No Arabic abstract
Context. Icy dust grains play an important role in the formation of complex inter- and circumstellar molecules. Observational studies show that polycyclic aromatic hydrocarbons (PAHs) are abundantly present in the ISM in the gas phase. It is likely that these non-volatile species freeze out onto dust grains as well and participate in the astrochemical solid-state network, but experimental PAH ice studies are largely lacking. Methods. Near UV/VIS spectroscopy is used to track the in situ VUV driven photochemistry of pyrene containing ices at temperatures ranging from 10 to 125 K. Results. The main photoproducts of VUV photolyzed pyrene ices are spectroscopically identified and their band positions are listed for two host ices, water and CO. Pyrene ionisation is found to be most efficient in water ices at low temperatures. The reaction products, triplet pyrene and the 1-hydro-1-pyrenyl radical are most efficiently formed in higher temperature water ices and in low temperature CO ice. Formation routes and band strength information of the identified species are discussed. Additionally, the oscillator strengths of Py, Py^+ and PyH are derived and a quantitative kinetic analysis is performed by fitting a chemical reaction network to the experimental data. Conclusions. Pyrene is efficiently ionised in water ice at temperatures below 50 K. Hydrogenation reactions dominate the chemistry in low temperature CO ice with trace amounts of water. The results are put in an astrophysical context by determining the importance of PAH ionisation in a molecular cloud. The photoprocessing of a sample PAH in ice described in this manuscript indicates that PAH photoprocessing in the solid state should also be taken into account in astrochemical models.
Whether ice in cold cosmic environments is physically separated from the silicate dust or mixed with individual silicate moieties is not known. However, different grain models give very different compositions and temperatures of grains. The aim of the present study is a comparison of the mid-IR spectra of laboratory silicate-grains/water-ice mixtures with astronomical observations to evaluate the presence of dust/ice mixtures in interstellar and circumstellar environments. The laboratory data can explain the observations assuming reasonable mass-averaged temperatures for the protostellar envelopes and protoplanetary disks demonstrating that a substantial fraction of water ice may be mixed with silicate grains. Based on the combination of laboratory data and infrared observations, we provide evidence of the presence of solid-state water in the diffuse interstellar medium. Our results have implications for future laboratory studies trying to investigate cosmic dust grain analogues and for future observations trying to identify the structure, composition, and temperature of grains in different astrophysical environments.
Under cosmic irradiation, the interstellar water ice mantles evolve towards a compact amorphous state. Crystalline ice amorphisation was previously monitored mainly in the keV to hundreds of keV ion energies. We experimentally investigate heavy ion irradiation amorphisation of crystalline ice, at high energies closer to true cosmic rays, and explore the water-ice sputtering yield. We irradiated thin crystalline ice films with MeV to GeV swift ion beams, produced at the GANIL accelerator. The ice infrared spectral evolution as a function of fluence is monitored with in-situ infrared spectroscopy (induced amorphisation of the initial crystalline state into a compact amorphous phase). The crystalline ice amorphisation cross-section is measured in the high electronic stopping-power range for different temperatures. At large fluence, the ice sputtering is measured on the infrared spectra, and the fitted sputtering-yield dependence, combined with previous measurements, is quadratic over three decades of electronic stopping power. The final state of cosmic ray irradiation for porous amorphous and crystalline ice, as monitored by infrared spectroscopy, is the same, but with a large difference in cross-section, hence in time scale in an astrophysical context. The cosmic ray water-ice sputtering rates compete with the UV photodesorption yields reported in the literature. The prevalence of direct cosmic ray sputtering over cosmic-ray induced photons photodesorption may be particularly true for ices strongly bonded to the ice mantles surfaces, such as hydrogen-bonded ice structures or more generally the so-called polar ices.
Several experimental and theoretical studies report instances of concerted or correlated multiple proton tunneling in solid phases of water. Here, we construct a pseudo-spin model for the quantum motion of protons in a hexameric H$_2$O ring and extend it to open system dynamics that takes environmental effects into account in the form of O$-$H stretch vibrations. We approach the problem of correlations in tunneling using quantum information theory in a departure from previous studies. Our formalism enables us to quantify the coherent proton mobility around the hexagonal ring by one of the principal measures of coherence, the $l_1$ norm of coherence. The nature of the pairwise pseudo-spin correlations underlying the overall mobility is further investigated within this formalism. We show that the classical correlations of the individual quantum tunneling events in long-time limit is sufficient to capture the behaviour of coherent proton mobility observed in low-temperature experiments. We conclude that long-range intra-ring interactions do not appear to be a necessary condition for correlated proton tunneling in water ice.
Identifying the source of Earths water is central to understanding the origins of life-fostering environments and to assessing the prevalence of such environments in space. Water throughout the solar system exhibits deuterium-to-hydrogen enrichments, a fossil relic of low-temperature, ion-derived chemistry within either (i) the parent molecular cloud or (ii) the solar nebula protoplanetary disk. Utilizing a comprehensive treatment of disk ionization, we find that ion-driven deuterium pathways are inefficient, curtailing the disks deuterated water formation and its viability as the sole source for the solar systems water. This finding implies that if the solar systems formation was typical, abundant interstellar ices are available to all nascent planetary systems.
The interstellar medium is characterized by a rich and diverse chemistry. Many of its complex organic molecules are proposed to form through radical chemistry in icy grain mantles. Radicals form readily when interstellar ices (composed of water and other volatiles) are exposed to UV photons and other sources of dissociative radiation, and, if sufficiently mobile, the radicals can react to form larger, more complex molecules. The resulting complex organic molecules (COMs) accompany star and planet formation, and may eventually seed the origins of life on nascent planets. Experiments of increasing sophistication have demonstrated that known interstellar COMs as well as the prebiotically interesting amino acids can form through ice photochemistry. We review these experiments and discuss the qualitative and quantitative kinetic and mechanistic constraints they have provided. We finally compare the effects of UV radiation with those of three other potential sources of radical production and chemistry in interstellar ices: electrons, ions and X-rays.