Fused vs. spiro: Kinetic,not thermodynamic preference may direct the reaction of α-carbonyl oxonium ylides

Rh(II)-catalyzed decomposition of certain cyclic α-diazocarbonyl compounds in the presence of cyclic ethers has been shown to give bicyclic ring expansion products. These are thought to arise from a [1,4]-alkyl shift toward the carbonyl oxygen atom and are in contrast with the recently observed spirocyclic products of a Stevens-type [1,2]-alkyl shift within the postulated oxonium ylide intermediate. Quantum chemical calculations performed at the B3LYP/6-31G* level of theory showed that the former reaction pathway (toward fused bicycles) is kinetically preferred.     

On the Populations of Neon Levels in the Low Temperature Plasma of a Hollow Cathode Discharge

Atomic levels population measurements constitute an essential contribution to various aspects of plasma research: balance and cross-section of inelastic processes, admixtures effects on level excitation mechanism, purposeful optimisation of plasma parameters etc. Atomic level populations in the negative glow of a hollow cathode discharge are of utmost interest in view of the peculiarities of the spectral source: a rich spectrum consisting of gas lines, lines of the cathode material and also lines of the substances introduced in the discharge; intensive atomic and ionic lines of high excitation potentials; small spectral linewidth, convenient for analytical purposes.     

Chemical Shift and Its Uses as an Electronic Parameter in Structure-Activity Correlations

Apparent correlations are found between the N-H chemical shifts of congeneric series of compounds and the dipole moments of the molecules, such as lactams and thiolactams, cyclic ureas and thioureas. When there is a high degree of correlation, either the N-H chemical shift or the dipole moment of the molecule can be used as an electronic parameter in correlating the biological activity with the chemical structure. In a series of substituted salicylaldehydes the Hammett σ constant gives better correlation with the biological activity than the O-H chemical shift. This is probably due to the anisotropic effect of the substituent besides the electronic effect. Other factors affecting the N-H chemical shift, e.g. intramolecular hydrogen-bonding of nitrosoureas and the deshielding effect of a benzene ring, in o-phenyleneureas are also presented. In spite of the limitations, the chemical shifts of many compounds can be obtained very easily, therefore, their uses in structure-activity correlations deserve further investigation.     

Energy Transfer from the Upper Triplet States of Aromatic Molecules

The energy transfer from the upper triplet states of diphenylamine, naphthalene and triphenylene to toluene and hexene-1 is studed. Two mechanisms of dissipation transferred energy in solvents are discussed.     

On the numerical solution of ill‐conditioned linear systems by regularization and iteration

We propose to reduce the (spectral) condition number of a given linear system by adding a suitable diagonal matrix to the system matrix, in particular by shifting its spectrum. Iterative procedures are then adopted to recover the solution of the original system. The case of real symmetric positive definite matrices is considered in particular, and several numerical examples are given. This approach has some close relations with Riley's method and with Tikhonov regularization. Moreover, we identify approximately the aforementioned procedure with a true action of preconditioning.     

High level ab initio,DFT, and RRKM calculations for the unimolecular decomposition reaction of ethylamine

Mechanisms for the decomposition reaction of ethylamine, CH₃CH₂NH₂, were investigated using ab initio, DFT, and RRKM calculations. Optimized geometries of reactants, transition states, intermediates, and products were determined at HF, MP2, and B3LYP levels of theory using the 6-31G(d) and 6-31+G(d) basis sets. Single point energies were also determined at G3MP2B3 and G3B3 levels of theory. Thermodynamic properties, activation energies, enthalpies and Gibbs energies of activation were calculated for each reaction pathway investigated. Intrinsic reaction coordinate (IRC) analysis was performed to characterize the transition states on the potential energy surface. The conformational change and planarity of the ethylamine moiety along with the twist angle of the amino group about the CN axis are examined. Four pathways for the decomposition reaction of ethylamine were studied. All pathways involve a 1,2-elimination reaction and 1,3-proton shift to produce ethene, ethanimine, ethenamine, and methanimine. All pathways are single-step mechanisms. Elimination of the NH₃ dominates the decomposition behavior up to 1200 K whereas after this temperature, secession of the C–N gradually holds more importance. While pathways signifying departures of NH₃ and NH₂ exhibit pressure-dependent behavior, branching ratios for these two channels are generally not influenced by variation in pressure higher than the atmospheric pressure.     

Direct calculation of time varying Aharonov-Bohm effect

The Aharonov-Bohm effect (ABE) for steady magnetic fields is a well known phenomenon. However, if the current in the infinite solenoid that creates the magnetic field is time-dependent, that is in the presence of both magnetic and electric fields, there is no agreement whether the effect would be present. In this note, we try to investigate time varying ABE by a direct calculation in a set-up with a weak time dependent magnetic field. We find that the electric field arising out of the time-varying magnetic field in the path of the electrons does not enter the action integral but only changes the path of the electron from the source to the slits and then on to the detector. We find a frequency dependent AB phase shift. At low frequencies the result smoothly approaches the one for a constant field as the frequency tends towards zero. On the other hand, for high frequencies such that the AB-phase induced in the path of the wave packet oscillates rapidly, the net effect will be very small which is borne out by our results.     

Tandem rearrangements of a cyclic bis-allene

Reaction of the bis-dibromocarbene adduct of cyclonona-1,4,7-triene with methyllithium leads to a mixture of meso and racemic cycloundeca-1,2,5,6,9-pentaenes; the former rearranges at ambient temperature through a set of pericyclic reactions.     

Linearization of nonlinear filter generators and its application to cryptanalysis of stream ciphers

Nonlinear filter generators are commonly used as keystream generators in stream ciphers. A nonlinear filter generator utilizes a nonlinear filtering function to combine the outputs of a linear feedback shift register (LFSR) to improve the linear complexity of keystream sequences. However, the LFSR-based stream ciphers are still potentially vulnerable to algebraic attacks that recover the key from some keystream bits. Although the known algebraic attacks only require polynomial time complexity of computations, all have their own constraints. This paper uses the linearization of nonlinear filter generators to cryptanalyze LFSR-based stream ciphers. Such a method works for any nonlinear filter generators. Viewing a nonlinear filter generator as a Boolean network that evolves as an automaton through Boolean functions, we first give its linearization representation. Compared to the linearization representation in Limniotis et al. (2008), this representation requires lower spatial complexity of computations in most cases. Based on the representation, the key recoverability is analyzed via the observability of Boolean networks. An algorithm for key recovery is given as well. Compared to the exhaustive search to recover the key, using this linearization representation requires lower time complexity of computations, though it leads to exponential time complexity.