Macroscopic Aharonov--Bohm Effect in Type-I Superconductors

In type-I superconducting cylinders bulk superconductivity is destroyed above the first critical current. Below the second critical current the `type-I mixed state' displays fluctuation superconductivity which contributes to the total current. A magnetic flux on the axis of the cylinder can change the second critical current by as much as 50 percent so that half a flux quantum can switch the cylinder from normal conduction to superconductivity: the Aharonov--Bohm effect manifests itself in macroscopically large resistance changes of the cylinder.Comment: five pages, one figur

Thermodynamics of pairing in mesoscopic systems

Using numerical and analytical methods implemented for different models we conduct a systematic study of thermodynamic properties of pairing correlation in mesoscopic nuclear systems. Various quantities are calculated and analyzed using the exact solution of pairing. An in-depth comparison of canonical, grand canonical, and microcanonical ensemble is conducted. The nature of the pairing phase transition in a small system is of a particular interest. We discuss the onset of discontinuity in the thermodynamic variables, fluctuations, and evolution of zeros of the canonical and grand canonical partition functions in the complex plane. The behavior of the Invariant Correlational Entropy is also studied in the transitional region of interest. The change in the character of the phase transition due to the presence of magnetic field is discussed along with studies of superconducting thermodynamics.Comment: 19 pages, 24 figure

A “Push–Pull” Stabilized Phosphinidene Supported by a Phosphine‐Functionalized β‐Diketiminato Ligand

The use of a bis(diphenyl)phosphine functionalized β‐diketiminato ligand, [HC{(CH$_{3}$)C}$_{2}${(ortho‐[P(C$_{6}$H$_{5}$)$_{2}$]$_{2}$C$_{6}$H$_{4}$)N}$_{2}$]$^{-}$ (PNac), as a support for germanium(II) and tin(II) chloride and phosphaketene compounds, is described. The conformational flexibility and hemilability of this unique ligand provide a versatile coordination environment that can accommodate the electronic needs of the ligated elements. For example, chloride abstraction from [(PNac)ECl] (E=Ge, Sn) affords the cationic germyliumylidene and stannyliumylidene species [(PNac)E]$^{+}$ in which the pendant phosphine arms associate more strongly with the Lewis acidic main group element centers, providing further electronic stabilization. In a similar fashion, chemical decarbonylation of the germanium phosphaketene [(PNac)Ge(PCO)] with tris(pentafluorophenyl)borane affords a “push–pull” stabilized phosphinidene in which one of the phosphine groups of the ligand backbone associates with the low valent phosphinidene center

A Phosphine Functionalized β‐Diketimine Ligand for the Synthesis of Manifold Metal Complexes

One-size-fits-all: A β-diketimine ligand and its corresponding anion, forming a PNNP-type pocket, can stabilize various coordination polyhedral. A complete series of complexes forming seven different coordination polyhedral and coordination numbers ranging from 2 to 6 were realized. A bis(diphenyl)-phosphine functionalized β-diketimine (PNac-H) was synthesized as a flexible ligand for transition metal complexes. The newly designed ligand features symmetrically placed phosphine moieties around a β-diketimine unit, forming a PNNP-type pocket. Due to the hard and soft donor atoms (N vs. P) the ligand can stabilize various coordination polyhedra. A complete series ranging from coordination numbers 2 to 6 was realized. Linear, trigonal planar, square planar, tetrahedral, square pyramidal, and octahedral coordination arrangements containing the PNac-ligand around the metal center were observed by using suitable metal sources. Hereby, PNac-H or its anion PNac− acts as mono-, bi- and tetradendate ligand. Such a broad flexibility is unusual for a rigid tetradentate system. The structural motifs were realized by treatment of PNac-H with a series of late transition metal precursors, for example, silver, gold, nickel, copper, platinum, and rhodium. The new complexes have been fully characterized by single crystal X-ray diffraction, NMR, IR, UV/Vis spectroscopy, mass spectrometry as well as elemental analysis. Additionally, selected complexes were investigated regarding their photophysical properties. Thus, PNac-H proved to be an ideal ligand platform for the selective coordination and stabilization of various metal ions in diverse polyhedra and oxidation states

Alkynyl-functionalized gold NHC complexes and their coinage metal clusters

Phenylpropynyl-functionalized imidazolium salts, as well as their gold complexes, were prepared in excellent yields affording suitable starting materials for metal cluster synthesis. The reactions of these gold complexes with coinage metal phenylacetylides [M(CCPh)]x (M = Cu, Ag) resulted in the formation of novel heterometallic hexanuclear clusters which exhibit mixed metallophillic interactions and intense white photoluminescence at low temperature

Giant Coulomb broadening and Raman lasing on ionic transitions

CW generation of anti-Stokes Raman laser on a number of blue-green argon-ion lines (4p-4s, 4p-3d) has been demonstrated with optical pumping from metastable levels 3d'^2G, 3d^4F. It is found, that the population transfer rate is increased by a factor of 3-5 (and hence, the output power of such Raman laser) owing to Coulomb diffusion in the velocity space. Measured are the excitation and relaxation rates for the metastable level. The Bennett hole on the metastable level has been recorded using the probe field technique. It has been shown that the Coulomb diffusion changes shape of the contour to exponential cusp profile while its width becomes 100 times the Lorentzian one and reaches values close to the Doppler width. Such a giant broadening is also confirmed by the shape of the absorption saturation curve.Comment: RevTex 18 pages, 5 figure