NMRON studies of ferromagnetic hcp and fcc Co

The high resolution hyperfine spectroscopy, modulated adiabatic passage of oriented nuclei (MAPON), has been applied for the first time to high purity, elemental systems. Detailed comparisons between the electric quadrupole hyperfine interactions (EQI’s) and, in particular, their distributions, are obtained for⁶⁰CoCo where the hosts are a single crystal of hcp cobalt and a polycrystalline cobalt foil of predominantly fcc character. For hcp Co, with the electronic magnetization, M, parallel to the c-axis, the mode value P/h=3e²qQ/4I(2I−1)h=−48.5(5) kHz. This fractional distribution implies the sharpest electric field gradient (efg) measured in a metal to date, using MAPON spectroscopy, in excess of two times sharper than that of the most dilute impurity efg in a crystallographically cubic ferromagnetic host. The mode efg is V_zz=−27.3(32)×10¹⁹ Vm⁻². For the polycrystalline, predominantly fcc foil, prepared by quenching, the EQI mode value is P/h=−6.2(4) kHz with a FWHM of 12.0(7) kHz yielding a mode efg of V_zz=−3.5(5)×10¹⁹ Vm⁻².     

Pulsed NMRON oscillatory free induction decay signals in the angular distribution of gamma radiation from plated60CoFe

Results for an inhomogeneously broadened⁶⁰CoFe NMRON sample have been obtained for gamma detected single pulse (nutation) and two pulse (free induction decay) experiments in the region of intermediate-to-lowR(=₁/). Here ₁ is the angular frequency measure of the strength of the ferromagnetically enhanced RF field at the nucleus and is the HWHM of the inhomogeneously broadened line. Comparisons of the oscillatory FID signals obtained are made with the theoretical predictions of the following paper [6].     

Single and double passage AFP NMR/ON studies of54MnNi

High resolution conventional AFP NMR/ON studies provide evidence for very small efg's of predominantly negative sign at the nucleus of the nominal S-state ion⁵⁴Mn in single crystal nickel when the applied field is paralled to the 111 direction. The form of the mid passage signals for opposing sweep directions indicates a unique efg super-imposed upon a random component of comparable magnitude. The advantages of a second analyzing sweep performed during spin lattice relaxation of a conventional post-passage AFP NMR/ON sweep are demonstrated.     

The polymerization of methyl methacrylate by ion pairs

The reactions of the polymethylmethacrylate anion have been investigated at 200 K and 250 K in both THF and 9/1 toluene/THF. Sodium-α methyl styrene tetramer and fluorenyl sodium were used as initiators. Only ion pair reactions were investigated. The rate constant of monomer addition to the ion pair at 200 K was determined to be 80 ± 6 M^?1 sec^?1. At 250 K in the presence of excess monomer, the poly MMA anion reacts with the monomer vinyl function and the monomer ester function at comparable rates. Once fully reacted, the poly MMA anion terminates very slowly in THF at 250 K by an intermolecular mechanism. This rate of termination is enhanced in the toluene/THF system. No evidence was found for different reaction mechanisms for the two initiators.     

Terminal Alkyne Coupling Reactions Through a Ring: Effect of Ring Size on Rate and Regioselectivity

