Coordination Chemistry of Gold Catalysts in Solution: A Detailed NMR Study

Coordination chemistry of gold catalysts bearing eight different ligands [L=PPh₃, JohnPhos (L2), Xphos (L3), DTBP, IMes, IPr, dppf, S‐tolBINAP (L8)] has been studied by NMR spectroscopy in solution at room temperature. Cationic or neutral mononuclear complexes LAuX (L=L2, L3, IMes, IPr; X=charged or neutral ligand) underwent simple ligand exchange without giving any higher coordinate complexes. For L2AuX the following ligand strength series was determined: MeOH?hex‐3‐yne <MeCN≈OTf^??Me₂S<2,6‐lutidine<4‐picoline<CF₃CO₂^?≈DMAP<TMTU<PPh₃<OH^?≈Cl^?. Some heteroligand complexes DTBPAuX exist in solution in equilibrium with the corresponding symmetrical species. Binuclear complexes dppf(AuOTf)₂ and S‐tolBINAP(AuOTf)₂ showed different behavior in exchange reactions with ligands depending on the ligand strength. Thus, PPh₃ causes abstraction of one gold atom to give mononuclear complexes LLAuPPh₃⁺ and (Ph₃P)_nAu⁺, but other N and S ligands give ordinary dicationic species LL(AuNu)₂²⁺. In reactions with different bases, LAu⁺ provided new oxonium ions whose chemistry was also studied: (DTBPAu)₃O⁺, (L2Au)₂OH⁺, (L2Au)₃O⁺, (L3Au)₂OH⁺, and (IMesAu)₂OH⁺. Ultimately, formation of gold hydroxide LAuOH (L=L2, L3, IMes) was studied. Ligand‐ or base‐assisted interconversions between (L2Au)₂OH⁺, (L2Au)₃O⁺, and L2AuOH are described. Reactions of dppf(AuOTf)₂ and S‐tolBINAP(AuOTf)₂ with bases provided more interesting oxonium ions, whose molecular composition was found to be [dppf(Au)₂]₃O₂²⁺, L8(Au)₂OH⁺, and [L8(Au)₂]₃O₂²⁺, but their exact structure was not established. Several reactions between different oxonium species were conducted to observe mixed heteroligand oxonium species. Reaction of L2AuNCMe⁺ with S^2? was studied; several new complexes with sulfide are described. For many reversible reactions the corresponding equilibrium constants were determined.     

Inclusive ϕ production inK − p interactions at 110 GeV/c and search for structure in φ π−

Results on inclusive ? production inK ^? p interactions at 110 GeV/c are presented. The production cross section is found to be larger than in πp andpp interactions at similar energies, suggesting OZI allowed \(s\bar s\) fusion to be the dominant mechanism in ? production. Thex distributions of ? and \(\bar K^{*0} \) are found to be similar to each other over the entirex range suggesting an overall strangeness suppression factor of 0.20±0.04 in the sea to be the dominant source of the difference in the cross section for ? and \(\bar K^{*0} \) . There is no evidence of a narrowφπ ^? state around 2.1 GeV/c² as suggested byK ⁺ experiments, but there is some excess of events in the region 1.94?1.98 GeV/c² consistent with theF-meson mass as observed ine ⁺ e ^? experiments.     

On the theory of the Kondo effect in two-dimensional metals

The Kondo effect in a (quasi-)two-dimensional metal is studied. The special feature of the two-dimensionality is the Van Hove singularity in the electron density of states. For the band filling choosen such, that the Fermi level is close to the saddle points of the band spectrum, the Van Hove singularity comes into play and changes the usual Kondo log to the log². It turnes out to be possible to carry out the first order parquet summation and to obtain the conditions for the Kondo antiferromagnetic resonance for an arbitrary geometry of the band spectrum. The connection with the Orthogonality Catastrophe is traced and it is shown, that the weak coupling Kondo problem just corresponds to the intermediate asymptotics of the metal's relaxation in a time-dependent external potential.     

Observation of the chaotic spin-wave soliton trains in magnetic films

The transition from stationary to chaotic spin-wave soliton trains has been observed. The experiment utilized cw excitation of envelope solitons through self-modulation instability of spin waves. By increasing the spin-wave power, the secondary self-modulation instability succeeded the primary modulation instability, resulting in after-modulation of the soliton train amplitude. Further increase of the spin-wave power led to development of the higher-order instabilities, resulting in formation of the chaotic soliton train.     

High average power large-pitch fiber amplifier with robust single-mode operation

Ytterbium-doped large-pitch fibers with very large mode areas are investigated in a high-power fiber amplifier configuration. An average output power of 294?W is demonstrated, while maintaining robust single-mode operation with a mode field diameter of 62?μm. Compared to previous active large-mode area designs, the threshold of mode instabilities is increased by a factor of about 3.     

Metal nanoslit lenses with polarization-selective design

We present comprehensive studies on thin diffraction lenses made of arrays of subwavelength, parallel nanoslits in a gold film. Such a nanoslit lens can operate either as a conventional convex or concave lens. The lenses can be designed to focus linearly polarized light with polarization either perpendicular (TM-lens) or parallel to the slits (TE-lens), while the orthogonal polarization diverges when passing through the lens. The designs of each lens are initially built on the dispersion relations for wave propagation through a parallel-plate waveguide. Both TM- and TE-lenses were realized experimentally, and full-wave numerical simulations fully support the experimental results.     

Assemblies from metallic and semiconducting nanocrystals

Optical properties of nanomaterials such as semiconductor and metal quantum dots are important for sensors and photovoltaic applications. We report on optical, microscopic, and AFM investigations on bulk and single nanoobjects such as metal and semiconducting nanoparticles. Firstly, of special interest is the investigation of Ag metal nanoaggregates formed in zeolites. Here, the defined structure of the zeolite serves both as size directing and a stabilizing agent. The size selected Ag aggregates fluoresce in the zeolite cages even after storage under ambient conditions for almost one year. In addition, single Ag particles escape the cages and can be investigated by fluorescence microscopy also with respect to sensor applications. Secondly, with respect to photovoltaic applications, energy transfer among organic dye molecules and semiconductor quantum dots is of great importance. We report on the extension of the optical absorption of ZnSe quantum dots into the UV regime and investigate excitation energy transfer within self-assembled nanoaggregates of surface functionalized QDs and fluorescent styrylpyridine dyes.     

Nonexistence of intrinsic spin currents

We describe the electron spin dynamics in the presence of Rashba spin-orbit interaction and disorder using the spin-density matrix method. We show that in the Born approximation in the scattering amplitude the spin current is zero for an arbitrary ratio of the spin-orbit splitting and the scattering rate. Various types of the disorder potential are studied. We argue that the bulk spin current always depends explicitly on scattering by impurities. In this sense universal intrinsic spin current does not exist.     

Photon echoes produced by switching electric fields

We demonstrate photon echoes in Eu3+:Y2SiO5 by controlling the inhomogeneous broadening of the Eu3+ 7F0<-->5D0 optical transition. This transition has a linear Stark shift, and we induce inhomogeneous broadening by applying an external electric field gradient. After optical excitation, reversing the polarity of the field rephases the ensemble, resulting in a photon echo. This is the first demonstration of such a photon echo, and its application as a quantum memory is discussed.     

Search for exclusive multibody non- decays at the resonance

Using data collected at the psi(3770) resonance with the CLEO-c detector at the Cornell e+e- storage ring, we present searches for 25 charmless decay modes of the psi(3770), mostly multibody final states. No evidence for charmless decays is found.