

1988-09-01

The Cahn balance technique was found to be suitable for estimating ignition temperature and its dependence on the H/C ratio of the coal. This temperature decreased with increasing H/C ratio of coals. For coals a linear correlation between H/C ratio and the temperature was established. Chars derived from the coals deviated from the linear correlation established on coals. 17 refs., 4 figs.

Interconversion of η3-H2SiRR' σ-complexes and 16-electron silylene complexes via reversible H-H or C-H elimination.

Science.gov (United States)

Lipke, Mark C; Neumeyer, Felix; Tilley, T Don

2014-04-23

Solid samples of η(3)-silane complexes [PhBP(Ph)3]RuH(η(3)-H2SiRR') (R,R' = Et2, 1a; PhMe, 1b; Ph2, 1c, MeMes, 1d) decompose when exposed to dynamic vacuum. Gas-phase H2/D2 exchange between isolated, solid samples of 1c-d3 and 1c indicate that a reversible elimination of H2 is the first step in the irreversible decomposition. An efficient solution-phase trap for hydrogen, the 16-electron ruthenium benzyl complex [PhBP(Ph)3]Ru[η(3)-CH2(3,5-Me2C6H3)] (3) reacts quantitatively with H2 in benzene via elimination of mesitylene to form the η(5)-cyclohexadienyl complex [PhBP(Ph)3]Ru(η(5)-C6H7) (4). This H2 trapping reaction was utilized to drive forward and quantify the elimination of H2 from 1b,d in solution, which resulted in the decomposition of 1b,d to form 4 and several organosilicon products that could not be identified. Reaction of {[PhBP(Ph)3]Ru(μ-Cl)}2 (2) with (THF)2Li(SiHMes2) forms a new η(3)-H2Si species [PhBP(Ph)3]Ru[CH2(2-(η(3)-H2SiMes)-3,5-Me2C6H2)] (5) which reacts with H2 to form the η(3)-H2SiMes2 complex [PhBP(Ph)3]RuH(η(3)-H2SiMes2) (1e). Complex 1e was identified by NMR spectroscopy prior to its decomposition by elimination of Mes2SiH2 to form 4. DFT calculations indicate that an isomer of 5, the 16-electron silylene complex [PhBP(Ph)3]Ru(μ-H)(═SiMes2), is only 2 kcal/mol higher in energy than 5. Treatment of 5 with XylNC (Xyl = 2,6-dimethylphenyl) resulted in trapping of [PhBP(Ph)3]Ru(μ-H)(═SiMes2) to form the 18-electron silylene complex [PhBP(Ph)3]Ru(CNXyl)(μ-H)(═SiMes2) (6). A closely related germylene complex [PhBP(Ph)3]Ru[CN(2,6-diphenyl-4-MeC6H2)](H)(═GeH(t)Bu) (8) was prepared from reaction of (t)BuGeH3 with the benzyl complex [PhBP(Ph)3]Ru[CN(2,6-diphenyl-4-MeC6H2)][η(1)-CH2(3,5-Me2C6H3)] (7). Single crystal XRD analysis indicated that unlike for 6, the hydride ligand in 8 is a terminal hydride that does not engage in 3c-2e Ru-H → Ge bonding. Complex 1b is an effective precatalyst for the catalytic Ge-H dehydrocoupling

One-loop calculations of photon splitting in a relativistic quantum plasma by the Green function method

International Nuclear Information System (INIS)

De Lya Insera, V.; Ferrer, Eh.; Shabad, A.E.

1986-01-01

Homogeneous and isotopic plasma of electrons and positrons is considered. Coefficients of covariant expansion of three-photon vertex in one-loop approximation of a technique of the Green temperature functions have been calculated and as a result amplitudes of different processes probability with the participation of three photons giving the data on the polarization state probability of incoming and outgoing photons in the splitting process. Sequences of all exact symmetries, which must be accomplished for vertex tensor, have been checked from calculational results. A case of charge-symmetrical plasma and a special case of photon collinearity have been considered

Photo- and radiation-chemical stability of molecules. Reactions of monomolecular hydrogen atom splitting off

International Nuclear Information System (INIS)

Plotnikov, V.G.; Ovchinnikov, A.A.

1978-01-01

In the review of works published up to 1978 one of the main problems of radiation chemistry is discussed, namely the relationship between the structure of organic molecules and their resistance to the effect of ionizing radiation. Theoretical aspects of this problem are considered for reactions of monomolecular hydrogen atom splitting off. It is shown that the radical yield in low-temperature radiation-chemical experiments is connected with the position of lower triplet states of molecules, ionization potentials, polarity of medium and the energy of C-H bonds in cation radicals

Specific primary ionization induced by minimum ionizing electrons in CH4, C2H6, C3H8, i-C4H10, Ar, DME,TEA and TMAE

International Nuclear Information System (INIS)

Melamud, G.; Breskin, A.; Chechik, R.; Pansky, A.

1992-10-01

Specific primary ionization induced by minimum ionizing electrons has been measured in several gases and vapors. Charges deposited by β-electrons in a low pressure gas, were collected, amplified by a multistep gaseous electron multiplier and counted. The high counting efficiency of the multiplier provided results of systematically higher values as compared to existing data. The respective values of the specific primary ionization in CH 4 C 2 H 6 , C 3 H 8 ,i-C 4 H 10 , Argon, Dimethylether, Triethylamine and Tetrakis(dimethylamino) ethylene are: 0.034, 0.065, 0.095, 0.12, 0.03, 0.082, 0.0195 and 0.370 clusters/cm*Torr. We present the experimental method and discuss the results and their accuracy. (authors)

Some effects of horizontal discretization on linear baroclinic and symmetric instabilities

Science.gov (United States)

Barham, William; Bachman, Scott; Grooms, Ian

2018-05-01

The effects of horizontal discretization on linear baroclinic and symmetric instabilities are investigated by analyzing the behavior of the hydrostatic Eady problem in ocean models on the B and C grids. On the C grid a spurious baroclinic instability appears at small wavelengths. This instability does not disappear as the grid scale decreases; instead, it simply moves to smaller horizontal scales. The peak growth rate of the spurious instability is independent of the grid scale as the latter decreases. It is equal to cf /√{Ri} where Ri is the balanced Richardson number, f is the Coriolis parameter, and c is a nondimensional constant that depends on the Richardson number. As the Richardson number increases c increases towards an upper bound of approximately 1/2; for large Richardson numbers the spurious instability is faster than the Eady instability. To suppress the spurious instability it is recommended to use fourth-order centered tracer advection along with biharmonic viscosity and diffusion with coefficients (Δx) 4 f /(32√{Ri}) or larger where Δx is the grid scale. On the B grid, the growth rates of baroclinic and symmetric instabilities are too small, and converge upwards towards the correct values as the grid scale decreases; no spurious instabilities are observed. In B grid models at eddy-permitting resolution, the reduced growth rate of baroclinic instability may contribute to partially-resolved eddies being too weak. On the C grid the growth rate of symmetric instability is better (larger) than on the B grid, and converges upwards towards the correct value as the grid scale decreases.

Spherically symmetric solutions, Newton's Law, and the infrared limit λ→1 in covariant Horava-Lifshitz gravity

International Nuclear Information System (INIS)

Alexandre, Jean; Pasipoularides, Pavlos

2011-01-01

In this note we examine whether spherically symmetric solutions in covariant Horava-Lifshitz gravity can reproduce Newton's Law in the IR limit λ→1. We adopt the position that the auxiliary field A is independent of the space-time metric [J. Alexandre and P. Pasipoularides, Phys. Rev. D 83, 084030 (2011).][J. Greenwald, V. H. Satheeshkumar, and A. Wang, J. Cosmol. Astropart. Phys. 12 (2010) 007.], and we assume, as in [A. M. da Silva, Classical Quantum Gravity 28, 055011 (2011).], that λ is a running coupling constant. We show that under these assumptions, spherically symmetric solutions fail to restore the standard Newtonian physics in the IR limit λ→1, unless λ does not run, and has the fixed value λ=1. Finally, we comment on the Horava and Melby-Thompson approach [P. Horava and C. M. Melby-Thompson, Phys. Rev. D 82, 064027 (2010).] in which A is assumed as a part of the space-time metric in the IR.

Superhard nanocomposite nc-TiC/a-C:H film fabricated by filtered cathodic vacuum arc technique

International Nuclear Information System (INIS)

Wang Yaohui; Zhang Xu; Wu Xianying; Zhang Huixing; Zhang Xiaoji

2008-01-01

Superhard nanocomposite nc-TiC/a-C:H films, with an excellent combination of high elastic recovery, low friction coefficient and good H/E ratio, were prepared by filtered cathodic vacuum arc technique using the C 2 H 2 gas as the precursor. The effect of C 2 H 2 flow rate on the microstructure, phase composition, mechanical and tribological properties of nanocomposite nc-TiC/a-C:H films have been investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy disperse spectroscopy (EDS), microindentation and tribotester measurements. It was observed that the C 2 H 2 flow rate significantly affected the Ti content and hardness of films. Furthermore, by selecting the proper value for C 2 H 2 flow rate, 20 sccm, one can deposit the nanocomposite film nc-TiC/a-C:H with excellent properties such as superhardness (66.4 GPa), high elastic recovery (83.3%) and high H/E ratio (0.13)

Proton relays in anomalous carbocations dictate spectroscopy, stability, and mechanisms: case studies on C2H5+ and C3H3.

Science.gov (United States)

Sager, LeeAnn M; Iyengar, Srinivasan S

2017-10-18

We present a detailed analysis of the anomalous carbocations: C 2 H 5 + and C 3 H 3 + . This work involves (a) probing electronic structural properties, (b) ab initio dynamics simulations over a range of internal energies, (c) analysis of reduced dimensional potential surfaces directed along selected conformational transition pathways, (d) dynamically averaged vibrational spectra computed from ab initio dynamics trajectories, and (e) two-dimensional time-frequency analysis to probe conformational dynamics. Key findings are as follows: (i) as noted in our previous study on C 2 H 3 + , it appears that these non-classical carbocations are stabilized by delocalized nuclear frameworks and "proton shuttles". We analyze this nuclear delocalization and find critical parallels between conformational changes in C 2 H 3 + , C 2 H 5 + , and C 3 H 3 + . (ii) The vibrational signatures of C 2 H 5 + are dominated by the "bridge-proton" conformation, but also show critical contributions from the "classical" configuration, which is a transition state at almost all levels of theory. This result is further substantiated through two-dimensional time-frequency analysis and is at odds with earlier explanations of the experimental spectra, where frequencies close to the classical region were thought to arise from an impurity. While this is still possible, our results here indicate an additional (perhaps more likely) explanation that involves the "classical" isomer. (iii) Finally, in the case of C 3 H 3 + our explanation of the experimental result includes the presence of multiple, namely, "cyclic", "straight", and propargyl, configurations. Proton shuttles and nuclear delocalization, reminiscent of those seen in the case of C 2 H 3 + , were seen all through and have a critical role in all our observations.

Mesotherapy for benign symmetric lipomatosis.

