Infrared photoprocessing of porous amorphous solid water with a free electron laser

Abstract: Water ice is the most abundant ice in the interstellar medium (ISM). Previous studies on porous amorphous solid water (pASW) have shown that the infrared radiation field in the ISM modeled with infrared free electron laser (FEL) irradiation can result in changes in the ice towards a more ordered structure, characterized by a change in the OH-stretching vibration band. This paper aims to study the restructuring in more detail by varying the irradiation intensity and irradiation time for irradiations on-resonance with the OH-stretching, bending and libration modes. In addition, desorption of H2O is monitored during the irradiations. The research presented in this paper considers 42 infrared FEL irradiations on pASW samples deposited at two different rates, using the infrared FELs of the HFML-FELIX laboratory. Restructuring is studied using reflection absorption infrared (RAIR) spectroscopy, with a mass spectrometer monitoring the desorption of H2O in an ultra-high vacuum system. Desorption and restructuring occur in parallel, with the strongest effects observed for irradiation on-resonance with the OH-stretching vibration. Both processes exhibit two distinct regimes: an initial strong restructuring and desorption, characterized by an exponential decrease in the intensity of the desorption peaks within the first 5 s of irradiation, followed by a second regime of less efficient, yet continued restructuring and constant desorption in an extended area, involving energy dissipation through the hydrogen-bonding network. The trends in restructuring and desorption, depending on the absorbed energy during irradiation, are significantly different, suggesting separate processes. The astrophysical relevance of in particular the second regime of constant desorption and restructuring is discussed.