Terminal alkyne coupling reactions promoted by rhodium(I) complexes of macrocyclic NHC-based pincer ligands—which feature dodecamethylene, tetradecamethylene or hexadecamethylene wingtip linkers viz. [Rh(CNC-n)(C₂H₄)][BAr^F₄] (n=12, 14, 16; Ar^F=3,5-(CF₃)₂C₆H₃)—have been investigated, using the bulky alkynes HC≡CtBu and HC≡CAr’ (Ar’=3,5-tBu₂C₆H₃) as substrates. These stoichiometric reactions proceed with formation of rhodium(III) alkynyl alkenyl derivatives and produce rhodium(I) complexes of conjugated 1,3-enynes by C−C bond reductive elimination through the annulus of the ancillary ligand. The intermediates are formed with orthogonal regioselectivity, with E-alkenyl complexes derived from HC≡CtBu and gem-alkenyl complexes derived from HC≡CAr’, and the reductive elimination step is appreciably affected by the ring size of the macrocycle. For the homocoupling of HC≡CtBu, E-tBuC≡CCH=CHtBu is produced via direct reductive elimination from the corresponding rhodium(III) alkynyl E-alkenyl derivatives with increasing efficacy as the ring is expanded. In contrast, direct reductive elimination of Ar'C≡CC(=CH₂)Ar’ is encumbered relative to head-to-head coupling of HC≡CAr’ and it is only with the largest macrocyclic ligand studied that the two processes are competitive. These results showcase how macrocyclic ligands can be used to interrogate the mechanism and tune the outcome of terminal alkyne coupling reactions, and are discussed with reference to catalytic reactions mediated by the acyclic homologue [Rh(CNC-Me)(C₂H₄)][BAr^F₄] and solvent effects.     

Recent experiments with mapon spectroscopy

Electric quadrupole interactions of impurity nuclei in single crystals of⁵⁴MnNi,¹²⁵SbNi and¹²⁵SbFe have been studied as a function of crystal field direction and applied magnetic field using MAPON. Distributions are in all cases broad compared with the mode values of the EQI's. For⁵⁴MnNi the mode efg is isotropic to better than 5% between the easy <111> axis and a hard <100> axis. The efg is +0.88 (15)x 10¹⁹ Vm⁻². The mode efg for¹²⁵SbFe along its easy <100> axis is one half of that along a hard <112> axis, and one third of that measured along the easy <111> axis of¹²⁵SbNi. The much larger efg mode and distribution seen in¹²⁵SbNi, for four to eight times greater dilution than for¹²⁵SbFe, suggests intrinsic contributions due to valence screening effects in the more itinerant nickel host.     

NMRON spin echo in a slowly varying magnetic field

Nuclear spin-spin relaxation of⁶⁰Co and⁵⁶Co in iron single crystals has been studied, using the three-pulse NMRON spin echo. A previously reported rapidT ₂ in⁶⁰CoFe is shown to have arisen from a modulation of the echo amplitude, caused by variations in the phase of the Larmor precession relative to the applied rf field. A lower limit ofT ₂∼0.2s is found in⁵⁶Co⁵⁶ Fe. Extension of this result to other CoFe samples is discussed.     

The influence of the skin effect on gamma detected pulsed NMRON signals

The influence of the skin effect on single and triple (spin echo) gamma detected pulsed NMRON signals is calculated using a density matrix approach within a pure Zeeman manifold. For single pulse NMRON the turn angle dependences of the signals for uniform and exponential profiles of the resonant nuclei are presented for a typical inhomogeneous broadening applicable to intermediate mass impurities in ferromagnetic hosts. For triple pulse NMRON the baseline and principal spin echo amplitudes for equal resonant rf pulses are presented for the same inhomogeneous broadening. It is found that the skin effect leads to the form of pulsed NMRON signals that are in accord with experiment.     

Aerodynamic interference between high-speed slender bodies

Under supersonic flow conditions, slender bodies in close proximity induce aerodynamic interference effects. This paper aims to quantify the magnitude of the resulting interference loads and to understand the underlying flow-physics mechanisms that cause them. A pair of identical slender bodies are investigated through a series of wind-tunnel experiments and supporting computational fluid dynamics (CFD) predictions. The bodies induce a complex interference flowfield, which tends to be bespoke to each configuration. The flow features include impinging shock and expansion waves, conical shock reflections, strong skewing of the boundary-layer flows and shock diffraction. The effects of axial stagger, lateral separation and the strength of the primary disturbance flow field are evaluated. The interference loads are found to be most sensitive to the initial location of the primary disturbance but are also affected by its strength. In addition, maximum interference loads which equate to an effective incidence of up to 6° are observed. Finally, very good agreement is found between the measurements and the CFD predicted normal force and pitching moment.