Science.gov (United States)

Hasegawa, Toshio; Matsukura, Tomoyuki; Ikeda, Shigaku

2010-04-01

Benign symmetric lipomatosis, also known as Madelung disease, is a rare disorder characterized by fat distribution around the shoulders, arms, and neck in the context of chronic alcoholism. Complete excision of nonencapsulated lipomas is difficult. However, reports describing conservative therapeutic measures for lipomatosis are rare. The authors present the case of a 42-year-old man with a diagnosis of benign symmetric lipomatosis who had multiple, large, symmetrical masses in his neck. Multiple phosphatidylcholine injections in the neck were administered 4 weeks apart, a total of seven times to achieve lipolysis. The patient's lipomatosis improved in response to the injections, and he achieved good cosmetic results. Intralesional injection, termed mesotherapy, using phosphatidylcholine is a potentially effective therapy for benign symmetric lipomatosis that should be reconsidered as a therapeutic option for this disease.

Dynamics of a split torque helicopter transmission. M.S. Thesis - Cleveland State Univ.

Science.gov (United States)

Krantz, Timothy L.

1994-01-01

Split torque designs, proposed as alternatives to traditional planetary designs for helicopter main rotor transmissions, can save weight and be more reliable than traditional designs. This report presents the results of an analytical study of the system dynamics and performance of a split torque gearbox that uses a balance beam mechanism for load sharing. The Lagrange method was applied to develop a system of equations of motion. The mathematical model includes time-varying gear mesh stiffness, friction, and manufacturing errors. Cornell's method for calculating the stiffness of spur gear teeth was extended and applied to helical gears. The phenomenon of sidebands spaced at shaft frequencies about gear mesh fundamental frequencies was simulated by modeling total composite gear errors as sinusoid functions. Although the gearbox has symmetric geometry, the loads and motions of the two power paths differ. Friction must be considered to properly evaluate the balance beam mechanism. For the design studied, the balance beam is not an effective device for load sharing unless the coefficient of friction is less than 0.003. The complete system stiffness as represented by the stiffness matrix used in this analysis must be considered to precisely determine the optimal tooth indexing position.

Reaction of the C2H radical with 1-butyne (C4H6): Low Temperature Kinetics and Isomer-Specific Product Detection

Energy Technology Data Exchange (ETDEWEB)

Soorkia, Satchin; Trevitt, Adam J.; Selby, Talitha M.; Osborn, David L.; Taatjes, Craig A.; Wilson, Kevin R.; Leone, Stephen R.

2009-12-22

The rate coefficient for the reaction of the ethynyl radical (C{sub 2}H) with 1-butyne (H-C{triple_bond}C-CH{sub 2}-CH{sub 3}) is measured in a pulsed Laval nozzle apparatus. Ethynyl radicals are formed by laser photolysis of acetylene (C{sub 2}H{sub 2}) at 193 nm and detected via chemiluminescence (C{sub 2}H + O{sub 2} {yields} CH (A{sup 2}{Delta}) + CO{sub 2}). The rate coefficients are measured over the temperature range of 74-295 K. The C{sub 2}H + 1-butyne reaction exhibits no barrier and occurs with rate constants close to the collision limit. The temperature dependent rate coefficients can be fit within experimental uncertainties by the expression k = (2.4 {+-} 0.5) x 10{sup -10} (T/295 K)-(0.04 {+-} 0.03) cm{sup 3} molecule{sup -1}s{sup -1}. Reaction products are detected at room temperature (295 K) and 533 Pa using a Multiplexed Photoionization Mass Spectrometer (MPIMS) coupled to the tunable VUV synchrotron radiation from the Advanced Light Source at the Lawrence Berkeley National Laboratory. Two product channels are identified for this reaction: m/z = 64 (C{sub 5}H{sub 4}) and m/z = 78 (C{sub 6}H{sub 6}) corresponding to the CH{sub 3}- and H-loss channels, respectively. Photoionization efficiency (PIE) curves are used to analyze the isomeric composition of both product channels. The C{sub 5}H{sub 4} products are found to be exclusively linear isomers composed of ethynylallene and methyldiacetylene in a 4:1 ratio. In contrast, the C{sub 6}H{sub 6} product channel includes two cyclic isomers, fulvene 18({+-}5)% and 3,4-dimethylenecyclobut-1-ene 32({+-}8)%, as well as three linear isomers, 2-ethynyl-1,3-butadiene 8({+-}5)%, 3,4-hexadiene-1-yne 28({+-}8)% and 1,3-hexadiyne 14({+-}5)%. Within experimental uncertainties, we do not see appreciable amounts of benzene and an upper limit of 10% is estimated. Diacetylene (C{sub 4}H{sub 2}) formation via the C{sub 2}H{sub 5}-loss channel is also thermodynamically possible but cannot be observed due to experimental

Splitting methods for split feasibility problems with application to Dantzig selectors

International Nuclear Information System (INIS)

He, Hongjin; Xu, Hong-Kun

2017-01-01

The split feasibility problem (SFP), which refers to the task of finding a point that belongs to a given nonempty, closed and convex set, and whose image under a bounded linear operator belongs to another given nonempty, closed and convex set, has promising applicability in modeling a wide range of inverse problems. Motivated by the increasingly data-driven regularization in the areas of signal/image processing and statistical learning, in this paper, we study the regularized split feasibility problem (RSFP), which provides a unified model for treating many real-world problems. By exploiting the split nature of the RSFP, we shall gainfully employ several efficient splitting methods to solve the model under consideration. A remarkable advantage of our methods lies in their easier subproblems in the sense that the resulting subproblems have closed-form representations or can be efficiently solved up to a high precision. As an interesting application, we apply the proposed algorithms for finding Dantzig selectors, in addition to demonstrating the effectiveness of the splitting methods through some computational results on synthetic and real medical data sets. (paper)

Salt splitting using ceramic membranes

Energy Technology Data Exchange (ETDEWEB)

Kurath, D.E. [Pacific Northwest National Lab., Richland, WA (United States)

1997-10-01

Many radioactive aqueous wastes in the DOE complex have high concentrations of sodium that can negatively affect waste treatment and disposal operations. Sodium can decrease the durability of waste forms such as glass and is the primary contributor to large disposal volumes. Waste treatment processes such as cesium ion exchange, sludge washing, and calcination are made less efficient and more expensive because of the high sodium concentrations. Pacific Northwest National Laboratory (PNNL) and Ceramatec Inc. (Salt Lake City UT) are developing an electrochemical salt splitting process based on inorganic ceramic sodium (Na), super-ionic conductor (NaSICON) membranes that shows promise for mitigating the impact of sodium. In this process, the waste is added to the anode compartment, and an electrical potential is applied to the cell. This drives sodium ions through the membrane, but the membrane rejects most other cations (e.g., Sr{sup +2}, Cs{sup +}). The charge balance in the anode compartment is maintained by generating H{sup +} from the electrolysis of water. The charge balance in the cathode is maintained by generating OH{sup {minus}}, either from the electrolysis of water or from oxygen and water using an oxygen cathode. The normal gaseous products of the electrolysis of water are oxygen at the anode and hydrogen at the cathode. Potentially flammable gas mixtures can be prevented by providing adequate volumes of a sweep gas, using an alternative reductant or destruction of the hydrogen as it is generated. As H{sup +} is generated in the anode compartment, the pH drops. The process may be operated with either an alkaline (pH>12) or an acidic anolyte (pH <1). The benefits of salt splitting using ceramic membranes are (1) waste volume reduction and reduced chemical procurement costs by recycling of NaOH; and (2) direct reduction of sodium in process streams, which enhances subsequent operations such as cesium ion exchange, calcination, and vitrification.

Coded Splitting Tree Protocols

DEFF Research Database (Denmark)

Sørensen, Jesper Hemming; Stefanovic, Cedomir; Popovski, Petar

2013-01-01

This paper presents a novel approach to multiple access control called coded splitting tree protocol. The approach builds on the known tree splitting protocols, code structure and successive interference cancellation (SIC). Several instances of the tree splitting protocol are initiated, each...... instance is terminated prematurely and subsequently iterated. The combined set of leaves from all the tree instances can then be viewed as a graph code, which is decodable using belief propagation. The main design problem is determining the order of splitting, which enables successful decoding as early...

Quantum plasmon and Rashba-like spin splitting in self-assembled Co x C60 composites with enhanced Co content (x > 15)

Science.gov (United States)

Lavrentiev, Vasily; Chvostova, Dagmar; Stupakov, Alexandr; Lavrentieva, Inna; Vacik, Jiri; Motylenko, Mykhaylo; Barchuk, Mykhailo; Rafaja, David; Dejneka, Alexandr

2018-04-01

Driving by interplay between plasmonic and magnetic effects in organic composite semiconductors is a challenging task with a huge potential for practical applications. Here, we present evidence of a quantum plasmon excited in the self-assembled Co x C60 nanocomposite films with x > 15 (interval of the Co cluster coalescence) and analyse it using the optical absorption (OA) spectra. In the case of Co x C60 film with x = 16 (LF sample), the quantum plasmon generated by the Co/CoO clusters is found as the 1.5 eV-centred OA peak. This finding is supported by the establishment of four specific C60-related OA lines detected at the photon energies E p > 2.5 eV. Increase of the Co content up to x = 29 (HF sample) leads to pronounced enhancement of OA intensity in the energy range of E p > 2.5 eV and to plasmonic peak downshift of 0.2 eV with respect to the peak position in the LF spectrum. Four pairs of the OA peaks evaluated in the HF spectrum at E p > 2.5 eV reflect splitting of the C60-related lines, suggesting great change in the microscopic conditions with increasing x. Analysis of the film nanostructure and the plasmon-induced conditions allows us to propose a Rashba-like spin splitting effect that suggests valuable sources for spin polarization.

Ligand-controlled, tunable silver-catalyzed C-H amination.

Science.gov (United States)

Alderson, Juliet M; Phelps, Alicia M; Scamp, Ryan J; Dolan, Nicholas S; Schomaker, Jennifer M

2014-12-03

The development of readily tunable and regioselective C-H functionalization reactions that operate solely through catalyst control remains a challenge in modern organic synthesis. Herein, we report that simple silver catalysts supported by common nitrogenated ligands can be used to tune a nitrene transfer reaction between two different types of C-H bonds. The results reported herein represent the first example of ligand-controlled and site-selective silver-promoted C-H amination.

Advanced TiC/a-C: H nanocomposite coatings deposited by magnetron sputtering

OpenAIRE

Pei, Y.T.; Galvan, D.; Hosson, J.Th.M. De; Strondl, C.

2006-01-01

TiC/a-C:H nanocomposite coatings have been deposited by magnetron Sputtering. They consist of 2-5 nm TiC nanocrystallites embedded in the amorphous hydrocarbon (a-C:H) matrix. A transition from a Columnar to a glassy microstructure has been observed in the nanocomposite coatings with increasing substrate bias or carbon content. Micro-cracks induced by nanoindentation or wear tests readily propagate through the column boundaries whereas the coatings without a columnar inicrostructure exhibit s...

