The reaction of Cp'2CeH (Cp' = 1,2,4-(Me3C)3C5H2 ) with MeOSiMe3 gives Cp'2CeOMe and HSiMe3 and the reaction of the metallacycle, Cp'[(Me3C)2C5H2C(Me) 2CH2]Ce, with MeOSiMe3 yields Cp'2CeOCH2SiMe3, formed from hypothetical Cp'2CeCH2OSiMe3 by a [1, 2] shift also known as a silyl-Wittig rearrangement. Although both cerium products are alkoxides, they are formed by different pathways. DFT calculations on the reaction of the model metallocene, Cp2CeH, and MeOSiMe3 show that the lowest energy pathway is a H for OMe exchange at Ce that occurs by way of a sigma-bond metathesis transition state as SiMe3 exchanges partners. The formation of Cp2CeOCH2SiMe3 occurs by way of a low activation barrier [1, 2]shift of the SiMe3 group in Cp2CeCH2OSiMe3. Calculations on a model metallacycle, Cp[C5H4C(Me)2CH2]Ce, show that the metallacycle favors CH bond activation over sigma-bond metathesis involving the transfer of the SiMe3 group in good agreement with experiment. The sigma-bond metathesis involving the transfer of SiMe3 and the [1, 2]shift of SiMe3 reactions have in common a pentacoordinate silicon at the transition states. A molecular orbital analysis illustrates the connection between these two Si-O bond cleavage reactions and traces the reason why they occur for a silyl but not for an alkyl group to the difference …

The Neutralized Drift Compression Experiment (NDCX-II) is an 11 M$ induction accelerator project currently in construction at Lawrence Berkeley National Laboratory for warm dense matter (WDM) experiments investigating the interaction of ion beams with matter at elevated temperature and pressure. The machine consists of a lithium injector, induction accelerator cells, diagnostic cells, a neutralized drift compression line, a final focus solenoid, and a target chamber. The induction cells and some of the pulsed power systems have been reused from the decommissioned Advanced Test Accelerator at Lawrence Livermore National Laboratory after refurbishment and modification. The machine relies on a sequence of acceleration waveforms to longitudinally compress the initial ion pulse from 600 ns to less than 1 ns in {approx} 12 m. Radial confinement of the beam is achieved with 2.5 T pulsed solenoids. In the initial hardware configuration, 50 nC of Li{sup +} will be accelerated to 1.25 MeV and allowed to drift-compress to a peak current of {approx}40 A. The project started in the summer of 2009. Construction of the accelerator will be completed in the fall of 2011 and will provide a worldwide unique opportunity for ion-driven warm dense matter experiments as well as research related to novel …

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A material subjected to radiation damage will usually experience changes in its physical properties. Measuring these changes in the physical properties provides a basis to study radiation damage in a material which is important for a variety of real world applications from reactor materials to semiconducting devices. When investigating radiation damage, the relative sensitivity of any given property can vary considerably based on the concentration and type of damage present as well as external parameters such as the temperature and starting material composition. By measuring multiple physical properties, these differing sensitivities can be leveraged to provide greater insight into the different aspects of radiation damage accumulation, thereby providing a broader understanding of the mechanisms involved. In this report, self-damage from {alpha}-particle decay in Pu is investigated by measuring two different properties: magnetic susceptibility and resistivity. The results suggest that while the first annealing stage obeys second order chemical kinetics, the primary mechanism is not the recombination of vacancy-interstitial close pairs.

The electrical and friction properties of omega-(trans-4-stilbene)alkylthiol self-assembled monolayers (SAMs) on Au(111) were investigated using atomic force microscopy (AFM) and near edge x-ray absorption fine structure spectroscopy (NEXAFS). The sample surface was uniformly covered with a molecular film consisting of very small grains. Well-ordered and flat monolayer islands were formed after the sample was heated in nitrogen at 120 oC for 1 h. While lattice resolved AFM images revealed a crystalline phase in the islands, the area between islands showed no order. The islands exhibit substantial reduction (50percent) in friction, supporting the existence of good ordering. NEXAFS measurements revealed an average upright molecular orientation in the film, both before and after heating, with a narrower tilt-angle distribution for the heated fim. Conductance-AFM measurements revealed a two orders of magnitude higher conductivity on the ordered islands than on the disordered phase. We propose that the conductance enhancement is a result of a better pi-pi stacking between the trans-stilbene molecular units as a result of improved ordering in islands.

In interstellar and interplanetary space, the size distribution and composition of dust grains play an important role. For example, dust grains determine optical and ultraviolet extinction levels in astronomical observations, dominate the cooling rate of our Galaxy, and sets the thermal balance and radiative cooling rates in molecular clouds, which are the birth place of stars. Dust grains are also a source of damage and failure to space hardware and thus present a hazard to space flight. To model the size distribution and composition of dust grains, and their effect in the above scenarios, it is vital to understand the mechanism of dust-shock interaction. We demonstrate a new experiment which employs a laser to subject dust grains to pressure spikes similar to those of colliding astrophysical dust, and which accelerates the grains to astrophysical velocities. The new method generates much larger data sets than earlier methods; we show how large quantities (thousands) of grains are accelerated at once, rather than accelerating individual grains, as is the case of earlier methods using electric fields.

Vacuum insulators composed of alternating layers of metal and dielectric, known as high-gradient insulators (HGIs), have been shown to withstand higher electric fields than conventional insulators. Primary or secondary electrons (emitted from the insulator surface) can be deflected by magnetic fields from external sources, the high-current electron beam, the conduction current in the transmission line, or the displacement current in the insulator. These electrons are deflected either toward or away from the insulator surface and this affects the performance of the vacuum insulator. This paper shows the effects of displacement current from short voltage pulses on the performance of high gradient insulators. Generally, vacuum insulator failure is due to surface flashover, initiated by electrons emitted from a triple junction. These electrons strike the insulator surface thus producing secondary electrons, and can lead to a subsequent electron cascade along the surface. The displacement current in the insulator can deflect electrons either toward or away from the insulator surface, and affects the performance of the vacuum insulator when the insulator is subjected to a fast high-voltage pulse. Vacuum insulators composed of alternating layers of metal and dielectric, known as high-gradient insulators (HGIs), have been shown to withstand higher electric fields than conventional …

This article discusses a study to examine the longitudinal trajectories in objectively measured physical activity (PA), to identify unknown (i.e., latent) subgroups with distinct trajectories, and to examine the correlates of latent subgroups among community dwelling women.

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This article investigates the influence of water temperature on cardiac plasticity in developing mahi-mahi.

Article discussing the reduction of student's exam grade performance when spending more time in an exam.