The reaction between silylene and ammonia: some gas-phase kinetic and quantum chemical studies

Time-resolved kinetic studies of the reaction of silylene, SiH2, generated by 193 nm laser flash photolysis of silacyclopent-3-ene, have been carried out in the presence of ammonia, NH3. Second order kinetics were observed. The reaction was studied in the gas phase at 10 Torr total pressure in SF6 bath gas at each of the three temperatures, 299, 340 and 400 K. The second order rate constants (laser pulse energy of 60 mJ/pulse) fitted the Arrhenius equation: log(k/cm3 molecule-1 s-1) = (-10.37 ± 0.17) + (0.36 ± 1.12 kJ mol-1)/RTln10 Experiments at other pressures showed that these rate constants were unaffected by pressure in the range 10-100 Torr, but showed small decreases in value at 3 and 1 Torr. There was also a weak intensity dependence, with rate constants decreasing at laser pulse energies of 30 mJ/pulse. Ab initio calculations at the G3 level of theory, show that SiH2 + NH3 should form an initial adduct (donor-acceptor complex), but that energy barriers are too great for further reaction of the adduct. This implies that SiH2 + NH3 should be a pressure dependent association reaction. The experimental data are inconsistent with this and we conclude that SiH2 decays are better explained by reaction of SiH2 with the amino radical, NH2, formed by photodissociation of NH3 at 193 nm. The mechanism of this previously unstudied reaction is discussed

Hyper-chaotic magnetisation dynamics of two interacting dipoles

The present work is a numerical study of the deterministic spin dynamics of two interacting anisotropic magnetic particles in the presence of a time-dependent external magnetic field using the Landau–Lifshitz equation. Particles are coupled through the dipole–dipole interaction. The applied magnetic field is made of a constant longitudinal amplitude component and a time-dependent transversal amplitude component. Dynamical states obtained are represented by their Lyapunov exponents and bifurcation diagrams. The dependence on the largest and the second largest Lyapunov exponents, as a function of the magnitude and frequency of the applied magnetic field, and the relative distance between particles, is studied. The system presents multiple transitions between regular and chaotic behaviour depending on the control parameters. In particular, the system presents consistent hyper-chaotic states

Generation of optimal trajectories for Earth hybrid pole sitters

A pole-sitter orbit is a closed path that is constantly above one of the Earth's poles, by means of continuous low thrust. This work proposes to hybridize solar sail propulsion and solar electric propulsion (SEP) on the same spacecraft, to enable such a pole-sitter orbit. Locally-optimal control laws are found with a semi-analytical inverse method, starting from a trajectory that satisfies the pole-sitter condition in the Sun-Earth circular restricted three-body problem. These solutions are subsequently used as first guess to find optimal orbits, using a direct method based on pseudospectral transcription. The orbital dynamics of both the pure SEP case and the hybrid case are investigated and compared. It is found that the hybrid spacecraft allows savings on propellant mass fraction. Finally, it is shown that for sufficiently long missions, a hybrid pole-sitter, based on mid-term technology, enables a consistent reduction in the launch mass for a given payload, with respect to a pure SEP spacecraft

Anomalous phase of MnP at very low field

Manganese phosphide MnP has been investigated for decades because of its rich magnetic phase diagram. It is well known that the MnP exhibits the ferromagnetic phase transition at \Tc=292 K and the helical magnetic phase below \TN=47 K at zero field. Recently, a novel magnetic phase transition was observed at $T^* = 282$ K when the magnetic field is lower than 5 Oe. However, the nature of the new phase has not been illuminated yet. In order to reveal it, we performed the AC and the DC magnetization measurements for a single crystal MnP at very low field. A divergent behavior of the real and the imaginary part of the AC susceptibility and a sharp increase of the DC magnetization was observed at $T^*$, indicating the magnetic phase transition at $T^*$. Furthermore a peculiar temperature hysteresis was observed: namely, the magnetization depends on whether cooling sample to the temperature lower than \TN or not before the measurements. This hysteresis phenomenon suggests the complicated nature of the new phase and a strong relation between the magnetic state of the new phase and the helical structure.Comment: 4 pages, 2 figure

New opportunities for secure communication networks using shaped femtosecond laser pulses inducing filamentation processes in the atmosphere

The current study discusses new opportunities for secure ground to satellite communications using shaped femtosecond pulses that induce spatial hole burning in the atmosphere for efficient communications with data encoded within super-continua generated by femtosecond pulses. Refractive index variation across the different layers in the atmosphere may be modelled using assumptions that the upper strata of the atmosphere and troposphere behaving as layered composite amorphous dielectric networks composed of resistors and capacitors with different time constants across each layer. Input-output expressions of the dynamics of the networks in the frequency domain provide the transmission characteristics of the propagation medium. Femtosecond pulse shaping may be used to optimize the pulse phase-front and spectral composition across the different layers in the atmosphere. A generic procedure based on evolutionary algorithms to perform the pulse shaping is proposed. In contrast to alternative procedures that would require ab initio modelling and calculations of the propagation constant for the pulse through the atmosphere, the proposed approach is adaptive, compensating for refractive index variations along the column of air between the transmitter and receiver

New opportunities for secure communication networks using shaped femtosecond laser pulses inducing filamentation processes in the atmosphere

The current study discusses new opportunities for secure ground to satellite communications using shaped femtosecond pulses that induce spatial hole burning in the atmosphere for efficient communications with data encoded within super-continua generated by femtosecond pulses. Refractive index variation across the different layers in the atmosphere may be modelled using assumptions that the upper strata of the atmosphere and troposphere behaving as layered composite amorphous dielectric networks composed of resistors and capacitors with different time constants across each layer. Input-output expressions of the dynamics of the networks in the frequency domain provide the transmission characteristics of the propagation medium. Femtosecond pulse shaping may be used to optimize the pulse phase-front and spectral composition across the different layers in the atmosphere. A generic procedure based on evolutionary algorithms to perform the pulse shaping is proposed. In contrast to alternative procedures that would require ab initio modelling and calculations of the propagation constant for the pulse through the atmosphere, the proposed approach is adaptive, compensating for refractive index variations along the column of air between the transmitter and receiver

Insulin Pumps: Beyond Basal-Bolus

Insulin pumps are a major advance in diabetes management, making insulin dosing easier and more accurate and providing great flexibility, safety, and efficacy for people who need basal-bolus insulin therapy. They are the preferred treatment for people with type 1 diabetes and many with type 2 diabetes who require insulin. This article reviews the basics of how insulin pumps work, who benefits from a pump, and how to manage inpatients and outpatients on insulin pumps

Revealing ensemble state transition patterns in multi-electrode neuronal recordings using hidden Markov models

In order to harness the computational capacity of dissociated cultured neuronal networks, it is necessary to understand neuronal dynamics and connectivity on a mesoscopic scale. To this end, this paper uncovers dynamic spatiotemporal patterns emerging from electrically stimulated neuronal cultures using hidden Markov models (HMMs) to characterize multi-channel spike trains as a progression of patterns of underlying states of neuronal activity. However, experimentation aimed at optimal choice of parameters for such models is essential and results are reported in detail. Results derived from ensemble neuronal data revealed highly repeatable patterns of state transitions in the order of milliseconds in response to probing stimuli