Reduced dimension rovibrational variational calculations of the S1 state of C2H2. I. Methodology and implementation

International Nuclear Information System (INIS)

Changala, P. Bryan

2014-01-01

The bending and torsional degrees of freedom in S 1 acetylene, C 2 H 2 , are subject to strong vibrational resonances and rovibrational interactions, which create complex vibrational polyad structures even at low energy. As the internal energy approaches that of the barrier to cis-trans isomerization, these energy level patterns undergo further large-scale reorganization that cannot be satisfactorily treated by traditional models tied to local minima of the potential energy surface for nuclear motion. Experimental spectra in the region near the cis-trans transition state have revealed these complicated new patterns. In order to understand near-barrier spectroscopic observations and to predict the detailed effects of cis-trans isomerization on the rovibrational energy level structure, we have performed reduced dimension rovibrational variational calculations of the S 1 state. In this paper, we present the methodological details, several of which require special care. Our calculation uses a high accuracy ab initio potential surface and a fully symmetrized extended complete nuclear permutation inversion group theoretical treatment of a multivalued internal coordinate system that is appropriate for large amplitude bending and torsional motions. We also discuss the details of the rovibrational basis functions and their symmetrization, as well as the use of a constrained reduced dimension rovibrational kinetic energy operator

Identification of solution products of lanthanoid (3) diethyldithiocarbamatohexamethyl phosphotriamide compounds from IR, electron and sup 1 H, sup 13 C, sup 31 P NMR absorption spectra. Identifikatsiya produktov rastvoreniya diehtilditiokarbamatogeksametil fosfotriamidnykh soedinenij lantanoidov (3) po IK, ehlektronnym i YaMR sup 1 H, sup 13 C, sup 31 P spektram pogloshcheniya

Energy Technology Data Exchange (ETDEWEB)

Skopenko, V V; Savost' yanova, A F; Trachevskij, V V; Gorbalyuk, A D; Sukhan, T A [Kievskij Gosudarstvennyj Univ., Kiev (Ukrainian SSR)

1991-01-01

By the methods of conductometry, IR, electron and {sup 1}H, {sup 13}C, {sup 31}P NMR spectroscopy nonaqueous solutions of the compounds (La(S{sub 2}CNEt{sub 2})Hmpa{sub 5})(BPh{sub 4}){sub 2}, Hmpa=OP(NMe{sub 2}){sub 3}; (Ln(S{sub 2}CNEt{sub 2}){sub 2}Hmpa{sub 3})BPh{sub 4}, Ln=Y, La-Lu; (Ln(S{sub 2}CNEt{sub 2}){sub 3}Hmpa{sub 2}), Ln=La-Gd, have been investigated. It is ascertained that bis-dithiocarbamate compounds are dissolved in all the studied solvents with preservation of composition and structure of lanthanide (3) inner coordination sphere. Tris-dithiocarbamates in nonaqueous solutions are subjected to reactions of ligand redistribution according to schemes depending on the solvent nature. In the process of dissolving of lanthanum monodithiocarbamate bond isomerization of dithiocarbamate groups occurs, which is pronounced in splitting of {sup 1}H and {sup 13}C NMR signals.

Analysis of operator splitting errors for near-limit flame simulations

Energy Technology Data Exchange (ETDEWEB)

Lu, Zhen; Zhou, Hua [Center for Combustion Energy, Tsinghua University, Beijing 100084 (China); Li, Shan [Center for Combustion Energy, Tsinghua University, Beijing 100084 (China); School of Aerospace Engineering, Tsinghua University, Beijing 100084 (China); Ren, Zhuyin, E-mail: zhuyinren@tsinghua.edu.cn [Center for Combustion Energy, Tsinghua University, Beijing 100084 (China); School of Aerospace Engineering, Tsinghua University, Beijing 100084 (China); Lu, Tianfeng [Department of Mechanical Engineering, University of Connecticut, Storrs, CT 06269-3139 (United States); Law, Chung K. [Center for Combustion Energy, Tsinghua University, Beijing 100084 (China); Department of Mechanical and Aerospace Engineering, Princeton University, Princeton, NJ 08544 (United States)

2017-04-15

High-fidelity simulations of ignition, extinction and oscillatory combustion processes are of practical interest in a broad range of combustion applications. Splitting schemes, widely employed in reactive flow simulations, could fail for stiff reaction–diffusion systems exhibiting near-limit flame phenomena. The present work first employs a model perfectly stirred reactor (PSR) problem with an Arrhenius reaction term and a linear mixing term to study the effects of splitting errors on the near-limit combustion phenomena. Analysis shows that the errors induced by decoupling of the fractional steps may result in unphysical extinction or ignition. The analysis is then extended to the prediction of ignition, extinction and oscillatory combustion in unsteady PSRs of various fuel/air mixtures with a 9-species detailed mechanism for hydrogen oxidation and an 88-species skeletal mechanism for n-heptane oxidation, together with a Jacobian-based analysis for the time scales. The tested schemes include the Strang splitting, the balanced splitting, and a newly developed semi-implicit midpoint method. Results show that the semi-implicit midpoint method can accurately reproduce the dynamics of the near-limit flame phenomena and it is second-order accurate over a wide range of time step size. For the extinction and ignition processes, both the balanced splitting and midpoint method can yield accurate predictions, whereas the Strang splitting can lead to significant shifts on the ignition/extinction processes or even unphysical results. With an enriched H radical source in the inflow stream, a delay of the ignition process and the deviation on the equilibrium temperature are observed for the Strang splitting. On the contrary, the midpoint method that solves reaction and diffusion together matches the fully implicit accurate solution. The balanced splitting predicts the temperature rise correctly but with an over-predicted peak. For the sustainable and decaying oscillatory

Symmetry breaking and spectral considerations of the surprisingly floppy c-C3H radical and the related dipole-bound excited state of c-C3H-

Science.gov (United States)

Bassett, Matthew K.; Fortenberry, Ryan C.

2017-06-01

The C3H radical is believed to be prevalent throughout the interstellar medium and may be involved in the formation of polycyclic aromatic hydrocarbons. C3H exists as both a linear and a cyclic isomer. The C2 v cyclopropenylidenyl radical isomer was detected in the dark molecular cloud TMC-1, and the linear propenylidenyl radical isomer has been observed in various dark molecular clouds. Even though the c-C3H radical has been classified rotationally, the vibrational frequencies of this seemingly important interstellar molecule have never been directly observed. Established, highly accurate quartic force field methodologies are employed here to compute useful geometrical data, spectroscopic constants, and vibrational frequencies. The computed rotational constants are consistent with the experimental results. Consequently, the three a1 (ν1, ν2, and ν3) and one b1 (ν6) anharmonic vibrational frequencies at 3117.7 cm-1, 1564.3 cm-1, 1198.5 cm-1, and 826.7 cm-1, respectively, are reliable predictions for these, as of yet unseen, observables. Unfortunately, the two b2 fundamentals (ν4 and ν5) cannot be treated adequately in the current approach due to a flat and possible double-well potential described in detail herein. The dipole-bound excited state of the anion suffers from the same issues and may not even be bound. However, the trusted fundamental vibrational frequencies described for the neutral radical should not be affected by this deformity and are the first robustly produced for c-C3H. The insights gained here will also be applicable to other structures containing three-membered bare and exposed carbon rings that are surprisingly floppy in nature.

Effect of doping (C or N) and co-doping (C+N) on the photoactive properties of magnetron sputtered titania coatings for the application of solar water-splitting.

Science.gov (United States)

Rahman, M; Dang, B H Q; McDonnell, K; MacElroy, J M D; Dowling, D P

2012-06-01

The photocatalytic splitting of water into hydrogen and oxygen using a photoelectrochemical (PEC) cell containing titanium dioxide (TiO2) photoanode is a potentially renewable source of chemical fuels. However, the size of the band gap (-3.2 eV) of the TiO2 photocatalyst leads to its relatively low photoactivity toward visible light in a PEC cell. The development of materials with smaller band gaps of approximately 2.4 eV is therefore necessary to operate PEC cells efficiently. This study investigates the effect of dopant (C or N) and co-dopant (C+N) on the physical, structural and photoactivity of TiO2 nano thick coating. TiO2 nano-thick coatings were deposited using a closed field DC reactive magnetron sputtering technique, from titanium target in argon plasma with trace addition of oxygen. In order to study the influence of doping such as C, N and C+N inclusions in the TiO2 coatings, trace levels of CO2 or N2 or CO2+N2 gas were introduced into the deposition chamber respectively. The properties of the deposited nano-coatings were determined using Spectroscopic Ellipsometry, SEM, AFM, Optical profilometry, XPS, Raman, X-ray diffraction UV-Vis spectroscopy and tri-electrode potentiostat measurements. Coating growth rate, structure, surface morphology and roughness were found to be significantly influenced by the types and amount of doping. Substitutional type of doping in all doped sample were confirmed by XPS. UV-vis measurement confirmed that doping (especially for C doped sample) facilitate photoactivity of sputtered deposited titania coating toward visible light by reducing bandgap. The photocurrent density (indirect indication of water splitting performance) of the C-doped photoanode was approximately 26% higher in comparison with un-doped photoanode. However, coating doped with nitrogen (N or N+C) does not exhibit good performance in the photoelectrochemical cell due to their higher charge recombination properties.

Triosmium cluster compounds containing isocyanide and hydride ligands. Crystal and molecular structures of (μ-H)(H)Os3(CO)10(CN-t-C4H9) and (μ-H)2Os3(CO)9(CN-t-C4H9)

International Nuclear Information System (INIS)

Adams, R.D.; Golembski, N.M.

1979-01-01

The structures of the compounds (μ-H)(H)Os 3 (CO) 10 (CN-t-C 4 H 9 ) and (μ-H) 2 Os 3 (CO) 9 (CN-t-C 4 H 9 ) have been revealed by x-ray crystallographic techniques. For (μ-H)(H)Os 3 (CO) 10 (CN-t-C 4 H 9 ): a = 9.064 (3), b = 12.225 (3), c = 20.364 (4) A; β = 98.73 (3) 0 ; space group P2 1 /c[C/sub 2h/ 5 ], No. 14; Z = 4; d/sub calcd/ = 2.79 g cm -3 . This compound contains a triangular cluster of three osmium atoms; Os(1)--Os(2) = 2.930 (1) A, Os(1)--Os(3) = 2.876 (1) A, and Os(2)--Os(3) = 3.000 (1) A. There are ten linear terminal carbonyl groups and one linear terminal isocyanide ligand which occupies an axial coordination site. The hydrogen atoms were not observed crystallographically, but their positions are strongly inferred from considerations of molecular geometry. For (μ-H) 2 Os 3 (CO) 9 (CN-t-C 4 H 9 ): a = 15.220 (8), b = 12.093 (6), c = 23.454 (5) A; space group Pbcn [D/sub 2h/ 14 ], No. 60; Z = 8; d/sub calcd/ = 2.79 g cm -3 . The compound is analogous to the parent carbonyl (μ-H) 2 Os 3 (CO) 10 and has two normal and one short osmium--osmium bonds: Os(1)--Os(2) = 2.827 (1) A, Os(1)--Os(3) = 2.828 (1) A, Os(2)--Os(3) = 2.691 (1) A. The isocyanide ligand resides in an equatorial coordination site on osmium Os(2). The hydrogen atoms were not observed but are believed to occupy bridging positions as in the parent carbonyl complex. 2 figures, 7 tables

An Examination Of Fracture Splitting Parameters Of Crackable Connecting Rods

Directory of Open Access Journals (Sweden)

Zafer Özdemir

2000-06-01

Full Text Available Fracture splitting method is an innovative processing technique in the field of automobile engine connecting rod (con/rod manufacturing. Compared with traditional method, this technique has remarkable advantages. Manufacturing procedures, equipment and tools investment can be decreased and energy consumption reduced remarkably. Furthermore, product quality and bearing capability can also be improved. It provides a high quality, high accuracy and low cost route for producing connecting rods (con/rods. With the many advantages mentioned above, this method has attracted manufacturers attention and has been utilized in many types of con/rod manufacturing. In this article, the method and the advantages it provides, such as materials, notches for fracture splitting, fracture splitting conditions and fracture splitting equipment are discussed in detail. The paper describes an analysis of examination of fracture splitting parameters and optik-SEM fractography of C70S6 crackable connectıng rod. Force and velocity parameters are investigated. That uniform impact force distrubition starting from the starting notch causes brittle and cleavage failure mode is obtained as a result. This induces to decrease the toughness.

