Laboratory evidence for the formation of hydrogenated fullerene molecules.

Experimental evidence for the formation of hydrogenated fullerene molecules is presented. Films of C60 were grown on a highly oriented pyrolytic graphite (substrate) and exposed to a beam of deuterium atoms. Thermal desorption combined with mass spectrometry was used to determine the deuterated fullerene products formed, revealing a maximum degree of deuteration corresponding to C60D36. Release of D2 from the deuterated C60 film occurs at a much higher temperature than for D-saturated graphite.

Deuteration of C60 on a highly oriented pyrolytic graphite surface.

Reactions on carbonaceous surfaces play an important role in processes such as H2 formation in the interstellar medium. We have investigated the adsorption of C60 molecules on a highly oriented pyrolytic graphite (HOPG) surface and then exposed them to a beam of deuterium atoms in order to investigate the formation of deuterated fullerenes. Scanning tunneling microscopy (STM) was used to probe the adsorbed molecules and their deuteration. Deuteration of C60 films results in increased thermal stability of the film, relative to films of pristine C60, along with an evolution towards higher deuterated species. The STM data provide confirmatory evidence for the formation of deuterated fullerene species.

XUV photodesorption of carbon cluster ions and ionic photofragments from a mixed methane-water ice.

The photochemical processing of a CH4 : D2O 1 : 3.3 ice mixture adsorbed on an HOPG surface in the XUV regime was investigated using pulses obtained from the Free-electron LASer in Hamburg (FLASH) facility. Ice films were exposed to femtosecond pulses with a photon energy of hν = 40.8 eV, consistent with the HeII resonance line. Cationic species desorbing directly from the ice films were detected using time-of-flight (ToF) mass spectrometry. Simple ions formed through the fragmentation of the parent molecules and subsequent recombination reactions were detected and are consistent with efficient D+ and H+ ejection from the parent species, similar to the case for low energy electron irradiation. The FEL fluence dependencies of these ions are linear or exhibit a non-linear order of up to 3. In addition, a series of Cn+ cluster ions (with n up to 12) were also identified. These ions display a highly non-linear desorption yield with respect to the FEL fluence, having an order of 6-10, suggesting a complex multi-step process involving the primary products of CH4 fragmentation. Two-pulse correlation measurements were performed to gain further insight into the underlying reaction dynamics of the photo-chemical reactions. The yield of the D2O derived products displayed a different temporal behaviour with respect to the Cn+ ions, indicating the presence of very different reaction pathways to the two families of ionic products.

Polycyclic aromatic hydrocarbons--catalysts for molecular hydrogen formation.

Polycyclic aromatic hydrocarbons (PAHs) have been shown to catalyse molecular hydrogen formation. The process occurs via atomic hydrogen addition reactions leading to the formation of super-hydrogenated PAH species, followed by molecular hydrogen forming abstraction reactions. Here, we combine quadrupole mass spectrometry data with kinetic simulations to follow the addition of deuterium atoms to the PAH molecule coronene. When exposed to sufficiently large D atom fluences, coronene is observed to be driven towards the completely deuterated state (C24D36) with the mass distribution peaking at 358 amu, just below the peak mass of 360 amu. Kinetic models reproduce the experimental observations for an abstraction cross-section of sigma(abs) = 0.01 angstroms2 per excess H/D atom, and addition cross-sections in the range of sigma(add) = 0.55-2.0 angstroms2 for all degrees of hydrogenation. These findings indicate that the cross-section for addition does not scale with the number of sites available for addition on the molecule, but rather has a fairly constant value over a large interval of super-hydrogenation levels.

Laboratory studies of electron and ion irradiation of solid acetonitrile (CH3CN).

The structure and bonding of solid acetonitrile (CH3CN) films on amorphous silica are studied, and chemical and physical processes under irradiation with 200 keV protons and 250-400 eV electrons are quantified using transmission infrared spectroscopy, reflection-absorption infrared spectroscopy and temperature-programmed desorption, with the assistance of basic computational chemistry and nuclear materials calculations. The thermal desorption profiles are found to depend strongly on the balance between CH3CN-surface and CH3CN-CH3CN interactions, passing from a sub-monolayer regime (binding energy: 35-50 kJ mol⁻¹) to a multilayer regime (binding energy: 38.2±1.0 kJ mol⁻¹) via a fractional order desorption regime characteristic of islanding as the coverage increases. Calculations using the SRIM code reveal that the effects of the ion irradiation are dominated by electronic stopping of incident protons, and the subsequent generation of secondary electrons. Therefore, ion irradiation and electron irradiation experiments can be quantitatively compared. During ion irradiation of thicker CH3CN films, a cross section for secondary electron-promoted chemical destruction of CH3CN of 4 (±1) × 10⁻¹8 cm² was measured, while electron-promoted desorption was not detected. A significantly higher cross section for electron-promoted desorption of 0.82-3.2 × 10⁻¹5 cm² was measured during electron irradiation of thinner CH3CN films, while no chemical products were detected. The differences between the experimental results can be rationalized by recognizing that chemical reaction is a bulk effect in the CH3CN film, whereas desorption is a surface sensitive process. In thicker films, electron-promoted desorption is expected to occur a rate that is independent of the film thickness; i.e. show zeroth-order kinetics with respect to the surface concentration.

Thermal desorption of C6H6 from surfaces of astrophysical relevance.

The thermal desorption of C(6)H(6) from two astrophysically relevant surfaces has been studied using temperature programmed desorption. Desorption from an amorphous SiO(2) substrate was used as a mimic for bare interstellar grains, while multilayer films of amorphous solid water (ASW) were used to study the adsorption of C(6)H(6) on grains surrounded by H(2)O dominated icy mantles. Kinetic parameters were obtained through a combination of kinetic modeling, leading edge analysis, and by considering a distribution of binding sites on the substrate. The latter is shown to have a significant impact on the desorption of small exposures of C(6)H(6) from the amorphous SiO(2) substrate. In the case of adsorption on ASW, dewetting behavior and fractional order desorption at low coverage strongly suggest the formation of islands of C(6)H(6) on the H(2)O surface. The astrophysical implications of these observations are briefly outlined.

Meteorite nanoparticles as models for interstellar grains: synthesis and preliminary characterisation.

Dust particles and their interaction with gases play important roles in star formation and in solar nebulae. Appropriate model dust grains are needed for the laboratory simulation of gas-grain interactions. Nanoparticles formed from carbonaceous meteorites may be particularly suitable, as these particles are formed from materials that were formed originally from interstellar/nebula dust. Extending our previous studies with grounded meteorite powders, we demonstrate here the production of nanoparticles formed from meteorites using the laser desorption/controlled condensation method developed in our laboratory. The product nanoparticle aggregates have porous, web-like morphologies similar to interstellar dust grains, indicating that they can present large specific surface areas for gas/grain interactions. In this paper, we present polarisation modulation reflection-absorption infrared spectra (PM-RAIRS) of supported thin films and compare these spectra with the known silicate bands in the spectra of interstellar dust recorded during the ISO mission. We also report an ultrahigh vacuum (UHV) temperature programmed desorption (TPD) study of the adsorption of CO on the supported nanoparticle films. The latter allow us to estimate the CO binding energy on the meteorite nanoparticles as 13.5 +/- 3.0 kJ mol(-1), cf. a value of 9.8 +/- 0.2 kJ mol(-1) for CO binding to a water ice substrate. Such thermochemical data can be useful for computational modelling of gas-grain interactions under the diverse conditions in interstellar clouds and solar nebulae.