Probing the Roughness of Porphyrin Thin Films with X-ray Photoelectron Spectroscopy

Thin-film growth of molecular systems is of interest for many applications, such as for instance organic electronics. In this study, we demonstrate how X-ray photoelectron spectroscopy (XPS) can be used to study the growth behavior of such molecular systems. In XPS, coverages are often calculated assuming a uniform thickness across a surface. This results in an error for rough films, and the magnitude of this error depends on the kinetic energy of the photoelectrons analyzed. We have used this kinetic-energy dependency to estimate the roughnesses of thin porphyrin films grown on rutile TiO₂(110). We used two different molecules: cobalt (II) monocarboxyphenyl-10,15,20-triphenylporphyrin (CoMCTPP), with carboxylic-acid anchor groups, and cobalt (II) tetraphenylporphyrin (CoTPP), without anchor groups. We find CoMCTPP to grow as rough films at room temperature across the studied coverage range, whereas for CoTPP the first two layers remain smooth and even; depositing additional CoTPP results in rough films. Although, XPS is not a common technique for measuring roughness, it is fast and provides information of both roughness and thickness in one measurement.     

Surface science goes liquid !

Ionic liquids are a new class of materials with most interesting properties. They are liquid at room temperature, but have a negligible vapour pressure. Consequently they can, in contrast to normal liquids, be investigated by all UHV-based methods of surface science. This allows to determine their properties with the same atomic level accuracy that is presently common for solid surfaces and conventional adsorbate systems. Apart from the investigation of the specific properties of ionic liquids, which are relevant for many applications, this also opens the possibility to obtain more detailed insight in the general physical and chemical properties of liquids. In that sense it opens the door to a new chapter of surface science – “Ionic Liquid Surface Science”.     

Exact Buffer Overflow Calculations for Queues via Martingales

Let _n be the first time a queueing process like the queue length or workload exceeds a level n. For the M/M/1 queue length process, the mean _n and the Laplace transform e^-sn is derived in closed form using a martingale introduced in Kella and Whitt (1992). For workload processes and more general systems like MAP/PH/1, we use a Markov additive extension given in Asmussen and Kella (2000) to derive sets of linear equations determining the same quantities. Numerical illustrations are presented in the framework of M/M/1 and MMPP/M/1 with an application to performance evaluation of telecommunication systems with long-range dependent properties in the packet arrival process. Different approximations that are obtained from asymptotic theory are compared with exact numerical results.     

13C NMR spectra of diazastilbenes. I—trans-styryldiazines

The ¹³C NMR spectra of all trans-styryldiazines, methyldiazines and trans-styrylpyridines have been fully assigned. Empirical shift increments were obtained for the chemical shifts of the carbon atoms; these are discussed in the light of theoretical considerations.     

«Push-Pull»-Acetylene als Hilfsmittel zur Synthese von Amiden

Amide Synthesis by Means of ‘Push-Pull’-Acetylenes ‘Push-Pull’-acetylenes react easily with carbon acids, Addition of amines to the crude reaction mixture gives amides in an excellent yield by a simple one-pot procedure. Because of the high selectivity of the acetylenes 1 towards carboxylic functions and of the high selectivity of the enol esters 4 towards amine functions, ‘push-pull’-acetylenes could be excellent reagents for peptide synthesis.