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Abstract

Carbon 1s excitation of methane, CH₄, has been studied in the gas phase using the ion trap integrated with the photon–ion instrument at PETRA III/DESY and soft X-rays from the beamline P04. The created photoions are stored within the ion trap so that in further steps the photoions can undergo reactions with neutral methane molecules. The ionic photoproducts as well as reaction products created thereby are mass-over-charge analyzed by an ion time-of-flight spectrometer. Besides the photoions, product ions with up to three carbon atoms are found. In contrast to experiments using vacuum ultraviolet radiation, especially highly reactive product ions with a small number of hydrogen atoms such as C₂H₂⁺ and C₂H₃⁺ are found, which are important precursors for larger hydrocarbons such as C₆H₆. Possible production routes of the product ions are analyzed on the basis of a model that considers the probabilities for photofragmentation and the first subsequent chemical reaction step. The model indicates that the high degree of fragmentation by photons with energies around 280 eV is favoring these products. The results of the measurements show that the products like C₂H₂⁺ and C₂H₃⁺ can be generated by a single collision of the ionization product with neutral methane. The results suggest that soft X-rays might be important for chemical reactions in planetary atmospheres, which has usually not been taken into account. However, due to the high degree of fragmentation and large cross sections involved, they can have a large influence even when the corresponding photon flux is rather small.