Diminishing blocking interval in particle-conveying channel bundles

We consider a channel bundle consisting of N_c parallel channels conveying a particulate flux. Particles enter these channels according to a homogeneous Poisson process and exit after a fixed transit time, τ. An individual channel blocks if N particles are simultaneously present. When a channel is blocked the flux previously entering it is redistributed evenly over the remaining open channels. We perform event driven simulations to examine the behaviour of an initially empty channel bundle with a total entering flux of intensity Λ. The mean blockage time of the kth channel is denoted by ? t_k ? ,k = 1,...,N_c. For N = 1, as shown previously, the interval between successive blockages is constant, while for N> 1 an accelerating cascade, i.e. one in which the interval between successive blockages decreases, is observed. After an initial transient regime we observe a well-defined universal regime that is characterized by\hbox{$\Delta_k^{(N)} = (-1)^{N-1}\frac{[(N-1)!]^2}{(\Lambda\tau)^N}$}Δk(N)=(?1)N?1[(N?1)!]2(Λτ)Nwhere \hbox{$\Delta_k^{(1)}=\langle t_k \rangle-\langle t_{k-1}\rangle$}Δk(1)=?tk???tk?1? and \hbox{$\Delta_k^{(j)}=\Delta_k^{(j-1)}-\Delta_{k-1}^{(j-1)}$}Δk(j)=Δk(j?1)?Δk?1(j?1) denotes the jth order difference.     

Homogeneous and unimolecular gas‐phase thermal decomposition kinetics of methyl benzoylformate: experimental and theoretical study

The kinetics of the gas‐phase thermal decomposition of the α‐ketoester methyl benzoylformate was carried out in a static system with reaction vessel deactivated with allyl bromide, and in the presence of the free radical inhibitor propene. The rate coefficients were determined over the temperature range of 440–481 °C and pressures from 32 to 80 Torr. The reaction was found to be homogenous, unimolecular and obey a first‐order rate law. The products are methyl benzoate and CO. The temperature dependence of the rate coefficient gives the following Arrhenius parameters: log₁₀ k (s^?1) = 13.56 ± 0.31 and E_a (kJ mol^?1) = 232.6 ± 4.4. Theoretical calculations of the kinetic and thermodynamic parameters are in good agreement with the experimental values using PBE1PBE/6‐311++g(d,p). A theoretical Arrhenius plot was constructed at this level of theory, and the good agreement with the experimental Arrhenius plot suggests that this model of transition state may describe reasonably the elimination process. These results suggest a concerted non‐synchronous semi‐polar three‐membered cyclic transition state type of mechanism. The most advanced coordinate is the bond breaking C^δ+‐‐‐^δ‐OCH₃ with an evolution of 66.7%, implying this as the limiting factor of the elimination process. Copyright © 2014 John Wiley & Sons, Ltd.     

Gas‐phase elimination kinetics of selected aliphatic α,β‐unsaturated aldehydes catalyzed by hydrogen chloride

The gas‐phase elimination of 2‐methyl‐2‐propenal catalyzed by HCl yields propene and CO gas, while E‐2‐pentenal with the same catalyst gives butene and CO gas. The kinetics determinations were carried out in a static system with the reaction vessels deactivated with allyl bromide and the presence of the free radical inhibitor toluene. Temperature and pressure ranges were 350.0–410.0 °C and 34–76 Torr. The elimination reactions are homogeneous and unimolecular, and follow a first‐order rate law. The rate coefficients for the reactions are expressible by the following Arrhenius equations: Data from the kinetic and thermodynamic parameters of these catalyzed elimination reactions implies a mechanism of a concerted five‐membered cyclic transition state structure for the formation of the corresponding olefin and carbon monoxide. Copyright © 2015 John Wiley & Sons, Ltd.     

Spin gunn effect

We predict that the flow of unpolarized current in electron-doped GaAs and InP at room temperature is unstable at high electric fields to the dynamic formation of spin-polarized current pulses. Spin-polarized current is spontaneously generated because the conductivity of a spin-polarized electron gas differs from that of an unpolarized electron gas, even in the absence of spin-orbit interaction. Magnetic fields are not required for the generation of these spin-polarized current pulses, although they can help align the polarization of sequential pulses along the same axis.     

Comment on ‘Ab initio study: the potential energy curves and rovibrational spectrum of low-lying excited states of HCl+ cation’ (Molecular Physics, 114:19, 2817–2823)

In a recent article, Y. Liu, X. Cheng, H. Cheng, J. Cheng and X. Song [Mol. Phys., 114:19, 2817–2823] report on the calculation of potential energy curves and the derivation of spectroscopic constants and line intensities for the lowest energy electronic states of HCl⁺. There are several shortcomings in the article; the most notable being the incorrect ordering of the ²П_3/2 and ²П_1/2 state energies, erroneous selection rules, which lead to the absence of a Q-branch in their predicted spectra, incorrect Höln–London factors, and a missing appendix.