Structural and phase properties of tetracosane (C24H50) monolayers adsorbed on graphite. Explicit Hydrogen Molecular Dynamics study

http://arxiv.org/ftp/arxiv/papers/0805/0805.1435.pdfWe discuss Molecular Dynamics (MD) computer simulations of a tetracosane (C24H50) monolayer physisorbed onto the basal plane of graphite. The adlayer molecules are simulated with explicit hydrogens, and the graphite substrate is represented as an all-atom structure having six graphene layers. The tetracosane dynamics modeled in the fully atomistic manner agree well with experiment. The low-temperature ordered solid organizes in rectangular centered structure, incommensurate with underlying graphite. Above T = 200 K, as the molecules start to lose their translational and orientational order via gauche defect formation, a weak smectic mesophase (observed experimentally but never reproduced in United Atom (UA) simulations) appears. The phase behavior of the adsorbed layer is critically sensitive to the way the electrostatic interactions are included in the model. If the electrostatic charges are set to zero (as it is in UA force field), the melting temperature increases by ~70 K with respect to the experimental value. When the non-bonded 1-4 interaction is not scaled, the melting temperature decreases by ~90 K. If the scaling factor is set to 0.5, the melting occurs at T = 350 K, in very good agreement with experimental data.Acknowledgment is made to the Donors of The American Chemical Society Petroleum Research Fund (PRF43277 - B5), and the University of Missouri Research Board, for the support of this research. This material is based upon work supported in part by the Department of Energy under Award Number DE-FG02-07ER46411

On the R-Matrix Formulation of Deformed Algebras and Generalized Jordan-Wigner Transformations

The deformed algebra $\cal{A(R)}$, depending upon a Yang-Baxter R- matrix, is considered. The conditions under which the algebra is associative are discussed for a general number of oscillators. Four types of solutions satisfying these conditions are constructed and two of them can be represented by generalized Jordan-Wigner transformations.Our analysis is in some sense an extension of the boson realization of fermions from single-mode to multimode oscillators.Comment: 10+ii pages,preprint RBI-TH-10/93,Latex,(to appear in Europhys.Lett.

2D Kagome Ordering in the 3D Frustrated Spinel Li2Mn2O4

muSR experiments on the geometrically frustrated spinel oxide, Li2Mn2O4, show the development of spin correlations over a range of length scales with decreasing temperature. Increased relaxation below 150 K is consistent with the onset of spin correlations. Below 50 K, spin order on a length scale, which is long range for the muSR probe, appears abruptly in temperature, consistent with prior neutron diffraction results. The oscillations in the zero field asymmetry are analyzed using a three frequency model. By locating the muon site this is shown to be consistent with the unexpected 2D q = root 3 x root 3 structure on the Kagome planes proposed originally from neutron data. Longitudinal field data demonstrate that some spin dynamics persist even at 2 K. Thus, a very complex magnetic ground state, featuring the co-existence of long length scale 2D ordering and significant spin dynamics, is proposed. This is unusual considering the 3D topology of the Mn3+ spins in this material.Comment: 9 pages, 9 figures, to be submitted to J. Phys. Cond. Mat

A Survey on Exotic Signatures for Post-quantum Blockchain: Challenges and Research Directions

Blockchain technology provides efficient and secure solutions to various online activities by utilizing a wide range of cryptographic tools. In this article, we survey the existing literature on post-quantum secure digital signatures that possess exotic advanced features and that are crucial cryptographic tools used in the blockchain ecosystem for (1) account management, (2) consensus efficiency, (3) empowering scriptless blockchain, and (4) privacy. The exotic signatures that we particularly focus on in this work are the following: multi-/aggregate, threshold, adaptor, blind, and ring signatures. Herein the term "exotic"refers to signatures with properties that are not just beyond the norm for signatures, e.g., unforgeability, but also imbue new forms of functionalities. Our treatment of such exotic signatures includes discussions on existing challenges and future research directions in the post-quantum space. We hope that this article will help to foster further research to make post-quantum cryptography more accessible so that blockchain systems can be made ready in advance of the approaching quantum threats

