Hans Niemantsverdriet

First-principles elucidation of the surface chemistry of the C2Hx (x = 0–6) adsorbate series on Fe(100)

Ab initio total-energy calculations of the elementary reaction steps leading to acetylene, ethylene and ethane formation and their decomposition on Fe(100) are described. Alongside the endothermicity of all the formation reactions, the crucial role played by adsorbed ethyl as main precursor towards both ethylene and ethane formation, characterises Fe(100) surface reactivity towards C2Hx (x = 0–6) hydrocarbon formation in the low coverage limit. A comprehensive scheme based on three viable mechanisms towards ethyl formation on Fe(100), including methyl/methylene coupling, methyl/methylidyne coupling followed by one hydrogenation and methyl/carbon coupling followed by two hydrogenations, is the main result of this article.

Toward measuring concentration gradients in polymer-dispersed liquid crystals with secondary ion mass spectrometry

Dynamic secondary ion mass spectrometry (SIMS) is usually applied to measure depth profiles in inorganic multi-layer systems. SIMS on organic multi-layer samples is highly complicated due to the complex fragmentation of the sample which results in fingerprint of masses representing the components in the sample. Using multivariate statistics, we succeeded to interpret the SIMS spectra and were able to identify layers with different compositions in artificially produced two-layer samples. The method is demonstrated for samples of a poly(isobornylmethacrylate) coating on a polymer dispersed liquid crystal consisting of the nematic liquid crystal (E7) and poly(isobornylmethacrylate). Quantification of the E7 concentration is complicated by evaporation in the vacuum system. Infrared spectroscopy proved that the loss of E7 from poly(isobornylmethacrylate) can be prevented by capping the sample with poly(vinyl alcohol). Cooling to cryogenic temperatures will be required to suppress further evaporation during SIMS analysis. The SIMS depth resolution of a two-layered sample was determined by discriminant function analysis to be 130 nm at a depth of one micrometer, which allows the application of SIMS for a typical optical grating.