Synthesis of Piano Stool Complexes Employing the Pentafluorophenyl Substituted Diphosphine (C6F5)2PCH2P(C6F5)2 and the Effect of Phosphine Modifiers on Hydrogen Transfer Catalysis.

Ruthenium, rhodium, and iridium piano stool complexes of the pentafluorophenyl-substituted diphosphine (C6F5)2PCH2P(C6F5)2 (2) have been prepared and structurally characterized by single-crystal X-ray diffraction. The Cp-P tethered complex [{(C5Me4CH2C6F4(C6F5)CH2P(C6F5)2}RhCl2] (9), in which only one phosphorus is coordinated to the rhodium, was prepared by thermolysis of a slurry of [Cp*RhCl(-Cl)]2 and 2 and was structurally characterized by single-crystal X-ray diffraction. The tethering occurs by intramolecular dehydrofluorinative coupling of the pentamethylcyclopentadienyl ligand and P,P-coordinated 2. The geometric changes that occur on tethering force dissociation of one of the phosphorus atoms. The effects of introducing phosphine ligands to the coordination sphere of piano stool hydrogen transfer catalysts have been studied. The complexes of fluorinated phosphine complexes are found to transfer hydrogen at rates that compare favorably with leading catalysts, particularly when the phosphine and cyclopentadienyl functionalities are tethered. The highly chelating Cp-PP complex [(C5Me4CH2-2-C5F3N-4-PPhCH2CH2PPh2)RhCl]BF4 (1) was found to outperform all other complexes tested. The mechanism of hydrogen transfer catalyzed by piano stool phosphine complexes is discussed with reference to the trends in activity observed.

Molecular Hydrogen Emission from Protoplanetary Disks: Effects of X-ray Irradiation and Dust Evolution

Detailed models for the density and temperature profiles of gas and dust in protoplanetary disks are constructed by taking into account X-ray and UV irradiation from a central T Tauri star, as well as dust size growth and settling toward the disk midplane. The spatial and size distributions of dust grains are numerically computed by solving the coagulation equation for settling dust particles, with the result that the mass and total surface area of dust grains per unit volume of the gas in the disks are very small, except at the midplane. The H2 level populations and line emission are calculated using the derived physical structure of the disks. X-ray irradiation is the dominant heating source of the gas in the inner disk and in the surface layer, while the UV heating dominates otherwise. If the central star has strong X-ray and weak UV radiation, the H2 level populations are controlled by X-ray pumping, and the X-rayinduced transition lines could be observable. If the UV irradiation is strong, the level populations are controlled by thermal collisions or UV pumping, depending on the dust properties. As the dust particles evolve in the disks, the gas temperature at the disk surface drops because the grain photoelectric heating becomes less efficient. This makes the level populations change from LTE to non-LTE distributions, which results in changes to the line ratios. Our results suggest that dust evolution in protoplanetary disks could be observable through the H2 line ratios. The emission lines are strong from disks irradiated by strong UV and X-rays and possessing small dust grains; such disks will be good targets in which to observe H2 emission.

Hydrocarbon Anions in Interstellar Clouds and Circumstellar Envelopes

The recent detection of the hydrocarbon anion C$_6$H$^-$ in the interstellar medium has led us to investigate the synthesis of hydrocarbon anions in a variety of interstellar and circumstellar environments. We find that the anion/neutral abundance ratio can be quite large, on the order of at least a few percent, once the neutral has more than five carbon atoms. Detailed modeling shows that the column densities of C$_6$H$^-$ observed in IRC+10216 and TMC-1 can be reproduced. Our calculations also predict that other hydrocarbon anions, such as C$_{4}$H$^{-}$ and C$_8$H$^-$, are viable candidates for detection in IRC+10216, TMC-1 and photon-dominated regions such as the Horsehead Nebula.

Determination of the degree of dissociation in an inductively coupled hydrogen plasma using optical emission spectroscopy and laser diagnostics

Gas temperature is of major importance in plasma based surface treatment, since the surface processes are strongly temperature sensitive. The spatial distribution of reactive species responsible for surface modification is also influenced by the gas temperature. Industrial applications of RF plasma reactors require a high degree of homogeneity of the plasma in contact with the substrate. Reliable measurements of spatially resolved gas temperatures are, therefore, of great importance. The gas temperature can be obtained, e.g. by optical emission spectroscopy (OES). Common methods of OES to obtain gas temperatures from analysis of rotational distributions in excited states do not include the population dynamics influenced by cascading processes from higher electronic states. A model was developed to evaluate this effect on the apparent rotational temperature that is observed. Phase resolved OES confirmed the validity of this model. It was found that cascading leads to higher apparent temperatures, but the deviation (~25 K) is relatively small and can be ignored in most cases. This analysis is applied to investigate axially and radially resolved temperature profiles in an inductively coupled hydrogen RF discharge.

Energy analysis of hyperthermal hydrogen atoms generated through surface neutralisation of ions

Hydrogen ions (H+, H-2(+) and H-3(+)) are produced in a magnetically confined inductively coupled radio frequency plasma. Ions are accelerated in the plasma boundary sheath potential, of several hundred volts, in front of a biased metal electrode immersed in the plasma. Backscattered hyperthermal hydrogen atoms are investigated by optical emission spectroscopy and an energy-resolved mass spectrometer. Ionisation of fast neutrals through electron stripping of atoms in the plasma allows energy analysis of the resulting ions. Thereby, the energy distribution function of the hyperthermal atoms can be deduced. The energy spectra can be explained as a superposition of individual spectra of the various ion species. The measured spectra also shows contributions of negative ions created at the electrode surface. In addition to experimental measurements, simulations of the neutral flux of backscattered atoms are carried out.