A systematic mid-infrared spectroscopic study of thermally processed H2S ices.

The positive identification of the molecular components of interstellar icy grain mantles is critically reliant upon the availability of laboratory-generated mid-infrared absorption spectra which can be compared against data acquired by ground- and space-borne telescopes. However, one molecule which remains thus far undetected in interstellar ices is H2S, despite its important roles in astrochemical and geophysical processes. Such a lack of a detection is surprising, particularly in light of its relative abundance in cometary ices which are believed to be the most pristine remnants of pre-solar interstellar ices available for study. In this paper, we present the results of an extensive and quantitative mid-infrared spectroscopic characterisation of H2S ices deposited at 20, 40, and 70 K and thermally processed to sublimation in an ultrahigh-vacuum system. We anticipate our results to be useful in confirming the detection of interstellar H2S ice using high-resolution and high-sensitivity instruments such as the James Webb Space Telescope, as well as in the identification of solid H2S in icy environments in the outer Solar System, such as comets and moons.

A systematic mid-infrared spectroscopic study of thermally processed SO2 ices.

The use of mid-infrared spectroscopy to characterise the chemistry of icy interstellar and Solar System environments will be exploited in the near future to better understand the chemical processes and molecular inventories in various astronomical environments. This is, in part, due to observational work made possible by the recently launched James Webb Space Telescope as well as forthcoming missions to the outer Solar System that will observe in the mid-infrared spectroscopic region (e.g., the Jupiter Icy Moons Explorer and the Europa Clipper missions). However, such spectroscopic characterisations are crucially reliant upon the generation of laboratory data for comparative purposes. In this paper, we present an extensive mid-infrared characterisation of SO2 ice condensed at several cryogenic temperatures between 20 and 100 K and thermally annealed to sublimation in an ultrahigh-vacuum system. Our results are anticipated to be useful in confirming the detection (and possibly thermal history) of SO2 on various Solar System bodies, such as Ceres and the icy Galilean moons of Jupiter, as well as in interstellar icy grain mantles.

Energetic electron irradiations of amorphous and crystalline sulphur-bearing astrochemical ices.

Laboratory experiments have confirmed that the radiolytic decay rate of astrochemical ice analogues is dependent upon the solid phase of the target ice, with some crystalline molecular ices being more radio-resistant than their amorphous counterparts. The degree of radio-resistance exhibited by crystalline ice phases is dependent upon the nature, strength, and extent of the intermolecular interactions that characterise their solid structure. For example, it has been shown that crystalline CH3OH decays at a significantly slower rate when irradiated by 2 keV electrons at 20 K than does the amorphous phase due to the stabilising effect imparted by the presence of an extensive array of strong hydrogen bonds. These results have important consequences for the astrochemistry of interstellar ices and outer Solar System bodies, as they imply that the chemical products arising from the irradiation of amorphous ices (which may include prebiotic molecules relevant to biology) should be more abundant than those arising from similar irradiations of crystalline phases. In this present study, we have extended our work on this subject by performing comparative energetic electron irradiations of the amorphous and crystalline phases of the sulphur-bearing molecules H2S and SO2 at 20 K. We have found evidence for phase-dependent chemistry in both these species, with the radiation-induced exponential decay of amorphous H2S being more rapid than that of the crystalline phase, similar to the effect that has been previously observed for CH3OH. For SO2, two fluence regimes are apparent: a low-fluence regime in which the crystalline ice exhibits a rapid exponential decay while the amorphous ice possibly resists decay, and a high-fluence regime in which both phases undergo slow exponential-like decays. We have discussed our results in the contexts of interstellar and Solar System ice astrochemistry and the formation of sulphur allotropes and residues in these settings.

Ozone production in electron irradiated CO2:O2 ices.

The detection of ozone (O3) in the surface ices of Ganymede, Jupiter's largest moon, and of the Saturnian moons Rhea and Dione, has motivated several studies on the route of formation of this species. Previous studies have successfully quantified trends in the production of O3 as a result of the irradiation of pure molecular ices using ultraviolet photons and charged particles (i.e., ions and electrons), such as the abundances of O3 formed after irradiation at different temperatures or using different charged particles. In this study, we extend such results by quantifying the abundance of O3 as a result of the 1 keV electron irradiation of a series of 14 stoichiometrically distinct CO2:O2 astrophysical ice analogues at 20 K. By using mid-infrared spectroscopy as our primary analytical tool, we have also been able to perform a spectral analysis of the asymmetric stretching mode of solid O3 and the variation in its observed shape and profile among the investigated ice mixtures. Our results are important in the context of better understanding the surface composition and chemistry of icy outer Solar System objects, and may thus be of use to future interplanetary space missions such as the ESA Jupiter Icy Moons Explorer and the NASA Europa Clipper missions, as well as the recently launched NASA James Webb Space Telescope.

Vacuum ultraviolet photoabsorption spectra of icy isoprene and its oligomers.

Isoprene and its oligomers, terpenes, are expected to be present, along with other complex organic molecules in the diverse environments of the ISM and in our solar system. Due to insufficient spectral information of these molecules at low temperature, detection and understanding the importance of these molecules has been rather incomplete. For this purpose, we have carried out the vacuum ultraviolet (VUV) photoabsorption measurements on pure molecular ices of isoprene and a few simple terpenes: limonene, α-pinene and ß-pinene by forming icy mantles on cold dust analogs. From these experiments, we report the first low temperature (10 K) VUV spectra of isoprene and its oligomers limonene, α-pinene and ß-pinene. VUV photoabsorption spectra of all the molecules reported here reveal similarities in the ice and gas phase as expected, with an exception of isoprene where a prominent red shift is observed in the ice phase absorption. This unqiue property of isoprene along with distinctive absorption at longer wavelengths supports its candidature for detection on icy bodies.

Infrared attenuation due to phase change from amorphous to crystalline observed in astrochemical propargyl ether ices.

Astrochemical ices are known to undergo morphological changes, from amorphous to crystalline, upon warming the ice from lower (10 K) to higher temperatures. Phase changes are mostly identified by the observation of significant changes in the InfraRed (IR) spectrum, where the IR bands that are broad in the amorphous phase are narrower and split when the ice turns crystalline. To-date all the molecules that are studied under astrochemical conditions are observed to follow such a behaviour without significant attenuation in the IR wavelength. However, in this paper we report a new observation when propargyl ether (C3H3OC3H3) is warmed from the amorphous phase, at 10 K, through the phase transition temperature of 170 K, the crystalline ice being found to strongly attenuate IR photons at the mid-IR wavelengths.

Residue from vacuum ultraviolet irradiation of benzene ices: Insights into the physical structure of astrophysical dust.

We have irradiated benzene ices deposited at 4 K on a cold, interstellar dust analog with vacuum ultraviolet (9 eV) irradiation for periods lasting from several hours to nearly a day, after which the irradiated ice was warmed to room temperature. Vacuum ultraviolet photoabsorption spectra of the aromatic residue left at room temperature were recorded and showed the synthesis of benzene derivatives. The residue was also imaged using an electron microscope and revealed crystals of various sizes and shapes. The result of our experiments suggests such geometrically shaped dust particles may be a key component of interstellar dust.