On the Reactivity of Tetrakis(trifluoromethyl)cyclopentadienone towards Carbon-Based Lewis Bases

The reactivitiy of tetrakis(trifluoromethyl)cyclopentadienone towards different C-based Lewis bases, such as N-heterocyclic carbenes (NHC), ylides and isonitriles, are reported. While sterically not hindered carbenes were found to yield kinetic adducts by regiospecific nucleophilic attack at the position adjacent to the carbonyl group of the ketone, bulkier nucleophiles afforded the thermodynamically more stable O-bridged zwitterions. Interestingly, isonitriles were found to dimerize and trimerize under the same reaction conditions, forming bicyclic products that evolve differently depending on the nature of the substituents

Persistence of instanton connections in chemical reactions with time dependent rates

The evolution of a system of chemical reactions can be studied, in the eikonal approximation, by means of a Hamiltonian dynamical system. The fixed points of this dynamical system represent the different states in which the chemical system can be found, and the connections among them represent instantons or optimal paths linking these states. We study the relation between the phase portrait of the Hamiltonian system representing a set of chemical reactions with constant rates and the corresponding system when these rates vary in time. We show that the topology of the phase space is robust for small time-dependent perturbations in concrete examples and state general results when possible. This robustness allows us to apply some of the conclusions on the qualitative behavior of the autonomous system to the time-dependent situation

Structural analysis, magnetic and transport properties of the (Ru1-xCox)Sr2GdCu2O8 system

The effects of Co substitution on structural and superconducting properties of RuSr2GdCu2O8 compound have been studied. Rietveld refinements of the X-ray diffraction patterns indicate that the cobalt ion progressively replaces ruthenium sites. This replacement induces significant changes on the crystal structure and on the magnetic and superconducting properties. The effects Co substitution on the superconducting behaviour, and more particulary on the changes induce by the hole doping mechanism, were investigated in (Ru1-xCox)Sr2GdCu2O8 by a "bond valence sum" analysis with Co content from x= 0.0 to x = 0.2. The weak ferromagnetic transition at Tm= 138.2 K is shifted to lower temperature, and suppressed at higher Co content. From the crystallographic point of view the Ru-O(1)-Cu bond angle, associated to the rotation of the RuO6 octahedra, around the c-axis remain essetially constant when Ru is substituted by Co. Furthermore, increasing Co content has the effect to increase the weak ferromagnetic moment, which may be interpreted as the main responsible for breaking the delicate balance between magnetic and superconducting ordering.Comment: 21 pages, 8 figure

Point-contact spectroscopy on URu2_2Si2_2

Tunnel and point contact experiments have been made in a URu$_2$Si$_2$ single crystal along the c-axis. The experiments were performed changing temperature and contact size in a low temperature scanning tunneling microscope. A resonance develops at the Fermi level at $T\sim 60$ K. This resonance splits and becomes asymmetric when the 17.5 K phase transition is crossed. These results are consistent with the existence of Kondo like bound states of the U$^{4+}$ ionic configurations and the conduction electrons. Below the transition, these configurations are split by the development of quadrupolar ordering. The peak separation can be interpreted as a direct measurement of the order parameter. Measurements on a policrystalline UAu_2Si_2$ sample are also reported, with a comparative study of the behavior of both materials.Comment: 4 pages (Latex) + 2 postscript figure

Feasibility study: investigation of car park-based V2G services in the UK central hub

The increasing uptake of electric vehicles, and the established practice of long-term parking at stations and airports, offers an opportunity to develop a flexible approach to help with the energy storage dilemma. This paper investigates the feasibility of using a number of EV batteries as an energy storage and grid balancing solution within the UK Central Hub area. Here, the capital cost of the vehicle is a sunk cost to the EV owner. The potential income generated, or discount on long-term parking, is an additional benefit of ownership. This paper considers the income available to a small and large size car park from the different market mechanisms to offer grid support in the UK and contrasts this with the complexity and costs of the EV charging infrastructure required within these types of scheme

