Non-thermal laser-induced desorption of metal atoms with bimodal kinetic energy distribution

Laser-induced desorption of metal atoms at low rate has been studied for pulsed excitation with wavelengths of = 266, 355, 532 and 1064 nm. For this purpose sodium adsorbed on quartz served as a model system. The detached Na atoms were photo-ionized with the light of a second laser operating at = 193 nm and their kinetic energy distribution was determined by time-of-flight measurements. For = 1064 nm a distribution typical of thermal bond breaking is observed. If desorption, however, is stimulated with light of = 266 or 532 nm, the kinetic energy distribution is non-thermal with a single maximum atE _kin = 0.16 ± 0.02 eV. For = 355 nm the non-thermal distribution is even bimodal with maxima appearing atE _kin = 0.16 ± 0.02 and 0.33 ± 0.02 eV. These values of the kinetic energies actually remain constant under variation of all experimental parameters. They appear to reflect the electronic and geometric properties of different binding sites from which the atoms are detached and thus constitute fingerprints of the metal surface. The non-thermal desorption mechanism is discussed in the framework of the Menzel-Gomer-Redhead scenario. The transition from non-thermal to thermal desorption at large fluentes of the laser light could also be identified.     

Funktionalgleichung und Differenzierbarkeit bei den trigonometrischen Funktionen

Ohne Zusammenfassung     

Computation and analysis of the dynamic structure factor S(k, ω) for small wave vectors

Molecular dynamics (MD) calculations have been performed for the Lennard-Jones (12-6) potential function using 2048 particles. Using conventional parameters the results may be compared with those for liquid argon.

The dynamic structure factor S(k, ω) has been determined both by Fourier inversion of the intermediate scattering function F(k, t) and from the longitudinal current-current correlation function C _∥(k, t). Particular attention was paid to the recurrence time of the system. The results for S(k, ω) by the two methods agree within 5 per cent for the whole region of small k-vectors considered. Double Fourier inversion of the van Hove function G(r, t) led to insufficiently accurate results for these small k-values. In view of the present data, the MD-results of Levesque et al. [1] for S(k, ω) have only a qualitative character. These latter data appear to contain truncation errors due to incomplete Fourier transformations.

Using a hydrodynamic assumption for F(k, t) we were able to extract the transport coefficients, the velocity of sound and the ratio of the specific heats in the limit of large wave lengths or small k. The velocity of sound was obtained by exploiting the MD generated anomalous dispersion curve of sound waves. Anomalous dispersion was found to set in for kσ ～ 0·25. A sound speed of 880 ms^-1 has been determined which is in excellent agreement with experimental values for liquid argon. The total error for the MD value amounts to about 5 per cent. In contrast, the ratio of the specific heats γ and the transport coefficients D _T and Γ (thermal diffusivity and sound attenuation) were determinable only with an accuracy of 15 per cent due to the need for larger extrapolations. Nevertheless, we found D _T, Γ and γ in agreement with experimental values within 5-10 per cent.     

Targeted next-generation sequencing by specific capture of multiple genomic loci using low-volume microfluidic DNA arrays

We report a flexible method for selective capture of sequence fragments from complex, eukaryotic genome libraries for next-generation sequencing based on hybridization to DNA microarrays. Using microfluidic array architecture and integrated hardware, the process is amenable to complete automation and does not introduce amplification steps into the standard library preparation workflow, thereby avoiding bias of sequence distribution and fragment lengths. We captured a discontiguous human genomic target region of 185 kb using a tiling design with 50mer probes. Analysis by high-throughput sequencing using an Illumina/Solexa 1G Genome Analyzer revealed 2150-fold enrichment with mean per base coverage between 4.6 and 107.5-fold for the individual target regions. This method represents a flexible and cost-effective approach for large-scale resequencing of complex genomes. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users. Stephan Bau and Nadine Schracke contributed equally to this work.     

