Characterization of low molecular weight hydrocarbon oligomers by laser desorption/ionization time-of-flight mass spectrometry using a solvent-free sample preparation method.

A new solvent-free sample preparation method using silver trifluoroacetate (AgTFA) was developed for the analysis of low molecular weight paraffins and microcrystalline waxes by laser desorption/ionization time-of-flight mass spectrometry (LDI-TOFMS). Experiments show that spectral quality can be enhanced by dispersing AgTFA directly in liquid paraffins without the use of additional solvents. This preparation mixture is applied directly to the MALDI probe. Solid waxes could be examined by melting prior to analysis. The method also provides sufficiently reproducible spectra that peak area ratios between mono- and bicyclic alkane peaks indicated variations in the cycloalkane content of paraffin samples. Dehydrogenation of hydrocarbons observed during the desorption/ionization process was studied by analysis of alkane standards.     

High resolution laser spectroscopy of Ba Rydberg atoms

The purpose of the present paper is to illustrate some selected aspects of high resolution laser spectroscopy of Rydberg atoms, rather than giving an extensive review of the state of the art. The following topics will be discussed: (i) Excitation and detection of Ba Rydberg atoms with principal quantum numbers up ton≲300; (ii) Stark effect and atomic diamagnetism of high-n Ba Rydberg states in thel-mixing region, (iii) Resonance in singlet-triplet mixing of 6snp¹P₁ and 6snd¹D₂ Ba Rydberg states deduced from hyperfine structure measurements.     

Combinatorial approach to the study of particle size effects in electrocatalysis: synthesis of supported gold nanoparticles

A high-throughput method for physical vapor deposition has been applied to the synthesis of libraries of supported gold particles on amorphous substoichiometric TiO(x)() and carbon supports. The TiO(x)() substrate stoichiometry can be varied or kept constant across a supporting sample, and subsequent deposition of particle sizes on supports are controlled through the nucleation and growth process. TEM measurements indicate nucleation and growth of Au particles takes place, with the smallest particles initially observed at 1.4 nm with a maximum density of 5.5 x 10(12) cm(-2) on titania, and 2.6 nm with concomitantly lower density on carbon. The 1.4-nm particles on titania exhibit a binding energy shift in the Au(4f) core level of 0.3 eV from bulk gold, and the shift is approximately 0.1 eV by the time particles grow to a mean size of 2.5 nm. These shifts are associated with final state effects, and the supported gold particles are metallic and appear to be relatively stable in air. When combined with appropriate substrates and screening techniques, this method provides a highly controllable method for the high-throughput synthesis of model supported catalyst.     

On Eigenvector Bounds

We show under very general assumptions that error bounds for an individual eigenvector of a matrix can be computed if and only if the geometric multiplicity of the corresponding eigenvalue is one. Basically, this is true if not computing exactly like in computer algebra methods. We first show, under general assumptions, that nontrivial error bounds are not possible in case of geometric multiplicity greater than one. This result is also extended to symmetric, Hermitian and, more general, to normal matrices. Then we present an algorithm for the computation of error bounds for the (up to normalization) unique eigenvector in case of geometric multiplicity one. The effectiveness is demonstrated by numerical examples.This revised version was published online in October 2005 with corrections to the Cover Date.