Pressure effect on the in-plane magnetic penetration depth in YBa_2Cu_4O_8

We report a study of the pressure effect (PE) on the in-plane magnetic field penetration depth lambda_{ab} in YBa_2Cu_4O_8 by means of Meissner fraction measurements. A pronounced PE on lambda_{ab}^{-2}(0) was observed with a maximum relative shift of \Delta\lambda^{-2}_{ab}/\lambda^{-2}_{ab}= 44(3)% at a pressure of 10.2 kbar. It arises from the pressure dependence of the effective in-plane charge carrier mass and pressure induced charge carrier transfer from the CuO chains to the superconducting CuO_2 planes. The present results imply that the charge carriers in YBa_2Cu_4O_8 are coupled to the lattice.Comment: 4pages 3 figure

Identifying the sources driving observed PM2.5 temporal variability over Halifax, Nova Scotia, during BORTAS-B

The source attribution of observed variability of total PM_2.5 concentrations over Halifax, Nova Scotia was investigated between 11 July–26 August 2011 using measurements of PM_2.5 mass and PM_2.5 chemical composition (black carbon, organic matter, anions, cations and 33 elements). This was part of the BORTAS-B (quantifying the impact of BOReal forest fires on Tropospheric oxidants using aircraft and satellites) experiment, which investigated the atmospheric chemistry and transport of seasonal boreal wild fire emissions over eastern Canada in 2011. The US EPA Positive Matrix Factorization (PMF) receptor model was used to determine the average mass (percentage) source contribution over the 45 days, which was estimated to be: Long-Range Transport (LRT) Pollution 1.75 μg m⁻³ (47%), LRT Pollution Marine Mixture 1.0 μg m⁻³ (27.9%), Vehicles 0.49 μg m⁻³ (13.2%), Fugitive Dust 0.23 μg m⁻³ (6.3%), Ship Emissions 0.13 μg m⁻³ (3.4%) and Refinery 0.081 μg m⁻³ (2.2%). The PMF model describes 87% of the observed variability in total PM_2.5 mass (bias = 0.17 and RSME = 1.5 μg m⁻³). The factor identifications are based on chemical markers, and they are supported by air mass back trajectory analysis and local wind direction. Biomass burning plumes, found by other surface and aircraft measurements, were not significant enough to be identified in this analysis. This paper presents the results of the PMF receptor modelling, providing valuable insight into the local and upwind sources impacting surface PM_2.5 in Halifax during the BORTAS-B mission

Lattice-switch Monte Carlo

We present a Monte Carlo method for the direct evaluation of the difference between the free energies of two crystal structures. The method is built on a lattice-switch transformation that maps a configuration of one structure onto a candidate configuration of the other by `switching' one set of lattice vectors for the other, while keeping the displacements with respect to the lattice sites constant. The sampling of the displacement configurations is biased, multicanonically, to favor paths leading to `gateway' arrangements for which the Monte Carlo switch to the candidate configuration will be accepted. The configurations of both structures can then be efficiently sampled in a single process, and the difference between their free energies evaluated from their measured probabilities. We explore and exploit the method in the context of extensive studies of systems of hard spheres. We show that the efficiency of the method is controlled by the extent to which the switch conserves correlated microstructure. We also show how, microscopically, the procedure works: the system finds gateway arrangements which fulfill the sampling bias intelligently. We establish, with high precision, the differences between the free energies of the two close packed structures (fcc and hcp) in both the constant density and the constant pressure ensembles.Comment: 34 pages, 9 figures, RevTeX. To appear in Phys. Rev.

The reductive activation of CO2 across a Ti═Ti double bond: synthetic, structural, and mechanistic studies

