2,931 research outputs found

    Ring Expansion Of Alkylidenecarbenes Derived From Lactams, Lactones, And Thiolactones Into Strained Heterocyclic Alkynes: A Theoretical Study

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    Strained cycloalkynes are of considerable interest to theoreticians and experimentalists, and possess much synthetic value as well. Herein, a series of cyclic alkylidenecarbenes—formally obtained by replacing the carbonyl oxygen of four-, five-, and six-membered lactams, lactones, and thiolactones with a divalent carbon—were modeled at the CCSD(T)/cc-pVTZ//B3LYP/6-311+G** and CCSD(T)/cc-pVTZ//CCSD/6-311+G** levels of theory. The singlet carbenes were found to be more stable than the triplets. The strained heterocyclic alkynes formed by ring expansion of these singlet carbenes were also modeled. Interestingly, the C≡C bonds in the five-membered heterocycles, obtained from the rearrangement of ÎČ-lactam- and ÎČ-lactone-derived alkylidenecarbenes, displayed lengths intermediate between formal double and triple bonds. Furthermore, 2-(1-azacyclobutylidene)carbene was found to be nearly isoenergetic with its ring-expanded isomer, and 1-oxacyclopent-2-yne was notably higher in energy than its precursor carbene. In all other cases, the cycloalkynes were lower in energy than the corresponding carbenes. The transition states for ring-expansion were always lower for the 1,2-carbon shifts than for 1,2-nitrogen or oxygen shifts, but higher than for the 1,2-sulfur shifts. These predictions should be verifiable using carbenes bearing appropriate isotopic labels. Computed vibrational spectra for the carbenes, and their ring-expanded isomers, are presented and could be of value to matrix isolation experiments

    Transfer of autocollimator calibration for use with scanning gantry profilometers for accurate determination of surface slope and curvature of state of the art x ray mirrors

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    X ray optics, desired for beamlines at free electron laser and diffraction limited storage ring x ray light sources, must have almost perfect surfaces, capable of delivering light to experiments without significant degradation of brightness and coherence. To accurately characterize such optics at an optical metrology lab, two basic types of surface slope profilometers are used the long trace profilers LTPs and nanometer optical measuring NOM like angular deflectometers, based on electronic autocollimator AC ELCOMAT 3000. The inherent systematic errors of the instrument s optical sensors set the principle limit to their measuring performance. Where autocollimator of a NOM like profiler may be calibrated at a unique dedicated facility, this is for a particular configuration of distance, aperture size, and angular range that does not always match the exact use in a scanning measurement with the profiler. Here we discuss the developed methodology, experimental set up, and numerical methods of transferring the calibration of one reference AC to the scanning AC of the Optical Surface Measuring System OSMS , recently brought to operation at the ALS Xray Optics Laboratory. We show that precision calibration of the OSMS performed in three steps, allows us to provide high confidence and accuracy low spatial frequency metrology and not print into measurements the inherent systematic error of tool in use. With the examples of the OSMS measurements with a state of the art x ray aspherical mirror, available from one of the most advanced vendors of X ray optics, we demonstrate the high efficacy of the developed calibration procedure. The results of our work are important for obtaining high reliability data, needed for sophisticated numerical simulations of beamline performance and optimization of beamline usage of the optics. This work was supported by the U. S. Department of Energy under contract number DE AC02 05CH1123

    Towards predicting post-editing productivity

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    Machine translation (MT) quality is generally measured via automatic metrics, producing scores that have no meaning for translators who are required to post-edit MT output or for project managers who have to plan and budget for transla- tion projects. This paper investigates correlations between two such automatic metrics (general text matcher and translation edit rate) and post-editing productivity. For the purposes of this paper, productivity is measured via processing speed and cognitive measures of effort using eye tracking as a tool. Processing speed, average fixation time and count are found to correlate well with the scores for groups of segments. Segments with high GTM and TER scores require substantially less time and cognitive effort than medium or low-scoring segments. Future research involving score thresholds and confidence estimation is suggested

    Controlling chaos in spatially extended beam-plasma system by the continuous delayed feedback

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    In present paper we discuss the control of complex spatio-temporal dynamics in a {spatially extended} non-linear system (fluid model of Pierce diode) based on the concepts of controlling chaos in the systems with few degrees of freedom. A presented method is connected with stabilization of unstable homogeneous equilibrium state and the unstable spatio-temporal periodical states analogous to unstable periodic orbits of chaotic dynamics of the systems with few degrees of freedom. We show that this method is effective and allows to achieve desired regular dynamics chosen from a number of possible in the considered system.Comment: 12 pages, 12 figure

    Dynamical Friction in a Gaseous Medium

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    Using time-dependent linear perturbation theory, we evaluate the dynamical friction force on a massive perturber M_p traveling at velocity V through a uniform gaseous medium of density rho_0 and sound speed c_s. This drag force acts in the direction -\hat V, and arises from the gravitational attraction between the perturber and its wake in the ambient medium. For supersonic motion (M=V/c_s>1), the enhanced-density wake is confined to the Mach cone trailing the perturber; for subsonic motion (M<1), the wake is confined to a sphere of radius c_s t centered a distance V t behind the perturber. Inside the wake, surfaces of constant density are hyperboloids or oblate spheroids for supersonic or subsonic perturbers, respectively, with the density maximal nearest the perturber. The dynamical drag force has the form F_df= - I 4\pi (G M_p)^2\rho_0/V^2. We evaluate I analytically; its limits are I\to M^3/3 for M>1. We compare our results to the Chandrasekhar formula for dynamical friction in a collisionless medium, noting that the gaseous drag is generally more efficient when M>1 but less efficient when M<1. To allow simple estimates of orbit evolution in a gaseous protogalaxy or proto-star cluster, we use our formulae to evaluate the decay times of a (supersonic) perturber on a near-circular orbit in an isothermal \rho\propto r^{-2} halo, and of a (subsonic) perturber on a near-circular orbit in a constant-density core. We also mention the relevance of our calculations to protoplanet migration in a circumstellar nebula.Comment: 17 pages, 5 postscript figures, to appear in ApJ 3/1/9

    Time-delayed feedback control in astrodynamics

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    In this paper we present time-delayed feedback control (TDFC) for the purpose of autonomously driving trajectories of nonlinear systems into periodic orbits. As the generation of periodic orbits is a major component of many problems in astodynamics we propose this method as a useful tool in such applications. To motivate the use of this method we apply it to a number of well known problems in the astrodynamics literature. Firstly, TDFC is applied to control in the chaotic attitude motion of an asymmetric satellite in an elliptical orbit. Secondly, we apply TDFC to the problem of maintaining a spacecraft in a periodic orbit about a body with large ellipticity (such as an asteroid) and finally, we apply TDFC to eliminate the drift between two satellites in low Earth orbits to ensure their relative motion is bounded

    Relation between coupled map lattices and kinetic Ising models

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    A spatially one dimensional coupled map lattice possessing the same symmetries as the Miller Huse model is introduced. Our model is studied analytically by means of a formal perturbation expansion which uses weak coupling and the vicinity to a symmetry breaking bifurcation point. In parameter space four phases with different ergodic behaviour are observed. Although the coupling in the map lattice is diffusive, antiferromagnetic ordering is predominant. Via coarse graining the deterministic model is mapped to a master equation which establishes an equivalence between our system and a kinetic Ising model. Such an approach sheds some light on the dependence of the transient behaviour on the system size and the nature of the phase transitions.Comment: 15 pages, figures included, Phys. Rev. E in pres
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