Solid‐State 73Ge NMR Spectroscopy of Simple Organogermanes

Germanium‐73 is an extremely challenging nucleus to examine by NMR spectroscopy due to its unfavorable NMR properties. Through the use of an ultrahigh (21.1 T) magnetic field, a systematic study of a series of simple organogermanes was carried out. In those cases for which X‐ray structural data were available, correlations were drawn between the NMR parameters and structural metrics. These data were combined with DFT calculations to obtain insight into the structures of several compounds with unknown crystal structures.     

The addition of amides to group 14 (di)-metallenes

The addition of a series of primary and secondary amides to the group 14 (di)metallenes Mes(2)Si=SiMes(2), Mes(2)Ge=GeMes(2) and (Me(3)Si)(2)Si=C(OSiMe(3))R, where R = t-Bu or R = 1-Ad, was examined. In general, the addition of primary and N-methyl amides gave amide adducts whereas the addition of N-phenyl amides gave imidate adducts. The regiochemistry of the additions was highly dependent upon the substituent bonded to the amide nitrogen. We propose that the formation of the adducts proceeds by way of a zwitterionic intermediate. The reactivity of tetramesityldigermene towards amides is used to predict the structure of the amide adducts formed on the Ge(100)-2 × 1 surface.     

Low-temperature spin diffusion in a highly ideal S=1/2 Heisenberg antiferromagnetic chain studied by muon spin relaxation

The organic radical-ion salt DEOCC-TCNQF4 contains linear chains of stacked molecules with significant Heisenberg antiferromagnet interactions along the chain and extremely weak interactions between the chains. Zero-field muSR has confirmed the absence of long-range magnetic order down to 20 mK and field-dependent muSR is found to be consistent with diffusive motion of the spin excitations. The anisotropic spin dynamics and the upper boundary for magnetic ordering temperature both indicate interchain magnetic coupling /J'/<7 mK. As the intrachain coupling J is 110 K, /J'/J/ is significantly less than 10(-4). This system therefore provides one of the most ideal examples of the one-dimensional S=1/2 Heisenberg antiferromagnet yet discovered.     

Spin dynamics and magnetic order in magnetically frustrated Tb2Sn2O7

We report a study of the geometrically frustrated magnetic material Tb2Sn2O7 by the positive muon-spin relaxation technique. No signature of a static magnetically ordered state is detected while neutron magnetic reflections are observed in agreement with a published report. This is explained by the dynamical nature of the ground state of Tb2Sn2O7: the Tb3+ magnetic moment characteristic fluctuation time is approximately 10(-10) s. The strong effect of the magnetic field on the muon-spin-lattice relaxation rate at low fields indicates a large field-induced increase of the magnetic density of states of the collective excitations at low energy.     

Least squares moving finite elements

The moving finite element (MFE) method, when applied to purelyhyperbolic partial differential equation, moves nodes with approximatelycharacteristic speeds, which makes the method useless for steady-stateproblems. We introduce the least squares MFE method (LSMFE)for steady-state pure convection problems which corrects thisdefect. We show results for a steady-state pure convection problemin one dimension in which the nodes are no longer swept downstreamas in MFE. The method is then extended to two dimensions andthe grid aligns automatically with the flow, thereby yieldingfar greater accuracy than the corresponding fixed node leastsquares results, as is shown in two-dimensional numerical trials.     

The Diverse Reactivity of Disilenes Toward Isocyanides

The addition of 2,6‐dimethylphenyl isocyanide and t‐butyl isocyanide to tetramesityldisilene was examined. In both cases, the initially formed product is an iminodisilirane; however, the iminodisiliranes are unstable under the reaction conditions and react with a second equivalent of the isocyanide to give either a 3‐silaazetidine or a novel bicyclic double enamine, respectively. Taken together with the previous examples in the literature, the results demonstrate that subtle differences in the steric bulk of the disilene or the electronic effects of the isocyanide can lead to dramatic differences in the reaction pathway.     

Muons as local probes of three-body correlations in the mixed state of type-II superconductors

The vortex glass state formed by magnetic flux lines in a type-II superconductor is shown to possess nontrivial three-body correlations. While such correlations are usually difficult to measure in glassy systems, the magnetic fields associated with the flux vortices allow us to probe these via muon-spin rotation measurements of the local field distribution. We show via numerical simulations and analytic calculations that these observations provide detailed microscopic insight into the local order of the vortex glass and more generally validate a theoretical framework for correlations in glassy systems.