Synthesis and crystal structure of the solid solution Co3(SeO3)3-x(PO3OH)x(H2O) involving crystallographic split positions of Se4+ and P5+.

Science.gov (United States)

Zimmermann, Iwan; Johnsson, Mats

2013-10-21

Three new cobalt selenite hydroxo-phosphates laying in the solid solution Co3(SeO3)3-x(PO3OH)x(H2O), with x = 0.8, x = 1.0, and x = 1.2 are reported. Single crystals were obtained by hydrothermal synthesis and the crystal structure was determined by single crystal X-ray diffraction. The structure can be described as a 3D framework having selenite and hydroxo-phosphate groups protruding into channels in the crystal structure. Se(4+) and P(5+) share a split position in the structure so that either SeO3 groups having a stereochemically active lone pair or tetrahedrally coordinated PO3OH groups are present. The OH-group is thus only present when the split position is occupied by P(5+). The crystal water is coordinated to a cobalt atom and TG and IR measurements show that the water and hydroxyl groups leave the structure at unusually high temperatures (>450 °C). Magnetic susceptibility measurements show antiferromagnetic coupling below 16 K and a magnetic moment of 4.02(3) μB per Co atom was observed.

Evaluation of Mandibular Anatomy Associated With Bad Splits in Sagittal Split Ramus Osteotomy of Mandible.

Science.gov (United States)

Wang, Tongyue; Han, Jeong Joon; Oh, Hee-Kyun; Park, Hong-Ju; Jung, Seunggon; Park, Yeong-Joon; Kook, Min-Suk

2016-07-01

This study aimed to identify risk factors associated with bad splits during sagittal split ramus osteotomy by using three-dimensional computed tomography. This study included 8 bad splits and 47 normal patients without bad splits. Mandibular anatomic parameters related to osteotomy line were measured. These included anteroposterior width of the ramus at level of lingula, distance between external oblique ridge and lingula, distance between sigmoid notch and inferior border of mandible, mandibular angle, distance between inferior outer surface of mandibular canal and inferior border of mandible under distal root of second molar (MCEM), buccolingual thickness of the ramus at level of lingula, and buccolingual thickness of the area just distal to first molar (BTM1) and second molar (BTM2). The incidence of bad splits in 625 sagittal split osteotomies was 1.28%. Compared with normal group, bad split group exhibited significantly thinner BTM2 and shorter sigmoid notch and inferior border of mandible (P bad splits. These anatomic data may help surgeons to choose the safest surgical techniques and best osteotomy sites.

Enzyme-controlled nitrogen-atom transfer enables regiodivergent C-H amination.

Science.gov (United States)

Hyster, Todd K; Farwell, Christopher C; Buller, Andrew R; McIntosh, John A; Arnold, Frances H

2014-11-05

We recently demonstrated that variants of cytochrome P450BM3 (CYP102A1) catalyze the insertion of nitrogen species into benzylic C-H bonds to form new C-N bonds. An outstanding challenge in the field of C-H amination is catalyst-controlled regioselectivity. Here, we report two engineered variants of P450BM3 that provide divergent regioselectivity for C-H amination-one favoring amination of benzylic C-H bonds and the other favoring homo-benzylic C-H bonds. The two variants provide nearly identical kinetic isotope effect values (2.8-3.0), suggesting that C-H abstraction is rate-limiting. The 2.66-Å crystal structure of the most active enzyme suggests that the engineered active site can preorganize the substrate for reactivity. We hypothesize that the enzyme controls regioselectivity through localization of a single C-H bond close to the iron nitrenoid.

Entropy Analysis of Solar Two-Step Thermochemical Cycles for Water and Carbon Dioxide Splitting

Directory of Open Access Journals (Sweden)

Matthias Lange

2016-01-01

Full Text Available The present study provides a thermodynamic analysis of solar thermochemical cycles for splitting of H2O or CO2. Such cycles, powered by concentrated solar energy, have the potential to produce fuels in a sustainable way. We extend a previous study on the thermodynamics of water splitting by also taking into account CO2 splitting and the influence of the solar absorption efficiency. Based on this purely thermodynamic approach, efficiency trends are discussed. The comprehensive and vivid representation in T-S diagrams provides researchers in this field with the required theoretical background to improve process development. Furthermore, results about the required entropy change in the used redox materials can be used as a guideline for material developers. The results show that CO2 splitting is advantageous at higher temperature levels, while water splitting is more feasible at lower temperature levels, as it benefits from a great entropy change during the splitting step.

Multiparty symmetric sum types

DEFF Research Database (Denmark)

Nielsen, Lasse; Yoshida, Nobuko; Honda, Kohei

2010-01-01

This paper introduces a new theory of multiparty session types based on symmetric sum types, by which we can type non-deterministic orchestration choice behaviours. While the original branching type in session types can represent a choice made by a single participant and accepted by others...... determining how the session proceeds, the symmetric sum type represents a choice made by agreement among all the participants of a session. Such behaviour can be found in many practical systems, including collaborative workflow in healthcare systems for clinical practice guidelines (CPGs). Processes...... with the symmetric sums can be embedded into the original branching types using conductor processes. We show that this type-driven embedding preserves typability, satisfies semantic soundness and completeness, and meets the encodability criteria adapted to the typed setting. The theory leads to an efficient...

Direct approaches to nitriles via highly efficient nitrogenation strategy through C-H or C-C bond cleavage.

Science.gov (United States)

Wang, Teng; Jiao, Ning

2014-04-15

Because of the importance of nitrogen-containing compounds in chemistry and biology, organic chemists have long focused on the development of novel methodologies for their synthesis. For example, nitrogen-containing compounds show up within functional materials, as top-selling drugs, and as bioactive molecules. To synthesize these compounds in a green and sustainable way, researchers have focused on the direct functionalization of hydrocarbons via C-H or C-C bond cleavage. Although researchers have made significant progress in the direct functionalization of simple hydrocarbons, direct C-N bond formation via C-H or C-C bond cleavage remains challenging, in part because of the unstable character of some N-nucleophiles under oxidative conditions. The nitriles are versatile building blocks and precursors in organic synthesis. Recently, chemists have achieved the direct C-H cyanation with toxic cyanide salts in the presence of stoichiometric metal oxidants. In this Account, we describe recent progress made by our group in nitrile synthesis. C-H or C-C bond cleavage is a key process in our strategy, and azides or DMF serve as the nitrogen source. In these reactions, we successfully realized direct nitrile synthesis using a variety of hydrocarbon groups as nitrile precursors, including methyl, alkenyl, and alkynyl groups. We could carry out C(sp(3))-H functionalization on benzylic, allylic, and propargylic C-H bonds to produce diverse valuable synthetic nitriles. Mild oxidation of C═C double-bonds and C≡C triple-bonds also produced nitriles. The incorporation of nitrogen within the carbon skeleton typically involved the participation of azide reagents. Although some mechanistic details remain unclear, studies of these nitrogenation reactions implicate the involvement of a cation or radical intermediate, and an oxidative rearrangement of azide intermediate produced the nitrile. We also explored environmentally friendly oxidants, such as molecular oxygen, to make our

Influence of photoperiod and running wheel access on the entrainment of split circadian rhythms in hamsters

Directory of Open Access Journals (Sweden)

Elliott Jeffrey A

2005-06-01

Full Text Available Abstract Background In the laboratory, behavioral and physiological states of nocturnal rodents alternate, with a period near 24 h, between those appropriate for the night (e.g., elevated wheel-running activity and high melatonin secretion and for the day (e.g., rest and low melatonin secretion. Under appropriate 24 h light:dark:light:dark conditions, however, rodents may be readily induced to express bimodal rest/activity cycles that reflect a global temporal reorganization of the central neural pacemaker in the hypothalamus. We examine here how the relative length of the light and dark phases of the environmental cycle influences this rhythm splitting and the necessity of a running wheel for expression of this entrainment condition. Results Rhythm splitting was observed in wheel-running and general locomotion of Siberian and Syrian hamsters. The latter also manifest split rhythms in body temperature. Access to a running wheel was necessary neither for the induction nor maintenance of this entrainment pattern. While rhythms were only transiently split in many animals with two 5 h nights, the incidence of splitting was greater with twice daily nights of shorter duration. Removal of running wheels altered the body temperature rhythm but did not eliminate its clear bimodality. Conclusion The expression of entrained, split circadian rhythms exhibits no strict dependence on access to a running wheel, but can be facilitated by manipulation of ambient lighting conditions. These circadian entrainment patterns may be of therapeutic value to human shift-workers and others facing chronobiological challenges.

Spin-Rotation Hyperfine Splittings at Moderate to High J Values in Methanol

Science.gov (United States)

Xu, Li-Hong; Hougen, Jon T.; Belov, Sergey; Golubiatnikov, G. Yu; Lapinov, Alexander; Ilyushin, V.; Alekseev, E. A.; Mescheryakov, A. A.

2015-06-01

In this talk we present a possible explanation, based on torsionally mediated proton-spin-overall-rotation interaction operators, for the surprising observation in Nizhny Novgorod several years ago of doublets in some Lamb-dip sub-millimeter-wave transitions between torsion-rotation states of E symmetry in methanol. These observed doublet splittings, some as large as 70 kHz, were later confirmed by independent Lamb-dip measurements in Kharkov. In this talk we first show the observed J-dependence of the doublet splittings for two b-type Q branches (one from each laboratory), and then focus on our theoretical explanation. The latter involves three topics: (i) group theoretically allowed terms in the spin-rotation Hamiltonian, (ii) matrix elements of these terms between the degenerate components of torsion-rotation E states, calculated using wavefunctions from an earlier global fit of torsion-rotation transitions of methanol in the vt = 0, 1, and 2 states, and (iii) least-squares fits of coefficients of these terms to about 35 experimentally resolved doublet splittings in the quantum number ranges of K = -2 to +2, J = 13 to 34, and vt = 0. Rather pleasing residuals are obtained for these doublet splittings, and a number of narrow transitions, in which no doublet splitting could be detected, are also in agreement with predictions from the theory. Some remaining disagreements between experiment and the present theoretical explanation will be mentioned. G. Yu. Golubiatnikov, S. P. Belov, A. V. Lapinov, "CH_3OH Sub-Doppler Spectroscopy," (Paper MF04) and S.P. Belov, A.V. Burenin, G.Yu. Golubiatnikov, A.V. Lapinov, "What is the Nature of the Doublets in the E-Methanol Lamb-dip Spectra?" (Paper FB07), 68th International Symposium on Molecular Spectroscopy, Columbus, Ohio, June 2013. Li-Hong Xu, J. Fisher, R.M. Lees, H.Y. Shi, J.T. Hougen, J.C. Pearson, B.J. Drouin, G.A. Blake, R. Braakman, "Torsion-Rotation Global Analysis of the First Three Torsional States (vt = 0, 1, 2

Electroremovable Traceless Hydrazides for Cobalt-Catalyzed Electro-Oxidative C-H/N-H Activation with Internal Alkynes.

