Reaction mechanism and rate constants of the CH+CH4 reaction: a theoretical study

Ab initio and density functional calculations have been performed to elucidate the mechanism of CH radical insertion into methane. The results show that the reaction can be viewed to occur via two stages. On the first stage, the CH radical approaches methane without large structural changes to acquire proper positioning for the subsequent stage, where H-migration occurs from CH₄ to CH, along with a C–C bond formation. Where the first stage ends and the second begins, a tight transition state was located using the B3LYP/6-311G(d,p) and MP4(SDQ)/6-311++G(d,p) methods. Using a rigid rotor – harmonic oscillator approach within transition state theory, we show that at the MP5/6-311++G(d,p)//MP4(SDQ)/6-311++G(d,p) level the calculated rate constants are in a reasonably good agreement with experiment in a broad temperature range of 145–581 K. Even at low temperatures, the insertion reaction bottleneck is found about the location of the tight transition state, rather than at long separations between the CH and CH₄ reactants. In addition, high level CCSD(T)-F12/CBS calculations of the remainder of the C₂H₅ potential energy surface predict the CH+CH₄ reaction to proceed via the initial insertion step to the ethyl radical which then can emit a hydrogen atom to form highly exothermic C₂H₄+H products.     

Beyond the standard model: Working group report

This report summarises the activities of the working group on ‘Physics beyond the Standard Model’. The results of investigations in incorporatingR-parity in grand unification, the possibility of a light charged Higgs boson in extension of MSSM and radiative generation of neutral vector boson self-couplings within the MSSM are described. Also given is an account of activities in neutrino physics, namely a proposal for a study of the atmospheric muon anomaly in deep underground mines, a field theoretic study of neutrino oscillations and a mechanism to generate appropriate masses of three active plus one sterile neutrino species.     

Elastic scattering of low-energy electrons by NO

We report elastic integral, momentum transfer and differential cross sections for electron scattering by N₂O for energies up to 50 eV. These results were obtained at the static-exchange approximation with the Schwinger Multichannel Method with Pseudopotentials [M.H.F. Bettega, L.G. Ferreira and M.A.P. Lima, Phys. Rev. A 47, 1111 (1993)]. In general our results show good agreement with experimental data and with other theoretical results but some discrepancies are found. We have also found a shape resonance around 4 eV in agreement with previous calculations using the R-matrix Method of Sarpal et al. [J. Phys. B 29, 857 (1996)]. On the other hand, the existence of a resonance at about 13 eV, clearly seen by the Schwinger Variational Iterative Method [Michelin et al., J. Phys. B 29, 2115 (1996)], can not be confirmed by our calculations. At this energy, our cross sections show a broad bump with no clear resonant behavior given by the eigenphase sum. Received: 13 November 1997 / Revised: 13 March 1998 / Accepted: 9 April 1998     

Magnetic interactions in the monoclinic ludwigite Cu FeO BO

The system Cu₂FeO₂BO₃ is an oxyborate belonging to the family of the ludwigites. In this paper we present AC susceptibility, magnetization measurements and M?ssbauer spectroscopy on this material which allows for a complete characterization of its complex magnetic behavior. We find an hierarchy of interactions which clearly defines three regimes with decreasing temperature. These are associated with, the freezing of the Fe moments, the antiferromagnetic ordering of the Cu sub-lattice and finally the coupling between both systems. Received 25 September 1998     

Copper and iron interactions with angiotensin-converting enzyme inhibitors. A study by fast-atom bombardment tandem mass spectrometry

Fast atom bombardment, combined with high-energy collision-induced tandem mass spectrometry, has been used to investigate gas-phase metal-ion interactions with captopril, enalaprilat and lisinopril, all angiotensin-converting enzyme inhibitors.Suggestions for the location of metal-binding sites are presented. For captopril, metal binding occurs most likely at both the sulphur and the nitrogen atom. For enalaprilat and lisinopril, binding preferably occurs at the amine nitrogen. Copyright 1999 John Wiley & Sons, Ltd.     

Analysis of confiscated fireworks using Raman spectroscopy assisted with SEM‐EDS and FTIR

A forensic analysis of several samples of pyrotechnic artefacts was performed by Raman spectroscopy assisted by scanning electron microscopy/energy‐dispersive X‐ray spectroscopy (SEM‐EDS) and Fourier transform infrared (FTIR) analysis. Among the components, several nitrates, ammonium perchlorate, nitrocellulose, metallic titanium particles and shellac were detected. The combination of Raman spectroscopy and SEM‐EDS showed very useful performance. All components were detected by Raman spectroscopy except for shellac, kaolinite and titanium particles, which were not conclusive enough and had to be determined by FTIR and EDS. In contrast, many compounds were not detected by FTIR. Copyright © 2011 John Wiley & Sons, Ltd.     

Nonlinear free vibrations of beams in space due to internal resonance

The geometrically nonlinear free vibrations of beams with rectangular cross section are investigated using a p-version finite element method. The beams may vibrate in space, hence they may experience longitudinal, torsional and non-planar bending deformations. The model is based on Timoshenko’s theory for bending and assumes that, under torsion, the cross section rotates as a rigid body and is free to warp in the longitudinal direction, as in Saint-Venant’s theory. The geometrical nonlinearity is taken into account by considering Green’s nonlinear strain tensor. Isotropic and elastic beams are investigated and generalised Hooke’s law is used. The equation of motion is derived by the principle of virtual work. Mostly clamped–clamped beams are investigated, although other boundary conditions are considered for validation purposes. Employing the harmonic balance method, the differential equations of motion are converted into a nonlinear algebraic form and then solved by a continuation method. One constant term, odd and even harmonics are assumed in the Fourier series and convergence with the number of harmonics is analysed. The variation of the amplitude of vibration with the frequency of vibration is determined and presented in the form of backbone curves. Coupling between modes is investigated, internal resonances are found and the ensuing multimodal oscillations are described. Some of the couplings discovered lead from planar oscillations to oscillations in the three dimensional space.     

Effect of glycine substitution on the ferroelectric phase of betaine arsenate [(CH3)3NCH2COO·H3AsO4]

The present work reports an experimental investigation on the influence of glycine (NH₂CH₂COOH) substitution in the polar properties and the critical dynamics of the molecular ferroelectric betaine arsenate, (CH₃)₃NCH₂COO·H₃AsO₄. The dielectric dispersion (20 Hz<ν<3 MHz) and the thermally induced displacement currents are investigated in detail over the extended Curie region of the system (130 K<T<100 K). The results obtained for a single crystal with nominal glycine content of 20% are analyzed, compared with those obtained for pure betaine arsenate and discussed within the scope of a phenomenological Landau model previously used to describe a system with competing ferroelectric and structural instabilities.