Photoemission study of the growth of the NdF3/Si(111) interface

Photoemission spectroscopy with synchrotron radiation was used to study the NdF₃/Si(111) interface as a function of annealing temperature for NdF₃ films. These films range in thickness from 1–20 monolayers and were deposited at room temperature. Without annealing, both F-Si and Nd-Si bonding is observed, indicating that the planar triangular NdF₃ molecules lie flat on the Si(111) substrate. At annealing temperatures between 400 and 500° C, the NdF₃/Si(111) interface is dominated by Nd-Si bonding as evidenced from a line-shape analysis of the Si 2 p and Nd 4 f core levels. By resonant excitation of the giant 4 d-4 f absorption resonance, the photoemission signal from the partially occupied 4 f orbitals is enhanced and can be distinguished from the photoemission signal of the overlapping F 2 p valence band. At higher temperatures F is completely lost due to the decomposition of NdF₃.     

Core hole screening and lifetimes in adsorbates on metallic surfaces

The C 1s photoemission lineshape and width has been studied for methoxy (CH₃O), formate (HCO₂) and CO on Cu(100). We find the Doniach-Sunjic asymmetry of the lineshape to be different for the three adsorbates and correlate these differences with the adsorption geometry. The observed shake up satellites exhibit a greatly increased width compared to the main lines, which is attributed to the reduced lifetime of the excited state of the C 1s core hole.     

BINOL-derived phosphoramidites in asymmetric hydrogenation: can the presence of a functionality in the amino group influence the catalytic outcome?

In discovering the remarkable catalytic properties of BINOL-derived phosphoramidites (binoP-NR(2)), Dutch researchers recently achieved a long-awaited breakthrough in asymmetric catalysis. For the first time, easily accessible monodentate chiral P(III) ligands turned out to provide high enantioselectivities when used in rhodium-catalysed olefin hydrogenation. The simplest ligand representative of this family is MonoPhos, which can be made straightforwardly from BINOL and hexamethylphosphorous triamide. Since the first publication dealing with such catalysts (J. Am. Chem. Soc., 2000), a variety of binoP-NRR' ligands have been reported in which the amino group bears a functional substituent or a stereogenic centre. This critical review examines the impact of the presence of such a functionality in the amino group on catalytic olefin hydrogenation reactions.