Science.gov (United States)

Mei, Ruhuai; Sauermann, Nicolas; Oliveira, João C A; Ackermann, Lutz

2018-06-27

Electrochemical oxidative C-H/N-H activations have been accomplished with a versatile cobalt catalyst in terms of [4 + 2] annulations of internal alkynes. The electro-oxidative C-H activation manifold proved viable with an undivided cell setup under exceedingly mild reaction conditions at room temperature using earth-abundant cobalt catalysts. The electrochemical cobalt catalysis prevents the use of transition metal oxidants in C-H activation catalysis, generating H 2 as the sole byproduct. Detailed mechanistic studies provided strong support for a facile C-H cobaltation by an initially formed cobalt(III) catalyst. The subsequent alkyne migratory insertion was interrogated by mass spectrometry and DFT calculations, providing strong support for a facile C-H activation and the formation of a key seven-membered cobalta(III) cycle in a regioselective fashion. Key to success for the unprecedented use of internal alkynes in electrochemical C-H/N-H activations was represented by the use of N-2-pyridylhydrazides, for which we developed a traceless electrocleavage strategy by electroreductive samarium catalysis at room temperature.

High resolution spectroscopy of 1,2-difluoroethane in a molecular beam: A case study of vibrational mode-coupling

Science.gov (United States)

Mork, Steven W.; Miller, C. Cameron; Philips, Laura A.

1992-09-01

The high resolution infrared spectrum of 1,2-difluoroethane (DFE) in a molecular beam has been obtained over the 2978-2996 cm-1 spectral region. This region corresponds to the symmetric combination of asymmetric C-H stretches in DFE. Observed rotational fine structure indicates that this C-H stretch is undergoing vibrational mode coupling to a single dark mode. The dark mode is split by approximately 19 cm-1 due to tunneling between the two identical gauche conformers. The mechanism of the coupling is largely anharmonic with a minor component of B/C plane Coriolis coupling. Effects of centrifugal distortion along the molecular A-axis are also observed. Analysis of the fine structure identifies the dark state as being composed of C-C torsion, CCF bend, and CH2 rock. Coupling between the C-H stretches and the C-C torsion is of particular interest because DFE has been observed to undergo vibrationally induced isomerization from the gauche to trans conformer upon excitation of the C-H stretch.

Rotationally symmetric structure in two extragalactic radio sources

International Nuclear Information System (INIS)

Lonsdale, C.J.; Morison, I.

1980-01-01

The new multi-telescope radio-linked interferometer (MTRLI) at Jodrell Bank was used during January and February 1980 at a frequency of 408 MHz to map the extragalactic radio sources 3C196 and 3C305 with a resolution of approximately 1 arc s. It is shown here that both the markedly symmetric structures observed and the spectral index distributions inferred from comparisons with previously published 5 GHz maps provide evidence for the source axes having rotated during the lifetime of the emitting regions. (U.K.)

13C, 1H spin-spin coupling constants. Pt. 4

International Nuclear Information System (INIS)

Aydin, R.; Guenther, H.

1979-01-01

One-bond, geminal, and vicinal 13 C, 1 H coupling constants have been determined for adamantane using α-and β-[D]adamantane and the relation sup(n)J( 13 C, 1 H)=6,5144sup(n)J( 13 C, 2 H) for the conversion of the measured sup(n)J( 13 C, 2 H) values. It is shown that the magnitude of 3 Jsub(trans) is strongly influenced by the substitution pattern. Relative H,D isotope effects for 13 C chemical shifts are given. (orig.) [de

Giant Rashba spin splitting in Bi2Se3: Tl

KAUST Repository

Singh, Nirpendra

2014-07-25

First-principles calculations are employed to demonstrate a giant Rashba spin splitting in Bi2Se3:Tl. Biaxial tensile and compressive strain is used to tune the splitting by modifying the potential gradient. The band gap is found to increase under compression and decreases under tension, whereas the dependence of the Rashba spin splitting on the strain is the opposite. Large values of αR = 1.57 eV Å at the bottom of the conduction band (electrons) and αR = 3.34 eV Å at the top of the valence band (holes) are obtained without strain. These values can be further enhanced to αR = 1.83 eV Å and αR = 3.64 eV Å, respectively, by 2% tensile strain. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Redox-neutral rhodium-catalyzed C-H functionalization of arylamine N-oxides with diazo compounds: primary C(sp(3))-H/C(sp(2))-H activation and oxygen-atom transfer.

Science.gov (United States)

Zhou, Bing; Chen, Zhaoqiang; Yang, Yaxi; Ai, Wen; Tang, Huanyu; Wu, Yunxiang; Zhu, Weiliang; Li, Yuanchao

2015-10-05

An unprecedented rhodium(III)-catalyzed regioselective redox-neutral annulation reaction of 1-naphthylamine N-oxides with diazo compounds was developed to afford various biologically important 1H-benzo[g]indolines. This coupling reaction proceeds under mild reaction conditions and does not require external oxidants. The only by-products are dinitrogen and water. More significantly, this reaction represents the first example of dual functiaonalization of unactivated a primary C(sp(3) )H bond and C(sp(2) )H bond with diazocarbonyl compounds. DFT calculations revealed that an intermediate iminium is most likely involved in the catalytic cycle. Moreover, a rhodium(III)-catalyzed coupling of readily available tertiary aniline N-oxides with α-diazomalonates was also developed under external oxidant-free conditions to access various aminomandelic acid derivatives by an O-atom-transfer reaction. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Improved Bunch Splitting for the 75ns LHC Beam

CERN Document Server

Damerau, H

2011-01-01

The 75ns variant was added to the PS arsenal of LHC-type beams by adapting the 20MHz cavity used to produce the 25 and 50ns variants to operate at a switchable 13MHz. This permitted splitting from harmonic 14 to 28, but at a cost in adiabaticity compared with the h=2142 splitting of the other two cases. Consequently, a delicate empirical optimization was necessary to bring the 75ns beam inside specification. More recently the speed at which the bunches, once fully distinct, are moved apart has been revisited and further optimization achieved. As a by-product, deliberately degrading the splitting by moving the bunches apart too quickly led to sufficient coherent motion in the resultant bunch pair to permit a voltage calibration of the 13MHz cavity by means of the influence on convergence of the rf voltage input into the iterative algorithm of the Tomoscope [1,2].

Compositional, structural and mechanical characteristics of nc-TiC/a-C:H nanocomposite films

International Nuclear Information System (INIS)

Wang Yaohui; Zhang Xu; Wu Xianying; Zhang Huixing; Zhang Xiaoji

2008-01-01

Nanocomposite nc-TiC/a-C:H films, with an unusual combination of superhardness, high elastic modulus and high elastic recovery, are prepared by filtered cathodic vacuum arc technique using the C 2 H 2 gas as the precursor. The effects of filter coil current on compositional, structural and mechanical properties of the nc-TiC/a-C:H films have been investigated by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), energy disperse spectroscopy (EDS), microindentation and tribotester measurements. XPS and Raman analyses show that composition and nanostructure of the nc-TiC/a-C:H films can be changed by varying the filter coil current. By selecting the proper value of filter coil current, 2.5 A, one can remarkably enhance the mechanical properties of films such as superhardness (43.6 GPa). The superhardness can be ascribed to the phase variation and the nanostructure.

Light Makes a Surface Banana-Bond Split: Photodesorption of Molecular Hydrogen from RuO ₂ (110)

Energy Technology Data Exchange (ETDEWEB)

Henderson, Michael A.; Mu, Rentao; Dahal, Arjun; Lyubinetsky, Igor; Dohnálek, Zdenek; Glezakou, Vassiliki-Alexandra; Rousseau, Roger

2016-07-20

The coordination of H2 to a metal center via polarization of its bond electron density, known as a Kubas complex, is the means by which H2 chemisorbs at Ru4+ sites on the rutile RuO2(110) surface. This distortion of electron density off an interatomic axis is often described as a ‘banana-bond.’ We show that the Ru-H2 banana-bond can be destabilized, and split, using visible light. Photodesorption of H2 (or D2) is evident by mass spectrometry and scanning tunneling microscopy. From time-dependent density functional theory, the key optical excitation splitting the Ru-H2 banana-bond involves an interband transition in RuO2 which effectively diminishes its Lewis acidity, and thereby weakening the Kubas complex. Such excitations are not expected to affect adsorbates on RuO2 given its metallic properties. Therefore, this common thermal co-catalyst employed in promoting water splitting is, itself, photo-active in the visible.

An Oxygen-Insensitive Hydrogen Evolution Catalyst Coated by a Molybdenum-Based Layer for Overall Water Splitting

KAUST Repository

Garcia Esparza, Angel T.; Shinagawa, Tatsuya; Ould-Chikh, Samy; Qureshi, Muhammad; Peng, Xuyuan; Wei, Nini; Anjum, Dalaver H.; Clo, Alain M.; Weng, Tsu-Chien; Nordlund, Dennis; Sokaras, Dimosthenis; Kubota, Jun; Domen, Kazunari; Takanabe, Kazuhiro

2017-01-01

For overall water-splitting systems, it is essential to establish O2 -insensitive cathodes that allow cogeneration of H2 and O2 . An acid-tolerant electrocatalyst is described, which employs a Mo-coating on a metal surface to achieve selective H2 evolution in the presence of O2 . In operando X-ray absorption spectroscopy identified reduced Pt covered with an amorphous molybdenum oxyhydroxide hydrate with a local structural order composed of polyanionic trimeric units of molybdenum(IV). The Mo layer likely hinders O2 gas permeation, impeding contact with active Pt. Photocatalytic overall water splitting proceeded using MoOx /Pt/SrTiO3 with inhibited water formation from H2 and O2 , which is the prevailing back reaction on the bare Pt/SrTiO3 photocatalyst. The Mo coating was stable in acidic media for multiple hours of overall water splitting by membraneless electrolysis and photocatalysis.

An Oxygen-Insensitive Hydrogen Evolution Catalyst Coated by a Molybdenum-Based Layer for Overall Water Splitting

KAUST Repository

Garcia Esparza, Angel T.

2017-04-13

For overall water-splitting systems, it is essential to establish O2 -insensitive cathodes that allow cogeneration of H2 and O2 . An acid-tolerant electrocatalyst is described, which employs a Mo-coating on a metal surface to achieve selective H2 evolution in the presence of O2 . In operando X-ray absorption spectroscopy identified reduced Pt covered with an amorphous molybdenum oxyhydroxide hydrate with a local structural order composed of polyanionic trimeric units of molybdenum(IV). The Mo layer likely hinders O2 gas permeation, impeding contact with active Pt. Photocatalytic overall water splitting proceeded using MoOx /Pt/SrTiO3 with inhibited water formation from H2 and O2 , which is the prevailing back reaction on the bare Pt/SrTiO3 photocatalyst. The Mo coating was stable in acidic media for multiple hours of overall water splitting by membraneless electrolysis and photocatalysis.

