Intramolecular hemiacetals. The acid-base-catalyzed ring-chain interconversion of 2-substituted 2-hydroxy-4,4-dimethylmorpholinium cations in aqueous solution.

The ring-chain tautomerism in aqueous solution of some aryl-substituted morpholinium salts (bromides), has been studied and equilibrium constants are reported. In the crystals the substrates exist entirely in their cyclic forms as hemiacetals, but in aqueous solution NMR measurements reveal that an equilibrium is established between the cyclic (hemiacetal) and the noncyclic (ketone) form, the degree of ring-opening being more pronounced with electron-donating aryl substituents at the carbonyl carbon. The kinetics of the ring-chain interconversion in water has been investigated spectrophotometrically by a 'pH jump' stopped-flow technique. General base catalysis is observed with a Br?nsted beta value apparently independent of substituent and equal to 0.60. The Hammett rho values for various base catalysts are close to those for very similar intermolecular reactions involving hemiacetal breakdown, leading to the suggestion of a 'normal' class n mechanism for base catalysis. For acid catalysis, however, a quite different situation is encountered, since no general acid but only (weak) catalysis by the hydronium ion can be detected. We believe this deviation from 'normal' general acid catalysis is caused by an electrostatic interaction, and we suggest that it might result from a change in the usual class e mechanism for general acid catalysis by a situation in which rate-limiting concerted proton transfer is replaced by rate-limiting preprotonation. This is supported by the observed drastic change in Hammett rho value for catalysis by the hydronium ion, compared with the 'normal' case. An interesting case is encountered for the 4-aminophenyl-substituted substrate, in which the amino group becomes protonated in acid solution, thus representing a new substituent. Despite this complication, the various equilibrium and rate constants may also be evaluated experimentally for this substrate.     

Variational bounds on shear-driven turbulence and turbulent Boussinesq convection

Based on earlier studies by Hopf (1941), Doering and Constantin (1992, 1994, 1995) have recently formulated a new “background” technique for obtaining upper bounds on turbulent fluid flow quantities. This method produces upper bounds on the limit supremum of long time averages, making no statistical assumptions about the flow in contrast to the well-known Howard-Busse approach. The full optimisation problems posed by this method for the momentum transport in turbulent Couette flow and the heat transport (with zero background flow) in turbulent Boussinesq convection are solved here for the first time at asymptotically large Reynolds number and Rayleigh number within Busse's multiple boundary layer approximation to extract the best (lowest) possible upper bounds available. Intriguingly, the original bounds isolated by Busse (1969, 1970) within the confines of statistical stationarity are recovered exactly using this new formalism. The optimal background velocity profile for turbulent Couette flow is found to be shearless in the interior thus differing from Busse's “ ” mean shear result. In the convective case, an interesting degeneracy in the formulation of the background variational problem leads to an indeterminacy in the optimal background temperature profile. Only for one special choice is the isothermal core feature of Busse's mean profile recovered.     

A generalised model and calculation of the hyperfine interaction constant for anomalous muonium in the crystalline lattice of silicon

A new microscopic model of anomalous muonium for the elemental semiconductors is proposed. The relevant configuration consisting of both a diamagrentic molecule Si−Mu and an unpaired orbital e⁻ is contained into a semivacancy of the real lattice. By using the unrestricted Hartree-Fock computational method the principal properties of the system are established. A dynamical version of the model together with a question on the formation of such system are discussed.     

The exactly resolved nonlattice model of random media based on Markov walks with a stable law for jumps

A random-medium model which is a correlated distribution of points (particles) randomly positioned in the 3-dimensional space is considered. The construction of the medium starts from a noncorrelated (Poisson) distribution of parent particles, each of them initiates a finite Markov chain of its descendants. The complete collection of correlation functions of all orders within the scope of the model have been obtained. The use of the 3-dimensional stable law (Lévy law) as a transition probability allows us to present the correlation function in an explicit form. Proceedings of the XVII Seminar on Stability Problems for Stochastic Models, Kazan, Russian, 1995, Part II.     

Linear systems of arbitrary genus

Kalman's theory is extended to a complete, smooth, and irreducible algebraic curve of arbitrary genus.     

Resistance of composite flywheel rim to radial tensile stresses from centrifugal forces based on results of pure bending of a rim segment

A method is proposed for evaluating the resistance of a flywheel rim to radial stresses in free rotation. The method is based on loading a rim segment in pure bending and calculating the limiting moment and the corresponding limiting angular velocity. Applicability of the method is substantiated theoretically by investigating the similarity of the radial stress diagrams in rotation and pure bending. The method is verified experimentally for the strained state of a rim segment in pure bending.Translated from Mekhanika Kompozitnykh Materialov, Vol. 29, No. 4, pp. 521–526, July–August, 1993.     

Hamiltonian and recursion operators for two-dimensional scalar fields

The equation for the Noether operator is obtained. It gives the necessary conditions for complete integrability of the field equations. For several double-component models the Hamiltonian pairs and the recursion operators are presented.