Mixed-metal cluster chemistry. 26 . Proclivity for “all-terminal” or “plane-of-bridging-carbonyls” ligand disposition in tungsten-triiridium clusters

Reaction of WH(CO)₃(η-C₅Me₅) with IrCl(CO)₂(4-H₂NC₆H₄Me) affords WIr₃(μ-CO)₃(CO)₈(η-C₅Me₅) in low yield. A structural study reveals a WIr₂-centred plane of bridging carbonyls, in contrast to the crystal structure of WIr₃(CO)₁₁(η-C₅H₅) (all-terminal carbonyl distribution). DFT calculations reveal an increasing proclivity to adopt an all-terminal CO disposition for clusters MIr₃(CO)₁₁(η-C₅H₅) in the gas phase on proceeding from M=Cr to Mo and then W, consistent with structural studies in the solid state for which the tungsten-containing cluster is the only all-terminal example. Increasing electron donation from the ligands in the tungsten system (either from phosphine substitution or cyclopentadienyl permethylation) suffices to impose a plane of bridging carbonyls in the ground state structure. ¹³C NMR fluxionality studies reveal that CO exchange mechanism(s) for WIr₃(CO)₁₁(η-C₅H₅) and the related tetrahedral cluster W₂Ir₂(CO)₁₀(η-C₅H₅)₂ are very fast and involve all carbonyls on the clusters. DFT calculations on MIr₃(CO)₁₁(η-C₅H₅) (M=Cr, Mo) substantiate a ‘merry-go-round’ mechanism for carbonyl scrambling in these systems, a result which is consistent with the scrambling behaviour seen in the NMR fluxionality studies on the W-containing congener.     

Characterisation of a nitrogen ECR plasma source for the MBE growth of the dilute nitride semiconductor GaAsN

The use of a nitrogen electron cyclotron resonance (ECR) plasma source has allowed the growth of GaAsN at GaAs substrate temperatures as high as 600 °C, unlike the case for growth using radio frequency (RF) plasma sources, for which there is significant loss of nitrogen at substrate temperatures as low as 480-520 °C. Photoluminescence (PL) intensities are significantly improved at a substrate temperature of 600 °C and are further improved slightly by using an ion trap to extract charged species from the beam. As the trap voltage is increased there is a reduction in the total nitrogen concentration, as measured by secondary ion mass spectrometry (SIMS), and a slight increase in the active nitrogen concentration, as measured by PL. These observations are consistent, for example, with charged and active nitrogen species together being involved in the formation of point defects, however more work is needed to clarify what may well prove to be a complex situation.     

Boundary depth in Floer theory and its applications to Hamiltonian dynamics and coisotropic submanifolds

We assign to each nondegenerate Hamiltonian on a closed symplectic manifold a Floer-theoretic quantity called its “boundary depth,” and establish basic results about how the boundary depths of different Hamiltonians are related. As applications, we prove that certain Hamiltonian symplectomorphisms supported in displaceable subsets have infinitely many nontrivial geometrically distinct periodic points, and we also significantly expand the class of coisotropic submanifolds which are known to have positive displacement energy. For instance, any coisotropic submanifold of contact type (in the sense of Bolle) in any closed symplectic manifold has positive displacement energy, as does any stable coisotropic submanifold of a Stein manifold. We also show that any stable coisotropic submanifold admits a Riemannian metric that makes its characteristic foliation totally geodesic, and that this latter, weaker, condition is enough to imply positive displacement energy under certain topological hypotheses.     

Differential cross-sections for pp → π−π+, K−K+ between 0.8 and 2.4 GeV/c

We present measurements from a spark chamber experiment of the differential cross-sections for $\text{p}$p → π^?π⁺, K^?K⁺ at 20 momenta in the range 0.8–2.4 GeV/c (c.m. energy 2.02 to 2.57 GeV). The c.m. angular range was $\text{?0.95 <}\text{cos}\text{θ}{}^1\text{< 0.95}$. There are about 2000π^?π⁺ events and about 300 K^?K⁺ events at each momentum.