Allylpalladium dimers with metals connected by binucleating dithiooxamidates in two different coordination modes: solution behavior and solid-state structure

A series of allylpalladium dimers having metals connected by binucleating dialkyldithiooxamidate [N(R)SC-CS(R)N](2-) [R = methyl, ethyl, isopropyl, benzyl, isoamyl, (S)-1-(1-phenyl)ethyl, meso-(1-phenyl)ethyl, and rac-(1-phenyl)ethyl] were prepared by reacting the monochelate [(η(3)-allyl)Pd(N(R)SC-CS(R)NH κ-S,S Pd)] with [(η(3)-allyl)PdCl](2) in chloroform. At low temperature (20 °C), the bimetallic complexes [(η(3)-allyl)Pd](2)(μ-dialkyldithiooxamidate κ-N,N' Pd, κ-S,S' Pd') (kinetic compounds) are formed in a short reaction time (10 min). At a higher temperature (50 °C) and a longer reaction time (24 h), the corresponding bimetallic isomers [(η(3)-allyl)Pd](2)(μ-dialkyldithiooxamidate κ-N,S Pd, κ-N',S' Pd') (thermodynamic compounds) are obtained. Both kinetic and thermodynamic compounds can exist as endo or exo isomers, depending on the reciprocal orientation of the allyl cuspids. Both endo and exo isomers are only detectable in solution when the alkyl substituents are chiral alkyl groups. Moreover, diffractometric modeling agrees with the presence of both isomers in the solid state even when the alkyl substituent is an achiral alkyl group. In a chloroform solution, endo and exo isomers undergo isomeric conversion owing to the apparent allyl rotation that follows the Pd-N bond rupture in the (η(3)-allyl)Pd(N^N) frame of kinetic compounds or in the (η(3)-allyl)Pd(N^S) frame of thermodynamic compounds. The dithiooxamidate [N(R)SC-CS(R)N](2-), when engaged in a κ-N,S Pd, κ-N',S' Pd' coordination mode, behaves as a hybrid hemilabile binucleating ligand. At room temperature and in a chloroform solution, the kinetic compounds rearrange into the thermodynamically more stable isomers in about 3 or 4 days. The higher stability of the thermodynamic species was evaluated by means of computational studies in accordance with the maximum hardness principle. Finally, the crystal structures of [(η(3)-allyl)Pd](2)(μ-diethyldithiooxamidate κ-N,S Pd, κ-N',S' Pd'), [(η(3)-allyl)Pd](2)(μ-meso-(1-phenyl)ethyldithiooxamidate κ-N,S Pd, κ-N',S' Pd'), and [(η(3)-allyl)Pd](2)(μ-rac-(1-phenyl)ethyldithiooxamidate κ-N,N' Pd, κ-S,S' Pd') are reported.     

Nonlinear optical and electrostatic force microscopy for ferroelectric polarization imaging

Second-harmonic generation (SHG)-based nonlinear optical microscopy is used for spatially resolved imaging of the polarization switching in lead zirconium titanate ferroelectric thin films. The local SHG hysteresis loops reveal a strong dependence on film composition and structure. The SHG microscopy results are in good agreement with the efficiency of electrostatic force microscopy writing and allow us to predict the microscopic dielectric memory efficiency, both in contact and contact-less ways. Received: 15 January 2001 / Revised version: 27 March 2002 / Published online: 6 June 2002     

Transverse momentum distributions of neutral pions from central and peripheral16O+Au collisions at 200A·GeV

The production of neutral pions by the interaction of 200A·GeV p and¹⁶O projectiles with a Au target has been studied in the pseudorapidity range 1.5≦η≦2.1. Transverse momentum spectra have been measured between 0.4 GeV/c and 3.6 GeV/c and their dependence on the centrality of the collision has been investigated. The peripheral-collision spectra display a marked change of slope with a hard component starting at about 1.8 GeV/c, in contrast to central-collision data. The data are discussed in comparison to p+p and α+α data from the ISR.     

Effect of quantum entanglement on Aharonov-Bohm oscillations, spin-polarized transport and current magnification effect

We present a simple model of transmission across a metallic mesoscopic ring. In one of its arm an electron interacts with a single magnetic impurity via an exchange coupling. We show that entanglement between electron and spin impurity states leads to reduction of Aharonov-Bohm oscillations in the transmission coefficient. The spin-conductance is asymmetric in the flux reversal as opposed to the two-probe electrical conductance which is symmetric. In the same model, in contradiction to the naive expectation of a current magnification effect, we observe enhancement as well as suppression of this effect depending on the system parameters. The limitations of this model to the general notion of dephasing or decoherence in quantum systems are pointed out.     

Quasimolecular states in the elastic α-scattering on 40Ca

Resonance states seen in α-⁴⁰Ca elastic scattering are treated in a microscopic model which describes the fragments by displaced oscillator shell model functions. The minima of the energy expectation value for various angular momenta are in good agreement with the experimental resonance energies, thus confirming the concept of an underlying quasimolecular structure.     

Target fragmentation in proton-nucleus and16O-nucleus reactions at 60 and 200 GeV/nucleon

Target remnants withZ<3 from proton-nucleus and¹⁶O-nucleus reactions at 60 and 200 GeV/nucleon were measured in the angular range from 30° to 160° (?1.7<η<1.3) employing the Plastic Ball detector. The excitation energy of the target spectator matter in central oxygen-induced collisions is found to be high enough to allow for complete disintegration of the target nucleus into fragments withZ<3. The average longitudinal momentum transfer per proton to the target in central collisions is considerably higher in the case of¹⁶O-induced reactions (≈300 MeV/c) than in proton-induced reactions (≈130 MeV/c). The baryon rapidity distributions are roughly in agreement with one-fluid hydrodynamical calculations at 60 GeV/nucleon¹⁶O+Au but are in disagreement at 200 GeV/nucleon, indicating the higher degree of transparency at the higher bombarding energy. Both, the transverse momenta of target spectators and the entropy produced in the target fragmentation region are compared to those attained in head-on collisions of two heavy nuclei at Bevalac energies. They are found to be comparable or do even exceed the values for the participant matter at beam energies of about 1–2 GeV/nucleon.     

Charged particle spectra in16O induced nuclear collisions at the CERN SPS

Charged particle multiplicity distributions and pseudo-rapidity density distributions from¹⁶O induced nuclear collisions at 200 and 60A GeV are presented. The data were taken, using a minimumbias trigger, with the WA80 set-up at the CERN SPS. In this presentation we focus on how the yield of charged particles depends on the projectile energy, the mass number of the target nucleus and the energy measured in a uranium-plastic sampling calorimeter covering angles close to zero degrees. The data are compared to simulations from the event generator FRITIOF.     

Comparative Raman studies of molecular interactions at a dye/polymer and a dye/glass interface

Integrated optical techniques and resonance Raman spectroscopy have been combined to investigate the intermolecular interactions at dye/polymer and dye/glass interfaces. Frequency shifts and intensity changes of bands assigned to the stretching vibrations of the bridged quinoline rings of the cyanine dye chromophore have been utilized to gain insight into the relative strength of adhesive forces at the surface. Polarized Raman measurements were made to determine the orientation of the chromophores on a poly(vinyl alcohol) surface. This was done to assess the possibility of hydrogen bond formation between the ring nitrogen atoms and the polar hydroxyl groups at the surface.