Molecular and crystal structure of nido-9-C5H5N-11-I-7,8-C2B9H10: supramolecular architecture via hydrogen bonding X-H...I (X = B, C)

International Nuclear Information System (INIS)

Polyanskaya, T.M.

2006-01-01

A monocrystal X-ray diffraction study of a new iodine-containing cluster compound 9-(pyridine)-11-iodo-decahydro-7,8-dicarba-nido-undecaborane [9-C 5 H 5 N-11-I-7,8-C 2 B 9 H 10 ] has been performed. Crystal data: C 7 H 15 B 9 NI, M = 337.39, monoclinic, space group P2 1 /c, unit cell parameters: a=9.348(1) A, b=11.159(1) A, c=13.442(2) A, β=98.13(1) deg, V=1388.1(5) A 3 , Z=4, d calc = 1.614 g/cm 3 , T = 295 K, F(000)=648, μ=2.276 mm -1 . The structure was solved by a direct method and refined in the full-matrix anisotropic approximation (isotropic for hydrogen atoms) to final agreement factors R 1 = 0.0254, wR 2 = 0.0454 for 2437 I hkl >2σ I from 3590 measured I hkl (an Enraf-Nonius CAD-4 diffractometer, λMoK α , graphite monochromator, θ/2θ-scanning). The molecules are joined into a supramolecular assembly by hydrogen bonds X-H...I (X = B, C) [ru

Propagation of symmetric and anti-symmetric surface waves in aself-gravitating magnetized dusty plasma layer with generalized (r, q) distribution

Science.gov (United States)

Lee, Myoung-Jae; Jung, Young-Dae

2018-05-01

The dispersion properties of surface dust ion-acoustic waves in a self-gravitating magnetized dusty plasma layer with the (r, q) distribution are investigated. The result shows that the wave frequency of the symmetric mode in the plasma layer decreases with an increase in the wave number. It is also shown that the wave frequency of the symmetric mode decreases with an increase in the spectral index r. However, the wave frequency of the anti-symmetric mode increases with an increase in the wave number. It is also found that the anti-symmetric mode wave frequency increases with an increase in the spectral index r. In addition, it is found that the influence of the self-gravitation on the symmetric mode wave frequency decreases with increasing scaled Jeans frequency. Moreover, it is found that the wave frequency of the symmetric mode increases with an increase in the dust charge; however, the anti-symmetric mode shows opposite behavior.

The synthesis of Org 3770 labelled with 3H, 13C and 14C

International Nuclear Information System (INIS)

Kaspersen, F.M.; Rooij, F.A.M. van; Sperling, E.G.M.; Wieringa, J.H.

1989-01-01

The syntheses of 1,2,3,4,10,14b-hexahydro-2-methylpyrazino[2,1-a]pyrido[2,3-c][2]benazepine (Org 3770) labelled with 3 H (and 2 H), 13 C and 14 C are described. Tritiated Org 3770 was prepared either by exchange under alkaline conditions with tritiated water or catalytic reductive dehalogenation of a chloro analogue with 3 H 2 . 13 C-labelled material was obtained in a seven-step synthesis starting from 13 C-labelled benzene whereas 14 C-Org 3770 was prepared in a three-step synthesis starting with 14 CO 2 . All labelled compounds were analyzed by TLC, HPLC, MS and NMR. (author)

The symmetric quartic map for trajectories of magnetic field lines in elongated divertor tokamak plasmas

Science.gov (United States)

Jones, Morgin; Wadi, Hasina; Ali, Halima; Punjabi, Alkesh

2009-04-01

The coordinates of the area-preserving map equations for integration of magnetic field line trajectories in divertor tokamaks can be any coordinates for which a transformation to (ψt,θ,φ) coordinates exists [A. Punjabi, H. Ali, T. Evans, and A. Boozer, Phys. Lett. A 364, 140 (2007)]. ψt is toroidal magnetic flux, θ is poloidal angle, and φ is toroidal angle. This freedom is exploited to construct the symmetric quartic map such that the only parameter that determines magnetic geometry is the elongation of the separatrix surface. The poloidal flux inside the separatrix, the safety factor as a function of normalized minor radius, and the magnetic perturbation from the symplectic discretization are all held constant, and only the elongation is κ varied. The width of stochastic layer, the area, and the fractal dimension of the magnetic footprint and the average radial diffusion coefficient of magnetic field lines from the stochastic layer; and how these quantities scale with κ is calculated. The symmetric quartic map gives the correct scalings which are consistent with the scalings of coordinates with κ. The effects of m =1, n =±1 internal perturbation with the amplitude that is expected to occur in tokamaks are calculated by adding a term [H. Ali, A. Punjabi, A. H. Boozer, and T. Evans, Phys. Plasmas 11, 1908 (2004)] to the symmetric quartic map. In this case, the width of stochastic layer scales as 0.35 power of κ. The area of the footprint is roughly constant. The average radial diffusion coefficient of field lines near the X-point scales linearly with κ. The low mn perturbation changes the quasisymmetric structure of the footprint, and reorganizes it into a single, large scale, asymmetric structure. The symmetric quartic map is combined with the dipole map [A. Punjabi, H. Ali, and A. H. Boozer, Phys. Plasmas 10, 3992 (2003)] to calculate the effects of magnetic perturbation from a current carrying coil. The coil position and coil current coil are

The symmetric quartic map for trajectories of magnetic field lines in elongated divertor tokamak plasmas

International Nuclear Information System (INIS)

Jones, Morgin; Wadi, Hasina; Ali, Halima; Punjabi, Alkesh

2009-01-01

The coordinates of the area-preserving map equations for integration of magnetic field line trajectories in divertor tokamaks can be any coordinates for which a transformation to (ψ t ,θ,φ) coordinates exists [A. Punjabi, H. Ali, T. Evans, and A. Boozer, Phys. Lett. A 364, 140 (2007)]. ψ t is toroidal magnetic flux, θ is poloidal angle, and φ is toroidal angle. This freedom is exploited to construct the symmetric quartic map such that the only parameter that determines magnetic geometry is the elongation of the separatrix surface. The poloidal flux inside the separatrix, the safety factor as a function of normalized minor radius, and the magnetic perturbation from the symplectic discretization are all held constant, and only the elongation is κ varied. The width of stochastic layer, the area, and the fractal dimension of the magnetic footprint and the average radial diffusion coefficient of magnetic field lines from the stochastic layer; and how these quantities scale with κ is calculated. The symmetric quartic map gives the correct scalings which are consistent with the scalings of coordinates with κ. The effects of m=1, n=±1 internal perturbation with the amplitude that is expected to occur in tokamaks are calculated by adding a term [H. Ali, A. Punjabi, A. H. Boozer, and T. Evans, Phys. Plasmas 11, 1908 (2004)] to the symmetric quartic map. In this case, the width of stochastic layer scales as 0.35 power of κ. The area of the footprint is roughly constant. The average radial diffusion coefficient of field lines near the X-point scales linearly with κ. The low mn perturbation changes the quasisymmetric structure of the footprint, and reorganizes it into a single, large scale, asymmetric structure. The symmetric quartic map is combined with the dipole map [A. Punjabi, H. Ali, and A. H. Boozer, Phys. Plasmas 10, 3992 (2003)] to calculate the effects of magnetic perturbation from a current carrying coil. The coil position and coil current coil are

Breakdown of the Coulomb friction law in TiC/a-C : H nanocomposite coatings

NARCIS (Netherlands)

Pei, Y.T.; Huizenga, P.; Galvan, D.; Hosson, J.Th.M. De

2006-01-01

Advanced TiC/a-C:H nanocomposite coatings have been produced via reactive deposition in a closed-field unbalanced magnetron sputtering system (Hauzer HTC-1000 or HTC 1200). In this paper, we report on the tribological behavior of TiC/a-C:H nanocomposite coatings in which ultralow friction is

Aging of oxygen and hydrogen plasma discharge treated a-C:H and ta-C coatings

Energy Technology Data Exchange (ETDEWEB)

Bachmann, Svenja [Physics of Surfaces, Institute of Materials Science, Technische Universität Darmstadt, Alarich-Weiss-Str. 16, 64287 Darmstadt (Germany); BMW Group, Hufelandstraße 4, 80788 Munich (Germany); Schulze, Marcus [Physics of Surfaces, Institute of Materials Science, Technische Universität Darmstadt, Alarich-Weiss-Str. 16, 64287 Darmstadt (Germany); Center of Smart Interfaces, Technische Universität Darmstadt, Alarich-Weiss-Str. 10, 64287 Darmstadt (Germany); Morasch, Jan [Institute of Materials Science, Technische Universität Darmstadt, Surface Science Division, Jovanka-Bonschits-Straße 2, 64287 Darmstadt (Germany); Hesse, Sabine [Physics of Surfaces, Institute of Materials Science, Technische Universität Darmstadt, Alarich-Weiss-Str. 16, 64287 Darmstadt (Germany); Center of Smart Interfaces, Technische Universität Darmstadt, Alarich-Weiss-Str. 10, 64287 Darmstadt (Germany); Hussein, Laith [Eduard-Zintl-Institut, Department of Chemistry, Technische Universität Darmstadt, Alarich-Weiss-Str. 12, 64287, Darmstadt (Germany); Krell, Lisa; Schnagl, Johann [BMW Group, Hufelandstraße 4, 80788 Munich (Germany); Stark, Robert W. [Physics of Surfaces, Institute of Materials Science, Technische Universität Darmstadt, Alarich-Weiss-Str. 16, 64287 Darmstadt (Germany); Center of Smart Interfaces, Technische Universität Darmstadt, Alarich-Weiss-Str. 10, 64287 Darmstadt (Germany); and others

2016-05-15

Highlights: • The water CA of O{sub 2} and H{sub 2} plasma treated a-C:H and ta-C changes from hydrophillic to hydrophobic on aging. • XPS study indicates that the decrease in surface energy of plasma treated a-C:H and ta-C could be due to adsorption of organic component from air. • The COFLFM of O{sub 2} and H{sub 2} plasma treated a-C:H and ta-C decreased upon aging. • The COF of glycerol lubricated ta-C showed no sign of change upon aging. - Abstract: Surface modification with gas plasma is an efficient and easy way to improve the surface energy and the tribological behavior of diamond-like carbon (DLC) coatings, e.g., in biomedical implants or as protective coatings. However, the long-term performance of the plasma treated DLC coatings is not fully clear. We thus studied the long-term stability of two kinds of DLC coatings, namely (a) hydrogenated amorphous carbon (a-C:H) and (b) tetrahedral amorphous carbon (ta-C) treated at different radio frequency (RF) power and time of oxygen (O{sub 2}) and hydrogen (H{sub 2}) plasma. Their surface properties, e.g. surface wettability, structure and tribological behavior, were studied at regular intervals for a period of two months using contact angle goniometer, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), lateral force microscopy (LFM) and ball on disc apparatus. The surface energy of both the coatings decreased upon aging. The higher the RF power and time of treatment, the higher was the hydrophobicity upon aging. XPS analysis showed that the increase in hydrophobicity could be due to adsorption of unavoidable volatile organic components in the atmosphere. The H{sub 2} plasma treated ta-C was capable of rearranging its structural bonds upon aging. The nano-friction measurements by LFM showed that the coefficient of friction of plasma treated a-C:H and ta-C decreased upon aging. The results indicate that the surface properties of plasma treated a‐C:H and ta‐C are not stable on long-term and are

Alkane Activation at Ambient Temperatures: Unusual Selectivities, C-C, C-H Bond Scission versus C-C Bond Coupling

NARCIS (Netherlands)

Trionfetti, C.; Agiral, A.; Gardeniers, Johannes G.E.; Lefferts, Leonardus; Seshan, Kulathuiyer

2008-01-01

Activating bonds: A cold plasma generated by dielectric barrier discharge in a microreactor converts alkanes (C1–C3) at atmospheric pressure. Large amounts of products with higher molecular weight than the starting hydrocarbons are observed showing that C-H activation at lower T favourably leads to

The Split-Brain Phenomenon Revisited: A Single Conscious Agent with Split Perception.