Machine Learning in Automated Text Categorization

The automated categorization (or classification) of texts into predefined categories has witnessed a booming interest in the last ten years, due to the increased availability of documents in digital form and the ensuing need to organize them. In the research community the dominant approach to this problem is based on machine learning techniques: a general inductive process automatically builds a classifier by learning, from a set of preclassified documents, the characteristics of the categories. The advantages of this approach over the knowledge engineering approach (consisting in the manual definition of a classifier by domain experts) are a very good effectiveness, considerable savings in terms of expert manpower, and straightforward portability to different domains. This survey discusses the main approaches to text categorization that fall within the machine learning paradigm. We will discuss in detail issues pertaining to three different problems, namely document representation, classifier construction, and classifier evaluation.Comment: Accepted for publication on ACM Computing Survey

Size-Dependent Dissociation of Carbon Monoxide on Cobalt Nanoparticles

[[abstract]]In situ soft X-ray absorption spectroscopy (XAS) was employed to study the adsorption and dissociation of carbon monoxide molecules on cobalt nanoparticles with sizes ranging from 4 to 15 nm. The majority of CO molecules adsorb molecularly on the surface of the nanoparticles, but some undergo dissociative adsorption, leading to oxide species on the surface of the nanoparticles. We found that the tendency of CO to undergo dissociation depends critically on the size of the Co nanoparticles. Indeed, CO molecules dissociate much more efficiently on the larger nanoparticles (15 nm) than on the smaller particles (4 nm). We further observed a strong increase in the dissociation rate of adsorbed CO upon exposure to hydrogen, clearly demonstrating that the CO dissociation on cobalt nanoparticles is assisted by hydrogen. Our results suggest that the ability of cobalt nanoparticles to dissociate hydrogen is the main parameter determining the reactivity of cobalt nanoparticles in Fischer–Tropsch synthesis.[[notice]]補正完畢[[incitationindex]]SCI[[booktype]]紙本[[booktype]]電子

Quasi-stationary regime of a branching random walk in presence of an absorbing wall

A branching random walk in presence of an absorbing wall moving at a constant velocity $v$ undergoes a phase transition as the velocity $v$ of the wall varies. Below the critical velocity $v_c$, the population has a non-zero survival probability and when the population survives its size grows exponentially. We investigate the histories of the population conditioned on having a single survivor at some final time $T$. We study the quasi-stationary regime for $v<v_c$ when $T$ is large. To do so, one can construct a modified stochastic process which is equivalent to the original process conditioned on having a single survivor at final time $T$. We then use this construction to show that the properties of the quasi-stationary regime are universal when $v\to v_c$. We also solve exactly a simple version of the problem, the exponential model, for which the study of the quasi-stationary regime can be reduced to the analysis of a single one-dimensional map.Comment: 2 figures, minor corrections, one reference adde

Noise Characterization and Filtering in the MicroBooNE Liquid Argon TPC

The low-noise operation of readout electronics in a liquid argon time projection chamber (LArTPC) is critical to properly extract the distribution of ionization charge deposited on the wire planes of the TPC, especially for the induction planes. This paper describes the characteristics and mitigation of the observed noise in the MicroBooNE detector. The MicroBooNE's single-phase LArTPC comprises two induction planes and one collection sense wire plane with a total of 8256 wires. Current induced on each TPC wire is amplified and shaped by custom low-power, low-noise ASICs immersed in the liquid argon. The digitization of the signal waveform occurs outside the cryostat. Using data from the first year of MicroBooNE operations, several excess noise sources in the TPC were identified and mitigated. The residual equivalent noise charge (ENC) after noise filtering varies with wire length and is found to be below 400 electrons for the longest wires (4.7 m). The response is consistent with the cold electronics design expectations and is found to be stable with time and uniform over the functioning channels. This noise level is significantly lower than previous experiments utilizing warm front-end electronics.Comment: 36 pages, 20 figure