Trends in surface and interface analysis

Summary The rapid progress in high technology constantly poses new challenges for Analytical Chemistry and prompts the development of new techniques and procedures. The influence is particularly strong in surface and interface analysis, which is developing at a rapid pace. This paper discusses some of the frontier areas like high-resolution depth-distribution analysis of trace elements, quantitative depth distribution analysis of ultra thin-layer systems, quantitative trace element analysis in monolayers, 3-dimensional stereometric analysis, molecular analysis, in-situ atomic resolution analysis of surfaces (chemical nanoscopy). Methodological approaches are discussed as well as results obtained mainly with solid state mass spectrometry and atomic force microscopy.Abbreviations and acronyms AES Auger Electron Spectrometry - AEM Analytical Electron Microscopy - AFM Atomic Force Microscopy - BSE Back Scattered Electrons - EPMA Electron Probe Micro Analysis - LRI-SNMS Laser Resonance Ionization Sputtered Neutrals Mass Spectrometry - SE Secondary Electrons - SEM Scanning Electron Microscopy - SIMS Secondary Ion Mass Spectrometry - STM Scanning Tunneling Microscopy - TEM Transmission Electron Microscopy - TOF-MS Time-of-Flight Mass Spectrometer - TXRF Total Reflection X-Ray Spectrometry - XPS X-Ray Photoelectron Spectroscopy Dedicated to Professor Dr. Wilhelm Fresenius on the occasion of his 80th birthday     

Stability analysis of gravity driven shear flows with free surface for power-law fluids

Summary We study the stability of thin films of fluids subject to gravity along inclined planes, obeying a power-law constitutive relation of the Ostwald-de Waele type. A first analysis, in which the inertia terms are ignored, shows such flow to be stable against small, linear perturbations; a second analysis, in which the inertia terms are included, proves that there are stable and unstable regimes that are separated by a critical Ostwald-de Waele number O. Numerical computations for selected values of O demonstrate the decay and growth rate behavior of some finite amplitude disturbances. Received 12 May 1997; accepted for publication 23 July 1997     

Maximum entropy deconvolution of AFM and STM images

The Maximum Entropy Method (MEM) has been applied successfully to the deconvolution of images obtained by Atomic Force (AFM) and Scanning Tunneling Microscopy (STM) using a NanoScope III system. The images have been taken on graphite (STM) and NaCl (AFM) substrates. Image processing has been performed running the Cambridge MaxEnt Fortran 77 library MEMSYS-5 on an IBM RISC 6000/360. Among the possible hypotheses the optimal solution was selected using the standard entropy method. ICF and response function have been generated artificially to fit the correlation of physical structures for atomically resolved images. Comparison of MEM and FFT revealed, that the main advantage of MEM is its ability to reproduce atomic defects on regular structures, whereas FFT deconvolution tends to eliminate these perturbations.     

Ionic liquids from Car-Parrinello simulations, part I: liquid AlCl3

The properties of isolated AlCl3 clusters and the bulk system are investigated by means of static and dynamic electronic structure methods. We find important structural motifs with the edge connectivity dominant in a dimer and the corner connectivity dominant in a trimer. Furthermore, the trimer cluster exhibits an interesting ring structure with large cooperative effects relative to the dimer. Comparing the found structural motifs in isolated molecule calculations with the structure of the liquid allows us to determine the dominance of edge connectivity in the liquid. The size of the clusters present in the liquid indicates indeed that the dimer is the most abundant species, but there are also trimers, tetramers, and pentamers present. From the local dipole analysis both for the isolated clusters as well as for the liquid, further proof for the edge connectivity is given. However, all results point to the fact that there is also some small percentage of corner connectivity present that might be attributed to the most stable corner-connected cluster, namely the trimer. Importantly, we find that energetic considerations of isolated (static) clusters only do not represent the findings in liquid phase. Instead, a quantum cluster equilibrium approach or simulations are needed.     

TOF-SIMS investigations on weathered silver surfaces

Silver-coated quartz crystal microbalance (QCM) disks were treated under different environmental conditions (including changes in parameters such as relative humidity (%RH) and SO₂/H₂S content) in atmospheres of synthetic air and pure N₂ for 24 h in a weathering chamber. The corroded surfaces were subjected to depth profiling by a time of flight (TOF) secondary ion mass spectrometry (SIMS) instrument, equipped with a Bi⁺ analysis gun and Cs⁺ sputter gun. The evaluation of the in-depth distribution of several elements and species provides evidence for the formation of a corrosion layer containing Ag₂SO₃, even in the absence of oxidizing agents, such as H₂O₂ or NO₂. Furthermore it could be elucidated that the thickness of the formed Ag₂SO₃ layer does not depend on the SO₂ concentration but rather on the humidity and oxygen content of the ambient atmosphere. In weathering experiments in atmospheres composed of synthetic air, humidity, and H₂S, the presence of different oxygen species (surface and bulk) and silver sulfide could be detected by TOF-SIMS depth profiling experiments. The obtained results for both acidifying gases are in good correlation with the corresponding tapping mode atomic force microscopy (TM-AFM) investigations and in situ QCM measurements.     

Effect of end group polarity upon the lower critical solution temperature of poly(2-isopropyl-2-oxazoline)

Thermo-sensitive poly(2-isopropyl-2-oxazoline)s (PiPrOx) were functionalized with end groups of different polarity by living cationic ring-opening polymerization using the initiator and/or termination method as well as sequential block copolymerization with 2-methyl-2-oxazoline. As end groups, methyl, n-nonyl, piperidine, piperazine as well as oligo(ethylenglygol) and oligo(2-methyl-2-oxazoline) were introduced quantitatively. The lower critical solution temperature (LCST) of the aqueous solutions was investigated. The introduction of hydrophobic end groups decreases the LCST, while hydrophilic polymer tails raise the cloud point. In comparison to poly(N-isopropyl acrylamide), the impact of the end group polarity upon the modulation of the LCST was found to be significantly stronger. Surprisingly, terminal oligoethylenegycol units also decrease the LCST of PiPrOx, thus acting as moieties of higher hydrophobicity as compared to the poly(2-oxazoline) main chain. Together with the possible variation of the side group polarity, this allows a broad modulation of the LCST of poly(2-oxazoline)s.     

The Gaussian and augmented-plane-wave density functional method for ab initio molecular dynamics simulations

A new algorithm for density-functional-theory-based ab initio molecular dynamics simulations is presented. The Kohn–Sham orbitals are expanded in Gaussian-type functions and an augmented-plane-wave-type approach is used to represent the electronic density. This extends previous work of ours where the density was expanded only in plane waves. We describe the total density in a smooth extended part which we represent in plane waves as in our previous work and parts localised close to the nuclei which are expanded in Gaussians. Using this representation of the charge we show how the localised and extended part can be treated separately, achieving a computational cost for the calculation of the Kohn–Sham matrix that scales with the system size N as O(NlogN). Furthermore, we are able to reduce drastically the size of the plane-wave basis. In addition, we introduce a multiple-cutoff method that improves considerably the performance of this approach. Finally, we demonstrate with a series of numerical examples the accuracy and efficiency of the new algorithm, both for electronic structure calculations and for ab initio molecular dynamics simulations. Received: 15 December 1998 /Accepted: 18 February 1999 /Published online: 14 July 1999