Science.gov (United States)

Pinto, Yair; de Haan, Edward H F; Lamme, Victor A F

2017-11-01

The split-brain phenomenon is caused by the surgical severing of the corpus callosum, the main route of communication between the cerebral hemispheres. The classical view of this syndrome asserts that conscious unity is abolished. The left hemisphere consciously experiences and functions independently of the right hemisphere. This view is a cornerstone of current consciousness research. In this review, we first discuss the evidence for the classical view. We then propose an alternative, the 'conscious unity, split perception' model. This model asserts that a split brain produces one conscious agent who experiences two parallel, unintegrated streams of information. In addition to changing our view of the split-brain phenomenon, this new model also poses a serious challenge for current dominant theories of consciousness. Copyright © 2017 Elsevier Ltd. All rights reserved.

Radial electric field and ion parallel flow in the quasi-symmetric and Mirror configurations of HSX

Science.gov (United States)

Kumar, S. T. A.; Dobbins, T. J.; Talmadge, J. N.; Wilcox, R. S.; Anderson, D. T.

2018-05-01

The radial electric field and the ion mean parallel flow are obtained in the helically symmetric experiment stellarator from toroidal flow measurements of C+6 ion at two locations on a flux surface, using the Pfirsch–Schlüter effect. Results from the standard quasi-helically symmetric magnetic configuration are compared with those from the Mirror configuration where the quasi-symmetry is deliberately degraded using auxiliary coils. For similar injected power, the quasi-symmetric configuration is observed to have significantly lower flows while the experimental observations from the Mirror geometry are in better agreement with neoclassical calculations. Indications are that the radial electric field near the core of the quasi-symmetric configuration may be governed by non-neoclassical processes.

Symmetric textures

International Nuclear Information System (INIS)

Ramond, P.

1993-01-01

The Wolfenstein parametrization is extended to the quark masses in the deep ultraviolet, and an algorithm to derive symmetric textures which are compatible with existing data is developed. It is found that there are only five such textures

Electrically active defects in n-type 4H- and 6H-SiC

Energy Technology Data Exchange (ETDEWEB)

Doyle, J.P. [Royal Inst. of Tech., Stockholm (Sweden). Dept. of Solid State Electronics]|[IBM Research Div., T.J. Watson Research Center, Yorktown Heights, NY (United States); Aboelfotoh, M.O. [Royal Inst. of Tech., Stockholm (Sweden). Dept. of Solid State Electronics]|[North Carolina State Univ., Dept. of Materials Science and Engineering, Raleigh, NC (United States); Svensson, B.G. [Royal Inst. of Tech., Stockholm (Sweden). Dept. of Solid State Electronics

1998-06-01

We have found that in 6H-SiC, irradiation induced defects can become mobile at temperatures as low as 200 C. Through isochronal and isothermal annealing a level at 0.51 eV below the conduction band (with a capture cross-section of 2 x 10{sup -14} cm{sup 2}), appears to disassociate through a first order process with an activation energy of 1.45 eV+/-0.1 eV. In 4H-SiC, we have observed two irradiation induced defects assigned the positions 0.62 eV and 0.68 eV below E{sub c} (with capture cross-sections of 4 x 10{sup -14} cm{sup 2} and 5 x 10{sup -15} cm{sup 2}, respectively) which are found to be unstable at room temperature with time. SIMS analysis indicates that in both 6H- and 4H-SiC the defect levels are not due to the incorporation of the transition metals Ti, V, or Cr. Additionally, in both polytypes of SiC that were examined, the defects are found to display acceptor-like behavior as no evidence of a Poole-Frenkel shift was observed during DLTS measurements. (orig.) 10 refs.

[Study of hydrogen bonds in the "catalytic triad" of trypsin by NMR spectra at 1H, 13C, and 15N nuclei].

Science.gov (United States)

Golubeb, N S; Gindin, V A; Ligaĭ, S S; Smirnov, S N

1994-05-01

The 1H and 13C NMR of trypsin stabilized by chemical modification with a hydrophilic polymer have been obtained in a wide range of pH (1.0-11.0). The spectral features referred to some nuclei of the "catalytic triad" have been identified using different NMR techniques as well as chemical modification with selective reagents. It was found that the monoprotonation of this system results in a quasi-symmetrical hydrogen bond formed between the basic groups which provided explanation for the discrepancies between the experimental findings obtained by different authors concerning the protonation site in this catalytic system. Simulation of the catalytic triad by a 15N-labelled low molecular model suggests that an increase in the OH-group acidity is unaccompanied by a discrete double proton transfer; however, a smooth shift of the bridging protons from one basic atom to another occurs with quasi-symmetrical hydrogen bonds formed in intermediate cases. On the basis of experimental data a new concept has been proposed for the mechanism of acid-base catalysis performed by pains of weak basic groups, such as His-Im and Asp(Glu)-COO- (pKa = 3-7) which are not capable of proton abstraction from alcoholic or water OH-groups (pKa > 13). The catalysis may consist in changing the charge densities on the reacting groups due to strong H-bonding and, on the other hand, in facilitating the free movement of a proton in the field of several basic atoms when going along the reaction coordinate. The energy of very strong hydrogen bonds thus formed diminishes the activation energy of the reaction.

Triadic split-merge sampler

Science.gov (United States)

van Rossum, Anne C.; Lin, Hai Xiang; Dubbeldam, Johan; van der Herik, H. Jaap

2018-04-01

In machine vision typical heuristic methods to extract parameterized objects out of raw data points are the Hough transform and RANSAC. Bayesian models carry the promise to optimally extract such parameterized objects given a correct definition of the model and the type of noise at hand. A category of solvers for Bayesian models are Markov chain Monte Carlo methods. Naive implementations of MCMC methods suffer from slow convergence in machine vision due to the complexity of the parameter space. Towards this blocked Gibbs and split-merge samplers have been developed that assign multiple data points to clusters at once. In this paper we introduce a new split-merge sampler, the triadic split-merge sampler, that perform steps between two and three randomly chosen clusters. This has two advantages. First, it reduces the asymmetry between the split and merge steps. Second, it is able to propose a new cluster that is composed out of data points from two different clusters. Both advantages speed up convergence which we demonstrate on a line extraction problem. We show that the triadic split-merge sampler outperforms the conventional split-merge sampler. Although this new MCMC sampler is demonstrated in this machine vision context, its application extend to the very general domain of statistical inference.

An oxygen-insensitive hydrogen evolution catalyst coated by a molybdenum-based layer for overall water splitting

Energy Technology Data Exchange (ETDEWEB)

Garcia-Esparza, Angel T.; Shinagawa, Tatsuya; Ould-Chikh, Samy; Qureshi, Muhammad; Peng, Xuyuan; Takanabe, Kazuhiro [KAUST Catalysis Center (KCC) and Physical Science and Engineering Division - PSE, King Abdullah University of Science and Technology (KAUST), Thuwal (Saudi Arabia); Wei, Nini; Anjum, Dalaver H. [Advanced Nanofabrication, Imaging and Characterization Core Lab, King Abdullah University of Science and Technology (KAUST), Thuwal (Saudi Arabia); Clo, Alain [Research Computing, King Abdullah University of Science and Technology (KAUST), Thuwal (Saudi Arabia); Weng, Tsu-Chien [Center for High Pressure Science and Technology Advanced Research, Shanghai (China); Nordlund, Dennis; Sokaras, Dimosthenis [Stanford Synchrotron Radiation Lightsource, Menlo Park, CA (United States); Kubota, Jun [Department of Chemical Engineering, Fukuoka University (Japan); Domen, Kazunari [Department of Chemical System Engineering, School of Engineering, The University of Tokyo (Japan)

2017-05-15

For overall water-splitting systems, it is essential to establish O{sub 2}-insensitive cathodes that allow cogeneration of H{sub 2} and O{sub 2}. An acid-tolerant electrocatalyst is described, which employs a Mo-coating on a metal surface to achieve selective H{sub 2} evolution in the presence of O{sub 2}. In operando X-ray absorption spectroscopy identified reduced Pt covered with an amorphous molybdenum oxyhydroxide hydrate with a local structural order composed of polyanionic trimeric units of molybdenum(IV). The Mo layer likely hinders O{sub 2} gas permeation, impeding contact with active Pt. Photocatalytic overall water splitting proceeded using MoO{sub x}/Pt/SrTiO{sub 3} with inhibited water formation from H{sub 2} and O{sub 2}, which is the prevailing back reaction on the bare Pt/SrTiO{sub 3} photocatalyst. The Mo coating was stable in acidic media for multiple hours of overall water splitting by membraneless electrolysis and photocatalysis. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Cleavage of sp3 C-O bonds via oxidative addition of C-H bonds.

Science.gov (United States)

Choi, Jongwook; Choliy, Yuriy; Zhang, Xiawei; Emge, Thomas J; Krogh-Jespersen, Karsten; Goldman, Alan S

2009-11-04

(PCP)Ir (PCP = kappa(3)-C(6)H(3)-2,6-[CH(2)P(t-Bu)(2)](2)) is found to undergo oxidative addition of the methyl-oxygen bond of electron-poor methyl aryl ethers, including methoxy-3,5-bis(trifluoromethyl)benzene and methoxypentafluorobenzene, to give the corresponding aryloxide complexes (PCP)Ir(CH(3))(OAr). Although the net reaction is insertion of the Ir center into the C-O bond, density functional theory (DFT) calculations and a significant kinetic isotope effect [k(CH(3))(OAr)/k(CD(3))(OAr) = 4.3(3)] strongly argue against a simple insertion mechanism and in favor of a pathway involving C-H addition and alpha-migration of the OAr group to give a methylene complex followed by hydride-to-methylene migration to give the observed product. Ethoxy aryl ethers, including ethoxybenzene, also undergo C-O bond cleavage by (PCP)Ir, but the net reaction in this case is 1,2-elimination of ArO-H to give (PCP)Ir(H)(OAr) and ethylene. DFT calculations point to a low-barrier pathway for this reaction that proceeds through C-H addition of the ethoxy methyl group followed by beta-aryl oxide elimination and loss of ethylene. Thus, both of these distinct C-O cleavage reactions proceed via initial addition of a C(sp(3))-H bond, despite the fact that such bonds are typically considered inert and are much stronger than C-O bonds.

