Although several research groups have studied the formation of H2 on interstellar dust grains using surface science techniques, few have explored the formation of more complex molecules. A small number of these reactions produce molecules that remain on the surface of interstellar dust grains and, over time, lead to the formation of icy mantles. The most abundant of these species within the ice is H2O and is of particular interest as the observed molecular abundance cannot be accounted for using gas-phase chemistry alone. This article provides a brief introduction to the astronomical implications and motivations behind this research and the requirement for a new dual atomic beam ultrahigh vacuum (UHV) system. Further details of the apparatus design, characterisation, and calibration of the system are provided along with preliminary data from atomic O and O2 beam dosing on bare silica substrate and subsequent temperature programmed desorption measurements. The results obtained in this ongoing research may enable more chemically accurate surface formation mechanisms to be deduced for this and other species before simulating the kinetic data under interstellar conditions.
Reflection-absorption infrared spectroscopy is used to study the impact of low-energy electron irradiation of acetonitrile-containing ices, under conditions close to those in the dense star-forming regions in the interstellar medium. Both the incident electron energy and the surface coverage were varied. The experiments reveal that solid acetonitrile is desorbed from its ultrathin solid films with a cross section of the order of 10−17 cm2. Evidence is presented for a significantly larger desorption cross section for acetonitrile molecules at the water–ice interface, similar to that previously observed for the benzene–water system.
The LASSIE network is a consortium of 13 institutions and 7 commercial associates that brings together leading European researchers in observational, experimental and computational surface and solid state astrochemistry, with experts in public engagement and industrial partners developing relevant laboratory instrumentation and computational software. It is funded under the European Commission's Seventh Framework Programme as a Marie Curie Initial Training Network (ITN), and seeks to address the key issue of the interaction of the astronomical gas phase with the dust that pervades the Universe. It supports 28 early stage (postgraduate level) researcher and 4 experienced (first postdoctoral level) researcher positions, and provides for extensive training and outreach activities over a four year duration.
Warm cores (or hot corinos) around low-mass protostellar objects show a rich chemistry with strong spatial variations. This chemistry is generally attributed to the sublimation of icy mantles on dust grains initiated by the warming effect of the stellar radiation. We have used a model of the chemistry in warm cores in which the sublimation process is based on extensive laboratory data; these data indicate that sublimation from mixed ices occurs in several well-defined temperature bands. We have determined the position of these bands for the slow warming by a solar-mass star. The resulting chemistry is dominated by the sublimation process and by subsequent gas-phase reactions; strong spatial and temporal variations in certain molecular species are found to occur, and our results are, in general, consistent with observational results for the well-studied source IRAS 16293-2422. The model used is similar to one that describes the chemistry of hot cores. We infer that the chemistry of both hot cores and warm cores may be described by the same model (suitably adjusted for different physical parameters).
The adsorption and desorption of CO on and from amorphous H2O ice at astrophysically relevant temperatures has been studied using temperature programmed desorption (TPD) and reflection-absorption infrared spectroscopy (RAIRS). Solid CO is able to diffuse into the porous structure of H2O at temperatures as low as 15 K. When heated, a phase transition between two forms of amorphous H2O ice occurs over the 30-70 K temperature range, causing the partial collapse of pores and the entrapment of CO. Trapped CO is released during crystallization and desorption of the H2O film. This behavior may have a significant impact on both gas-phase and solid-phase chemistry in a variety of interstellar environments.
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.
The kinetic energy of benzene and water molecules photodesorbed from astrophysically relevant ices on a sapphire substrate under irradiation by a UV laser tuned to the S1←S0 π→π* transition of benzene has been measured using time-of-flight mass spectrometry. Three distinct photodesorption mechanisms have been identified—a direct adsorbate-mediated desorption of benzene, an indirect adsorbate-mediated desorption of water, and a substrate-mediated desorption of both benzene and water. The translational temperature of each desorbing population was well in excess of the ambient temperature of the ice matrix.
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