UV-induced photodesorption of ice is a non-thermal evaporation process that can explain the presence of cold molecular gas in a range of interstellar regions. Information on the average UV photodesorption yield of astrophysically important ices exists for broadband UV lamp experiments. UV fields around low-mass pre-main sequence stars, around shocks and in many other astrophysical environments are however often dominated by discrete atomic and molecular emission lines. It is therefore crucial to consider the wavelength dependence of photodesorption yields and mechanisms. In this work, for the first time, the wavelength-dependent photodesorption of pure CO ice is explored between 90 and 170 nm. The experiments are performed under ultra high vacuum conditions using tunable synchrotron radiation. Ice photodesorption is simultaneously probed by infrared absorption spectroscopy in reflection mode of the ice and by quadrupole mass spectrometry of the gas phase. The experimental results for CO reveal a strong wavelength dependence directly linked to the vibronic transition strengths of CO ice, implying that photodesorption is induced by electronic transition (DIET). The observed dependence on the ice absorption spectra implies relatively low photodesorption yields at 121.6 nm (Lyman α), where CO barely absorbs, compared to the high yields found at wavelengths coinciding with transitions into the first electronic state of CO (A 1 Π at 150 nm); the CO photodesorption rates depend strongly on the UV profiles encountered in different star formation environments.

Wavelength dependent photodesorption rates have been determined using synchrotron radiation, for condensed pure and mixed methanol ice in the 7 -14 eV range. The VUV photodesorption of intact methanol molecules from pure methanol ices is found to be of the order of 10 −5 molecules/photon, that is two orders of magnitude below what is generally used in astrochemical models. This rate gets even lower (< 10 −6 molecules/photon) when the methanol is mixed with CO molecules in the ices. This is consistent with a picture in which photodissociation and recombination processes are at the origin of intact methanol desorption from pure CH 3 OH ices. Such low rates are explained by the fact that the overall photodesorption process is dominated by the desorption of the photofragments CO, CH 3 , OH, H 2 CO and CH 3 O/CH 2 OH, whose photodesorption rates are given in this study. Our results suggest that the role of the photodesorption as a mechanism to explain the observed gas phase abundances of methanol in cold media is probably overestimated. Nevertheless, the photodesorption of radicals from methanol-rich ices may stand at the origin of the gas phase presence of radicals such as CH 3 O, therefore opening new gas phase chemical routes for the formation of complex molecules.