Probabilistic cloning of three symmetric states

International Nuclear Information System (INIS)

Jimenez, O.; Bergou, J.; Delgado, A.

2010-01-01

We study the probabilistic cloning of three symmetric states. These states are defined by a single complex quantity, the inner product among them. We show that three different probabilistic cloning machines are necessary to optimally clone all possible families of three symmetric states. We also show that the optimal cloning probability of generating M copies out of one original can be cast as the quotient between the success probability of unambiguously discriminating one and M copies of symmetric states.

Quantified pH imaging with hyperpolarized (13) C-bicarbonate.

Science.gov (United States)

Scholz, David Johannes; Janich, Martin A; Köllisch, Ulrich; Schulte, Rolf F; Ardenkjaer-Larsen, Jan H; Frank, Annette; Haase, Axel; Schwaiger, Markus; Menzel, Marion I

2015-06-01

Because pH plays a crucial role in several diseases, it is desirable to measure pH in vivo noninvasively and in a spatially localized manner. Spatial maps of pH were quantified in vitro, with a focus on method-based errors, and applied in vivo. In vitro and in vivo (13) C mapping were performed for various flip angles for bicarbonate (BiC) and CO2 with spectral-spatial excitation and spiral readout in healthy Lewis rats in five slices. Acute subcutaneous sterile inflammation was induced with Concanavalin A in the right leg of Buffalo rats. pH and proton images were measured 2 h after induction. After optimizing the signal to noise ratio of the hyperpolarized (13) C-bicarbonate, error estimation of the spectral-spatial excited spectrum reveals that the method covers the biologically relevant pH range of 6 to 8 with low pH error (< 0.2). Quantification of pH maps shows negligible impact of the residual bicarbonate signal. pH maps reflect the induction of acute metabolic alkalosis. Inflamed, infected regions exhibit lower pH. Hyperpolarized (13) C-bicarbonate pH mapping was shown to be sensitive in the biologically relevant pH range. The mapping of pH was applied to healthy in vivo organs and interpreted within inflammation and acute metabolic alkalosis models. © 2014 Wiley Periodicals, Inc.

Boomerang deformity of cervical spinal cord migrating between split laminae after laminoplasty.

Science.gov (United States)

Kimura, S; Gomibuchi, F; Shimoda, H; Ikezawa, Y; Segawa, H; Kaneko, F; Uchiyama, S; Homma, T

2000-04-01

Patients with cervical compression myelopathy were studied to elucidate the mechanism underlying boomerang deformity, which results from the migration of the cervical spinal cord between split laminae after laminoplasty with median splitting of the spinous processes (boomerang sign). Thirty-nine cases, comprising 25 patients with cervical spondylotic myelopathy, 8 patients with ossification of the posterior longitudinal ligament, and 6 patients with cervical disc herniation with developmental canal stenosis, were examined. The clinical and radiological findings were retrospectively compared between patients with (B group, 8 cases) and without (C group, 31 cases) boomerang sign. Moderate increase of the grade of this deformity resulted in no clinical recovery, although there was no difference in clinical recovery between the two groups. Most boomerang signs developed at the C4/5 and/or C5/6 level, where maximal posterior movement of the spinal cord was achieved. Widths between lateral hinges and between split laminae in the B group were smaller than in the C group. Flatness of the spinal cord in the B group was more severe than in the C group. In conclusion, the boomerang sign was caused by posterior movement of the spinal cord, narrower enlargement of the spinal canal and flatness of the spinal cord.

A symmetrical rail accelerator

International Nuclear Information System (INIS)

Igenbergs, E.

1991-01-01

This paper reports on the symmetrical rail accelerator that has four rails, which are arranged symmetrically around the bore. The opposite rails have the same polarity and the adjacent rails the opposite polarity. In this configuration the radial force acting upon the individual rails is significantly smaller than in a conventional 2-rail configuration and a plasma armature is focussed towards the axis of the barrel. Experimental results indicate a higher efficiency compared to a conventional rail accelerator

Split and delay photon correlation spectroscopy with a visible light

International Nuclear Information System (INIS)

Rasch, Marten

2016-04-01

The development and performance of a setup constructed with the aim for the split pulse photon correlation spectroscopy is presented in this thesis. The double pulse time structure is accomplished with help of an Acusto-Optic Modulator (AOM) crystal, which mimics the splitting and delaying of photon pulses. The setup provides double pulses and allows to control the pulse width and delay and to synchronize them into one camera exposure window. The performance of the setup was successfully verified in a proof of principle experiment with a model system of polystyrene particles following Brownian motion. The measured radius of particles obtained with from the split pulse experiment (R h =(2.567±0.097) μm) is in agreement with the particle size provided by the manufacturer (R=(2.26±0.08) μm). The achieved results show higher statistics compared to a standard Dynamic Light Scattering (DLS) measurement.

A split hand-split foot (SHFM3) gene is located at 10q24{yields}25

Energy Technology Data Exchange (ETDEWEB)

Gurrieri, F.; Genuardi, M.; Nanni, L.; Sangiorgi, E.; Garofalo, G. [Catholic Univ. of Rome (Italy)] [and others

1996-04-24

The split hand-split foot (SHSF) malformation affects the central rays of the upper and lower limbs. It presents either as an isolated defect or in association with other skeletal or non-skeletal abnormalities. An autosomal SHSF locus (SHFM1) was previously mapped to 7q22.1. We report the mapping of a second autosomal SHSF locus to 10q24{yields}25 region. Maximum lod scores of 3.73, 4.33 and 4.33 at a recombination fraction of zero were obtained for the loci D10S198, PAX2 and D10S1239, respectively. An 19 cM critical region could be defined by haplotype analysis and several genes with a potential role in limb morphogenesis are located in this region. Heterogeneity testing indicates the existence of at least one additional autosomal SHSF locus. 36 refs., 3 figs., 3 tabs.

Water splitting-biosynthetic system with CO₂ reduction efficiencies exceeding photosynthesis.

Science.gov (United States)

Liu, Chong; Colón, Brendan C; Ziesack, Marika; Silver, Pamela A; Nocera, Daniel G

2016-06-03

Artificial photosynthetic systems can store solar energy and chemically reduce CO2 We developed a hybrid water splitting-biosynthetic system based on a biocompatible Earth-abundant inorganic catalyst system to split water into molecular hydrogen and oxygen (H2 and O2) at low driving voltages. When grown in contact with these catalysts, Ralstonia eutropha consumed the produced H2 to synthesize biomass and fuels or chemical products from low CO2 concentration in the presence of O2 This scalable system has a CO2 reduction energy efficiency of ~50% when producing bacterial biomass and liquid fusel alcohols, scrubbing 180 grams of CO2 per kilowatt-hour of electricity. Coupling this hybrid device to existing photovoltaic systems would yield a CO2 reduction energy efficiency of ~10%, exceeding that of natural photosynthetic systems. Copyright © 2016, American Association for the Advancement of Science.

Sequence Variations in the Flagellar Antigen Genes fliC H25 and fliC H28 of Escherichia coli and Their Use in Identification and Characterization of Enterohemorrhagic E. coli (EHEC) O145:H25 and O145:H28

Science.gov (United States)

Beutin, Lothar; Delannoy, Sabine; Fach, Patrick

2015-01-01

Enterohemorrhagic E. coli (EHEC) serogroup O145 is regarded as one of the major EHEC serogroups involved in severe infections in humans. EHEC O145 encompasses motile and non-motile strains of serotypes O145:H25 and O145:H28. Sequencing the fliC-genes associated with the flagellar antigens H25 and H28 revealed the genetic diversity of the fliC H25 and fliC H28 gene sequences in E. coli. Based on allele discrimination of these fliC-genes real-time PCR tests were designed for identification of EHEC O145:H25 and O145:H28. The fliC H25 genes present in O145:H25 were found to be very similar to those present in E. coli serogroups O2, O100, O165, O172 and O177 pointing to their common evolution but were different from fliC H25 genes of a multiple number of other E. coli serotypes. In a similar way, EHEC O145:H28 harbor a characteristic fliC H28 allele which, apart from EHEC O145:H28, was only found in enteropathogenic (EPEC) O28:H28 strains that shared some common traits with EHEC O145:H28. The real time PCR-assays targeting these fliC H25[O145] and fliC H28[O145] alleles allow better characterization of EHEC O145:H25 and EHEC O145:H28. Evaluation of these PCR assays in spiked ready-to eat salad samples resulted in specific detection of both types of EHEC O145 strains even when low spiking levels of 1–10 cfu/g were used. Furthermore these PCR assays allowed identification of non-motile E. coli strains which are serologically not typable for their H-antigens. The combined use of O-antigen genotyping (O145wzy) and detection of the respective fliC H25[O145] and fliC H28[O145] allele types contributes to improve identification and molecular serotyping of E. coli O145 isolates. PMID:26000885

Production and detection at SSC of Higgs bosons in left-right symmetric theories

International Nuclear Information System (INIS)

Gunion, J.; Kayser, B.; Mohapatra, R.N.; Deshpande, N.G.; Grifols, J.; Mendez, A.; Olness, F.; Pal, P.B.

1986-12-01

We discuss the production and detection at SSC of charged and neutral Higgs bosons of the left-right symmetric theories. The H + , which is largely a member of a left-right ''bidoublet,'' should be detectable. The H 2 0 , a more unusual Higgs particle which, apart from mixing, is in a right-handed triplet and does not couple to quarks, may be detectable too

Characterization of a n+3C/n−4H SiC heterojunction diode

Energy Technology Data Exchange (ETDEWEB)

Minamisawa, R. A.; Mihaila, A. [Department of Power Electronics, ABB Corporate Research Center, CH-5405 Baden-Dättwil (Switzerland); Farkas, I.; Hsu, C.-W.; Janzén, E. [Semiconductor Materials, IFM, Linköping University, SE-58183 Linköping (Sweden); Teodorescu, V. S. [National Institute of Material Physics, R-077125 Bucharest-Măgurele (Romania); Afanas' ev, V. V. [Semiconductor Physics Laboratory, KU Leuven, 3001 Leuven (Belgium); Rahimo, M. [ABB Semiconductors, Fabrikstrasse 3, CH-5600 Lenzburg (Switzerland)

2016-04-04

We report on the fabrication of n + 3C/n-4H SiC heterojunction diodes (HJDs) potentially promising the ultimate thermal stability of the junction. The diodes were systematically analyzed by TEM, X-ray diffraction, AFM, and secondary ion mass spectroscopy, indicating the formation of epitaxial 3C-SiC crystal on top of 4H-SiC substrate with continuous interface, low surface roughness, and up to ∼7 × 10{sup 17 }cm{sup −3} dopant impurity concentration. The conduction band off-set is about 1 V as extracted from CV measurements, while the valence bands of both SiC polytypes are aligned. The HJDs feature opening voltage of 1.65 V, consistent with the barrier height of about 1.5 eV extracted from CV measurement. We finally compare the electrical results of the n + 3C/n-4H SiC heterojunction diodes with those featuring Si and Ge doped anodes in order to evaluate current challenges involved in the fabrication of such devices.

Non-splitting in Kirchberg's Ideal-related KK-Theory

DEFF Research Database (Denmark)