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.