Generalized Newton’s method based on graphical derivatives

This paper concerns developing a numerical method of the Newton type to solve systems of nonlinear equations described by nonsmooth continuous functions. We propose and justify a new generalized Newton algorithm based on graphical derivatives, which have never been used to derive a Newton-type method for solving nonsmooth equations. Based on advanced techniques of variational analysis and generalized differentiation, we establish the well-posedness of the algorithm, its local superlinear convergence, and its global convergence of the Kantorovich type. Our convergence results hold with no semismoothness and Lipschitzian assumptions, which is illustrated by examples. The algorithm and main results obtained in the paper are compared with well-recognized semismooth and B-differentiable versions of Newton’s method for nonsmooth Lipschitzian equations.     

Influence of molecular adsorbate layers on the optical spectra of small metal particles

2 , N₂O, CO₂ or N₂ on the particle surface. Depending on the molecules to which the clusters are exposed, different changes of the surface plasmon resonance in the spectra can be identified. The most essential experimental results are as follows. First, changes of the optical spectra are found if the clusters are covered by less than a molecular monolayer. Secondly, the observed variations of the spectra allow to distinguish between physisorption and chemisorption, i.e. characterize the strength of the surface chemical bond. Third, in sharp contrast to the usual shift of the plasmon frequency to longer wavelengths by change of the dielectric surrounding, a blue shift of the resonance has been observed upon dosage of CO₂. Finally, diffusion of adsorbate molecules into the bulk of the particles can be identified. Received: 11 September 1997     

Theoretical and numerical comparison of relaxation methods for mathematical programs with complementarity constraints

Mathematical programs with equilibrium constraints (MPECs) are difficult optimization problems whose feasible sets do not satisfy most of the standard constraint qualifications. Hence MPECs cause difficulties both from a theoretical and a numerical point of view. As a consequence, a number of MPEC-tailored solution methods have been suggested during the last decade which are known to converge under suitable assumptions. Among these MPEC-tailored solution schemes, the relaxation methods are certainly one of the most prominent class of solution methods. Several different relaxation schemes are available in the meantime, and the aim of this paper is to provide a theoretical and numerical comparison of these schemes. More precisely, in the theoretical part, we improve the convergence theorems of several existing relaxation methods. There, we also take a closer look at the properties of the feasible sets of the relaxed problems and show which standard constraint qualifications are satisfied for these relaxed problems. Finally, the numerical comparison is based on the MacMPEC test problem collection.     

Synthesis of Diacetylene‐Containing Peptide Building Blocks and Amphiphiles,Their Self‐Assembly and Topochemical Polymerization in Organic Solvents

A series of functional iodoacetylenes was prepared and converted into the corresponding diacetylene‐substituted amino acids and peptides via Pd/Cu‐promoted sp–sp carbon cross‐coupling reactions. The unsymmetrically substituted diacetylenes can be incorporated into oligopeptides without a change in the oligopeptide strand's directionality. Thus, a series of oligopeptide‐based, amphiphilic diacetylene model compounds was synthesized, and their self‐organization as well as their UV‐induced topochemical polymerizability was investigated in comparison to related polymer‐substituted macromonomers. Solution‐phase IR spectroscopy, gelation experiments, and UV spectroscopy helped to confirm that a minimum of five N‐H???O?C hydrogen‐bonding sites was required in order to obtain reliable aggregation into stable β‐sheet‐type secondary structures in organic solvents. Furthermore, the non‐equidistant spacing of these hydrogen‐bonding sites was proven to invariably lead to β‐sheets with a parallel β‐strand orientation, and the characteristic IR‐spectroscopic signatures of the latter in organic solution was identified. Scanning force micrographs of the organogels revealed that compounds with six hydrogen‐bonding sites gave rise to high aspect ratio nanoscopic fibrils with helical superstructures but, in contrast to the related macromonomers, did not lead to uniform supramolecular polymers. The UV‐induced topochemical polymerization within the β‐sheet aggregates was successful, proving parallel β‐strand orientation and highlighting the effect of the number and pattern of N‐H???O?C hydrogen‐bonding sites as well as the hydrophobic residue in the molecular structure on the formation of higher structures and reactivity.