[Image: see text] The reactivity of the bis(pentalene)dititanium double-sandwich compound Ti(2)Pn(†)(2) (1) (Pn(†) = 1,4-{Si(i)Pr(3)}(2)C(8)H(4)) with CO(2) is investigated in detail using spectroscopic, X-ray crystallographic, and computational studies. When the CO(2) reaction is performed at −78 °C, the 1:1 adduct 4 is formed, and low-temperature spectroscopic measurements are consistent with a CO(2) molecule bound symmetrically to the two Ti centers in a μ:η(2),η(2) binding mode, a structure also indicated by theory. Upon warming to room temperature the coordinated CO(2) is quantitatively reduced over a period of minutes to give the bis(oxo)-bridged dimer 2 and the dicarbonyl complex 3. In situ NMR studies indicated that this decomposition proceeds in a stepwise process via monooxo (5) and monocarbonyl (7) double-sandwich complexes, which have been independently synthesized and structurally characterized. 5 is thermally unstable with respect to a μ-O dimer in which the Ti–Ti bond has been cleaved and one pentalene ligand binds in an η(8) fashion to each of the formally Ti(III) centers. The molecular structure of 7 shows a “side-on” bound carbonyl ligand. Bonding of the double-sandwich species Ti(2)Pn(2) (Pn = C(8)H(6)) to other fragments has been investigated by density functional theory calculations and fragment analysis, providing insight into the CO(2) reaction pathway consistent with the experimentally observed intermediates. A key step in the proposed mechanism is disproportionation of a mono(oxo) di-Ti(III) species to yield di-Ti(II) and di-Ti(IV) products. 1 forms a structurally characterized, thermally stable CS(2) adduct 8 that shows symmetrical binding to the Ti(2) unit and supports the formulation of 4. The reaction of 1 with COS forms a thermally unstable complex 9 that undergoes scission to give mono(μ-S) mono(CO) species 10. Ph(3)PS is an effective sulfur transfer agent for 1, enabling the synthesis of mono(μ-S) complex 11 with a double-sandwich structure and bis(μ-S) dimer 12 in which the Ti–Ti bond has been cleaved

Standardized Hepatitis B Virus RNA Quantification in Untreated and Treated Chronic Patients: a Promising Marker of Infection Follow-Up.

The measurement and interpretation of HBV DNA and RNA levels in HBV infected patients treated with antiviral therapy supports the objective of HBV disease management. Here, we quantified circulating HBV RNA through a standardized and sensitive assay in follow-up samples from both naive and treated patients as a marker of infection evolution. HBV DNA (HBV DNA for use in Cobas 6800/8800 Automated Roche Molecular Systems), RNA (Roche HBV RNA Investigational Assay for use in the Cobas 6800/8800; Roche), HBeAg and HBsAg (Elycsys HBsAg chemiluminescence immunoassay by Cobas 8000; Roche), and core-related antigen (Lumipulse G chemiluminescence assay; Fujirebio) levels were measured in cohorts of untreated or nucleos(t)ide treated, HBV-infected subjects in an outpatient hospital setting. HBV DNA levels in untreated people were 3.6 log10 higher than corresponding RNA levels and were stable over 5 years of observation. While only five of 52 treated patients had DNA levels below the lower limit of quantification (10 IU/mL) at the end of follow-up, 13 had HBV RNA levels persistently above this limit, including eight with undetectable DNA. In samples with undetectable core-related antigen we observed a median HBsAg titer 2.7-fold higher than in samples with undetectable RNA (adjusted P = 0.012). Detectable HBV RNA with undetectable HBV DNA was a negative predictor of HBsAg decrease to a level ≤100 IU/mL (P = 0.03). In naive patients the difference between HBV DNA and RNA was higher than previously reported. HBV RNA rapidly decreased during treatment. However, in some cases, it was detectable even after years of effective therapy, being a negative predictor of HBsAg decrease. The investigational RNA assay for use on the Cobas 6800/8800 instruments is a sensitive and standardized method that could be applied in general management of HBV infection. IMPORTANCE This study focused on the quantification of circulating HBV RNA by using a standardized and sensitive assay. Thanks to this system we observed a higher difference between circulating HBV DNA and RNA than previously reported. In treated patients, HBV RNA decreased together with DNA, although some patients presented detectable levels even after years of successful antiviral treatment, suggesting a persistent viral transcription. Of note, the detection of viral RNA when HBV DNA is undetectable was a negative predictor of HBsAg decrease to a level ≤100 IU/mL. This assay could be extremely helpful in HBV patients management to study viral transcription and to identify those treated patients that may achieve sustained viral suppression

Topological chaos: what may this mean ?

We confront existing definitions of chaos with the state of the art in topological dynamics. The article does not propose any new definition of chaos but, starting from several topological properties that can be reasonably called chaotic, tries to sketch a theoretical view of chaos. Among the main ideas in this article are the distinction between overall chaos and partial chaos, and the fact that some dynamical properties may be considered more chaotic than others