Solvent influence on photochemical isomerizations: Photophysics of DODCI

We have studied the photophysics of DODCI dissolved in a series of polar solvents. Through measurements of the temperature dependence of the photoisomer quantum yield, fluorescence lifetime and fluorescence quantum yields we clarify the kinetic mechanism for nonradiative decay. By measuring the isomerization rate as a function of temperature at constant viscosity we are able to separate the innuence of internal barriers and solvent viscous drag. The apparent activation energy observed in solutions is less than the sum of the internal and viscosity activation energies. This is shown to be consistent with the full Kramer's rate expression for diffusive barrier crossing. We also establish the temperature dependence of a second “direct” internal conversion process which does not lead to photoisomer formation and dominates the nonradiative decay of DODCI at low temperatures or in a rigid matrix.     

Bridging the gap between homogeneous and heterogeneous catalysis: ortho/para H(2) conversion, hydrogen isotope scrambling, and hydrogenation of olefins by Ir(CO)Cl(PPh(3))(2)

Some transition metal complexes are known to catalyze ortho/para hydrogen conversion, hydrogen isotope scrambling, and hydrogenation reactions in liquid solution. Using the example of Vaska's complex, we present here evidence by NMR that the solvent is not necessary for these reactions to occur. Thus, solid frozen solutions or polycrystalline powdered samples of homogeneous catalysts may become heterogeneous catalysts. Comparative liquid- and solid-state studies provide novel insight into the reaction mechanisms.     

Quantum percolation in two-dimensional antiferromagnets

The interplay of geometric randomness and strong quantum fluctuations is an exciting topic in quantum many-body physics, leading to the emergence of novel quantum phases in strongly correlated electron systems. Recent investigations have focused on the case of homogeneous site and bond dilution in the quantum antiferromagnet on the square lattice, reporting a classical geometric percolation transition between magnetic order and disorder. In this study we show how inhomogeneous bond dilution leads to percolative quantum phase transitions, which we have studied extensively by quantum Monte Carlo simulations. Quantum percolation introduces a new class of two-dimensional spin liquids, characterized by an infinite percolating network with vanishing antiferromagnetic order parameter.     

Entanglement and factorized ground states in two-dimensional quantum antiferromagnets

Making use of exact results and quantum Monte Carlo data for the entanglement of formation, we show that the ground state of anisotropic two-dimensional S=1/2 antiferromagnets in a uniform field takes the classical-like form of a product state for a particular value and orientation of the field, at which the purely quantum correlations due to entanglement disappear. Analytical expressions for the energy and the form of such states are given, and a novel type of exactly solvable two-dimensional quantum models is therefore singled out. Moreover, we show that the field-induced quantum phase transition present in the models is unambiguously characterized by a cusp minimum in the pairwise-to-global entanglement ratio R, marking the quantum-critical enhancement of multipartite entanglement.     

Quantum localization in bilayer Heisenberg antiferromagnets with site dilution

The field-induced antiferromagnetic ordering in systems of weakly coupled S = 1/2 dimers at zero temperature can be described as a Bose-Einstein condensation of triplet quasiparticles (singlet quasiholes) in the ground state. For the case of a Heisenberg bilayer, it is here shown how the above picture is altered in the presence of site dilution of the magnetic lattice. Geometric randomness leads to quantum localization of the quasiparticles or quasiholes and to an extended Bose-glass phase in a realistic disordered model. This localization phenomenon drives the system towards a quantum-disordered phase well before the classical geometric percolation threshold is reached.     

Derivative discontinuities in time-dependent density-functional theory

Based on the Runge-Gross theorem for ensembles we investigate the influence of particle-number-changes on the exchange-correlation potential in time-dependent density-functional theory. We show that the potential changes discontinuously when the particle number crosses an integer value. Real-time simulations of an atomic ionization process demonstrate that this discontinuity appears naturally in the theory of the time-dependent optimized effective potential. The importance of such a discontinuity for physical processes, even such ones in which the particle number is a constant, is discussed.     

Correlations and counting statistics of an atom laser

We demonstrate time-resolved counting of single atoms extracted from a weakly interacting Bose-Einstein condensate of 87Rb atoms. The atoms are detected with a high-finesse optical cavity and single atom transits are identified. An atom laser beam is formed by continuously output coupling atoms from the Bose-Einstein condensate. We investigate the full counting statistics of this beam and measure its second order correlation function g((2))(tau) in a Hanbury Brown-Twiss type experiment. For the monoenergetic atom laser we observe a constant correlation function g((2))(tau)=1.00 +/- 0.01 and an atom number distribution close to a Poissonian statistics. A pseudothermal atomic beam shows a bunching behavior and a Bose distributed counting statistics.     

Spin correlations and magnetic order in nonsuperconducting Nd(2-x)Ce(x)CuO(4+/-delta)

We report quantitative neutron scattering measurements of the evolution with doping of the Néel temperature, the antiferromagnetic correlations, and the ordered moment of as-grown, nonsuperconducting Nd(2-x)Ce(x)CuO(4+/-delta) (0相似文献   

Real-Time Detection of Polymerase Activity Using Supercritical Angle Fluorescence

We investigated the incorporation efficiencies of different fluorescently labelled dNTPs with polymerases by complementary strand synthesis. For this reason single stranded DNA was immobilized on a coverslip and the increase of fluorescence due to the synthesis of the corresponding strand with tagged dNTPs was detected with a supercritical angle fluorescence biosensor in real-time. By comparison of the observed signal intensities it was possible to conclude that the system Cy5-dCTP-Klenow (exonuclease free) fragment gives the best incorporation yield of the investigated enzymes and dNTPs.