Selective saturation and inversion of multiple resonances in high-resolution solid-state 13C experiments using slow spinning CP/MAS and tailored DANTE pulse sequences.

Taking advantage of the long 13C T1 values generally encountered in solids, selective saturation and inversion of more than one resonance in 13C CP/MAS experiments can be achieved by sequentially applying several DANTE pulse sequences centered at different transmitter frequency offsets. A new selective saturation pulse sequence is introduced composed of a series of 90 degrees DANTE sequences separated by interrupted decoupling periods during which the selected resonance is destroyed. Applications of this method, including the simplification of the measurement of the principal values of the 13C chemical shift tensor under slow MAS conditions, are described. The determination of the aromaticity of coal using a relatively slow MAS rate is also described.     

Expression of theSU(2) rotation matrices D( j ) in terms of normalized irreducible tensorial matrices

TheSU(2) rotation matricesD ^(j), specified in terms of axis and angle of rotation, are expressed as linear combination of normalized irreducible tensorial matricces (NITM) of rankl = 0 to 2j rotated to the polar angles of the axis. The rotated NITM are constructed from spherical harmonics of the same rank. Since this formulation requires no matrix products, it may be computationally more efficient than Euler angle formulas, particularly for largej. Rotated NITM and formulas for theD ^(j) withj = 1/2 andj = 1 are written out explicitly. A formula for the structure constants of the products of conformable NITM is also given in terms of 3-j and 6-j symbols.     

On the existence of <Emphasis Type="Bold">1, 3</Emphasis>P <Emphasis Type="Bold">o</Emphasis> resonances in H<Superscript>-</Superscript> between n = 2 and 3 H thresholds

We examine the influence of relativistic and QED effects on the existence of the ^1,3P ^o H^- resonances between n = 2 and 3 hydrogen thresholds, the relativistic and QED corrections and the coupling effects between the high singlet and triplet states are considered as first-order perturbations. We firstly obtain accurate non-relativistic resonant energies and widths of fifteen ¹P ^o resonances, and fifteen ³P ^o resonances. The fifteen ¹P ^o resonances are classified to be ₃ (2, 0) ^- _n ( 4 ? n ? 12) and ₃ (1, 1) ⁺ _n ( 3 ? n ? 8). The fifteen ³P ^o resonances are classified to be ₃ (2, 0) ⁺ _n ( 3 ? n ? 12) and ₃ (1, 1) ^- _n ( 4 ? n ? 8). We found there exist six Feshbach resonances for ₃ (2, 0) ^- _n (¹P ^o ) series, four Feshbach resonances for ₃ (1, 1) ⁺ _n (¹P ^o ) series, seven Feshbach resonances for ₃ (2, 0) ⁺ _n (³P ^o ) series, and three Feshbach resonances for ₃ (1, 1) ^- _n (¹P ^o ) series. Received 22 February 2002 Published online 24 September 2002     

On finite element approximation and stabilization methods for compressible viscous flows

This work is devoted to the numerical solution of the Navier–Stokes equations for compressible viscous fluids. Finite element approximations and stabilization techniques are addressed. We present methods to implement discontinuous approximations for the pressure and the density. An upwinding methodology is being investigated which combines the ideas behind the stream line Petrov–Galerkin method and the flux limiter methods aiming to introduce numerical diffusion only where it is necessary.     

THE USE OF THERMOELASTICITY TO EVALUATE STRESS REDISTRIBUTION AND NOTCH SENSITIVITY IN CERAMIC MATRIX COMPOSITES

Thermoelastic stress analysis was used to document the effect of composite damage on the stress distribution in three ceramic matrix composites. Composite damage was found to significantly alter the thermoelastic response of each material, with the greatest effect noted in SiC/CAS. Thermoelastic imaging of these materials affords a more complete picture of how the various damage mechanisms affect the stress distribution. In particular, a stress concentration factor computed from thermoelastic images, serves as an indicator of stress redistribution. The stress concentration factors were computed by comparing notch root to far field temperatures, and monitored after the introduction of various amounts of damage. In each material, the stress concentration factor diminished as the damaging load approached the ultimate stress. Reduction in the stress concentration is associated with local changes in modulus, mechanistically arising from combinations of fiber, matrix and interface fracture. Stress redistribution occurs as a consequence of modulus changes, leading to lower notch sensitivity in each of the tested composites.     

Aqueous solution and solid state interactions of lanthanide ions with a methacrylic ester polymer bearing pendant 15‐crown‐5 moieties

The interaction between trivalent lanthanide ions and poly(1,4,7,10,13‐pentaoxacyclopentadecan‐2‐yl‐methyl methacrylate), PCR5, in aqueous solution and in the solid state have been studied. In aqueous solution, evidence of a weak interaction between the lanthanides and PCR5 comes from the small red shift of the Ce(III) emission spectra and the slight broadening of the Gd(III) EPR spectra. From the Tb(III) lifetimes in the presence of H₂O and D₂O the loss of one or two water coordinated molecules is confirmed when Tb(III) is bound to PCR5. An association constant of the order of 200 M^?1 was obtained for a 1:1 (lanthanide:15‐crown‐5) complex from the shift of the polymer NMR signals induced by Tb(III). A similar association constant is obtained from the differences of the molar conductivity of Ce(III) solution at various concentrations in presence and absence of PCR5. When Tb(III) is adsorbed on PCR5 membranes, lifetime experiments in H₂O and D₂O confirm the loss of 5 or 6 water coordinated molecules indicating that in solid state the lanthanide(III)‐PCR5 interaction is stronger than in solution. The adsorption of Ce(III) in PCR5 membranes shows a Langmuir type isotherm, from which an equilibrium constant of 39 M^?1 has been calculated. SEM shows that the membrane morphology is not much affected by lanthanide adsorption. Support for lanthanide ion–crown interactions comes from ab initio calculations on 15‐crown‐5/La(III) complex. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1788–1799, 2007     

Letters to the Editor

The Mathematical Intelligencer encourages comments about the material in this issue. Letters to the editor should be sent to either of the editors-in-chief, Chandler Davis or Marjorie Senechal.     

Degradative chain transfer in vinyl acetate polymerizations using toluene as solvent

In this work, we propose that retardation in vinyl acetate polymerization rate in the presence of toluene is due to degradative chain transfer. The transfer constant to toluene (C_trs) determined using the Mayo method is equal to 3.8 × 10^?3, which is remarkably similar to the value calculated from the rate data, assuming degradative chain transfer (2.7 × 10^?3). Simulations, including chain‐length‐dependent termination, were carried out to compare our degradative chain transfer model with experimental results. The conversion–time profiles showed excellent agreement between experiment and simulation. Good agreement was found for the M_n data as a function of conversion. The experimental and simulation data strongly support the postulate that degradative chain transfer is the dominant kinetic mechanism. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3620–3625, 2007