Chlorine‐Enhanced Surface Mobility of Au(100)

Motivated by experimental studies of two‐dimensional Ostwald ripening on Au(100) electrodes in chlorine‐containing electrolytes, we have studied diffusion processes using density functional theory. We find that chlorine has a propensity to temporary form AuCl complexes, which diffuse significantly faster than gold adatoms. With and without chlorine, the lowest activation energy is found for the exchange mechanism. Chlorine furthermore reduces the activation energy for the detachment from kink sites. Kinetic Monte Carlo simulations were performed on the basis of extensive density functional theory calculations. The island‐decay rate obtained from these Monte Carlo simulations, as well as the decay rate obtained from the theoretical activation energies and frequency factors when inserted into analytical solutions for Ostwald ripening, are in agreement with experimental island‐decay rates in chlorine‐containing electrolytes.     

Very Large Cyclic Compounds

Very large ring systems, containing more than 50 ring members, are becoming increasingly important in different topics in natural sciences. These so-called gigantocycles differ from smaller macrocycles in physical properties, special structural features and chemical behaviour. This article is meant to be the first summary of such ring systems and a synopsis of the most remarkable examples with their fascinating nano-scaled structures and ingenious synthesis. To restrict the scope of the article, only isolated and completely characterized, monodisperse compounds are presented. Furthermore, attention is mainly directed at organic gigantocycles. Some ultracycles with more than 100 ring members, mainly occurring in polymer chemistry and nature, will also be described.     

Angular distribution of EELS intensities: CO on Pt(111)

We present the angular distribution of inelastic intensities corresponding to the excitation of the vibrational modes of CO chemisorbed on Pt(111). The experimental values are compared with those predicted by dipole scattering. All the vibrational modes, including the C-metal, stretch, show experimental values larger than theoretical ones. The difference is attributed to vibrational excitation by impact scattering. The impact scattering cross section is found to be energy dependent and increases for low primary energies (2 eV). The differential cross section is, however, smaller than that observed for resonant scattering in free CO.     

Surface vibrations and the nature of the adsorption state: C2H2 on Pt(111)

Molecular vibrations of C₂H₂ and C₂D₂ adsorbed on Pt(111) at 140 K and ∼300K have been measured by high resolution electron energy loss spectroscopy. The comparison of C₂H₂ and C₂D₂ spectra allows an unambiguous assignment of the observed losses to the excitation of C−H bending, C−H stretching, and C−C stretching modes of nondissociatively adsorbed acetylene. From the relative intensities of losses the hybridisation state is determined to be nearsp ². The C−C stretching frequency indicates a C−C bond order of ∼1.8.     

Experimental study of the vibrations of acetylene chemisorbed on Ni(111)

High resolution electron energy-loss measurements of normal and deuterated acetylene chemisorbed on Ni(111) have been obtained. Observed vibrational modes are identified using the frequency shifts for the deuterated species and comparisons to the free molecule and a di-cobalt compound of acetylene. These vibrational frequencies indicate that chemisorbed acetylene is strongly rehybridized having a state of hybridization between ~sp^2.5 and sp³. Consideration of the types of modes observed, their assignments and the surface selection rule suggests a molecular orientation with the C-C bond axis slightly skewed relative to the surface and with the plane of the distorted molecule normal to the surface. A bonding geometry is proposed which has the carbon atoms residing above two adjacent 3 fold hollow sites of the Ni surface. This molecular geometry differs from that deduced previously by electron energy-loss spectroscopy for molecularly adsorbed acetylene on Pt(111).     

The bonding of water molecules to platinum surfaces

Using high resolution electron energy loss spectroscopy in ultra-high vacuum we have studied the vibrational spectrum of submonolayer and multilayer quantities of water adsorbed on platinum (100) surfaces. For adsorbed multilayers the spectrum resembles the spectrum of ice I. For submonolayer quantities of H₂O we find three different OH stretching vibrations, 2850, 3380, and 3670 cm^?1. The highest frequency is attributed to free OH groups. The vibration around 3380 cm^?1 indicates H bonding between oxygen atoms. It is therefore concluded that the water molecules cluster even at low coverage. The lowest OH stretching frequency is attributed to H bonding to platinum. We find also evidence for additional oxygen lone pair orbital bonding to the surface which disappears however when the first monolayer is completed. The relation to currently considered models in electrochemistry of aqueous solutions is discussed.