Successive coordination of palladium(II)-ions and terpyridine-ligands to a pyridyl-terminated self-assembled monolayer on gold

The deposition of palladium on a novel, reversibly protonatable, pyridyl-terminated self-assembled monolayer on gold substrates has been studied by X-ray photoelectron spectroscopy (XPS), near-edge X-ray absorption fine structure spectroscopy (NEXAFS spectroscopy) and time of flight-secondary ion mass spectrometry (ToF-SIMS). For this purpose, 12-(pyridin-4-yl)dodecane-1-thiol, consisting of a surface-active head group, an unfunctionalized hydrocarbon backbone and a terminal pyridyl group, has been synthesized and deposited on gold surfaces. Coordination of Pd(II) ions to the pyridyl group was examined. Furthermore, a reversible protonation/deprotonation cycle has been applied, and the relation between protonation and the amount of complexed palladium was studied. Investigation of the SAM by angle-resolved NEXAFS spectroscopy revealed the aliphatic backbone to be preferentially upright oriented with the aromatic head group being not preferentially oriented. The palladium layer was further coordinated with a CF₃-labeled terpyridine ligand in order to prove the accessibility of the Pd(II) ions to further complexation and the platform useful for deposition of further layers toward a multi-layered system.     

Direct evaluation of the subgrid scale scalar flux in turbulent premixed flames with conditioned dual-plane stereo PIV

With the dual-plane stereo PIV technique the instantaneous three-dimensional resolved rate-of-strain tensor is directly measured in turbulent premixed flames. Simultaneously, also the instantaneous subgrid scale (SGS) scalar flux is measured with fine resolution, where for the latter term the conditioned particle image velocimetry (CPIV) technique is applied. The subgrid resolution reaches 118 μm, allowing a 9 × 9 resolution of a subgrid filter with width Δ = 1 mm. This combined measurement approach allows the a-priori comparison of models for the SGS scalar flux term with direct measurements which is important for large eddy simulation methods in turbulent premixed flames. Two different flame conditions of a premixed V-shaped turbulent flame are investigated where the turbulence intensity is varied by a factor of nearly three. The instantaneous radial and axial SGS fluxes are compared with the following three models: gradient model with Smagorinsky approach for the turbulent viscosity, Clark model, and extended gradient model with an anisotropy term. None of these models shows a good correlation with the directly measured flux. The anisotropy term alone (being nearly similar to the Clark model) shows, however, a right trend behaviour. An analysis of the data indicates a significant dependency of the experimentally determined SGS flux on the Favre averaged reaction progress (spatially averaged over the SGS area). A relatively simple closure for the SGS flux, which describes the dilatation due to the gasdynamic expansion, and which is a function proportional to , shows a rather good correlation with direct measurement for some of the components. A successful SGS scalar flux model for premixed turbulent flames most likely needs to include at least two different effects.     

Laser ionization in β decay studies of Zn and Mn nuclei

Resonance ionization laser ion source (RILIS) technique has been used in the β-decay studies of ⁵⁹Mn and ⁵⁸Zn. The importance of the RILIS for production of these elements is discussed. The properties of the low-lying levels of the studied nuclei are discussed. This revised version was published online in August 2006 with corrections to the Cover Date.     

Generalized clausius inequality for nonequilibrium quantum processes

We show that the nonequilibrium entropy production for a driven quantum system is larger than the Bures length, the geometric distance between its actual state and the corresponding equilibrium state. This universal lower bound generalizes the Clausius inequality to arbitrary nonequilibrium processes beyond linear response. We further derive a fundamental upper bound for the quantum entropy production rate and discuss its connection to the Bremermann-Bekenstein bound.     

Nonparametric Estimation of Regression Functions in Point Process Models

We prove that the empirical L ²-risk minimizing estimator over some general type of sieve classes is universally, strongly consistent for the regression function in a class of point process models of Poissonian type (random sampling processes). The universal consistency result needs weak assumptions on the underlying distributions and regression functions. It applies in particular to neural net classes and to radial basis function nets. For the estimation of the intensity functions of a Poisson process a similar technique yields consistency of the sieved maximum likelihood estimator for some general sieve classes. This revised version was published online in August 2006 with corrections to the Cover Date.     

Theory of ion neutralisation scattering from surfaces

A method for the calculation of the probability of neutralisation of an ion, which is scattered from the surface of a solid is presented. It assumes the ion to move along a classical trajectory and solves for the time evolution operator for the electronic system. For one electron Hamiltonians the solution can be carried out exactly. Results are presented for scattering from a semi-infinite linear chain.     

Electron transfer in the reflection of atoms from metal surfaces

The resonance mechanism for positive and negative ionization of an atom reflected from a metal surface is treated in the time-dependent Hartree-Fock approximation assuming that the atom moves on its classical trajectory. A simple model is parameterized to describe 30–500 eV Na atoms reflected from tungsten, and the ionization probabilities are calculated by numerical integration of the equation of motion of the time evolution operator. Significant ionization can only occur if either the ionization level, or the affinity level of the atom crosses the Fermi level beyond the range of the atom-metal hopping interaction. On clean tungsten, the former situation applies, and the probability of positive ionization is nearly unity, and of negative ionization nearly zero.     

Hydrogen control of ferromagnetism in a dilute magnetic semiconductor

We show that upon exposure to a remote dc hydrogen plasma, the magnetic and electronic properties of the dilute magnetic semiconductor Ga1-xMnxAs change qualitatively. While the as-grown Ga1-xMnxAs thin films are ferromagnetic at temperatures T less, similar 70 K, the samples are found to be paramagnetic after the hydrogenation, with a Brillouin-type magnetization curve even at T=2 K. Comparing magnetization and electronic transport measurements, we conclude that the density of free holes p is significantly reduced by the plasma process, while the density of Mn magnetic moments does not change.