摘要：Context.In dense clouds, hydrogenation reactions on icy dust grains are key in the formation of molecules, like formaldehyde, methanol, and complex organic molecules (COMs). These species form through the sequential hydrogenation of CO ice. Although molecular hydrogen (H2) abundances can be four orders of magnitude higher than those of free H-atoms in dense clouds, H2surface chemistry has been largely ignored; several laboratory studies show that H2does not actively participate in “non-energetic” ice chemistry because of the high activation energies required.Aims.For the example of CO ice hydrogenation, we experimentally investigated the potential role of H2molecules on the surface chemistry when energetic processing (i.e., UV photolysis) is involved. We test whether additional hydrogenation pathways become available upon UV irradiation of a CO:H2ice mixture and whether this reaction mechanism also applies to other chemical systems.Methods.Ultra-high vacuum (UHV) experiments were performed at 8–20 K. A pre-deposited solid mixture of CO:H2was irradiated with UV-photons. Reflection absorption infrared spectroscopy (RAIRS) was used as an in situ diagnostic tool. Single reaction steps and possible isotopic effects were studied by comparing results from CO:H2and CO:D2ice mixtures.Results.After UV-irradiation of a CO:H2ice mixture, two photon-induced products, HCO and H2CO, are unambiguously detected. The proposed reaction mechanism involves electronically excited CO in the following reaction steps: CO + hν→CO*, CO*+ H2→HCO + H where newly formed H-atoms are then available for further hydrogenation reactions. The HCO formation yields have a strong temperature dependence for the investigated regime, which is most likely linked to the H2sticking coefficient. Moreover, the derived formation cross section reflects a cumulative reaction rate that mainly determined by both the H-atom diffusion rate and initial concentration of H2at 8–20 K and that is largely determined by the H2sticking coefficient. Finally, the astronomical relevance of this photo-induced reaction channel is discussed.
