Rotranslational dynamics of confined water. II. Spectroscopic evidence of confinement effects on the far-infrared spectra of water isotopologues in argon and krypton matrices.

Water molecules trapped in rare gas matrices exhibit conspicuous shifts in their far-infrared (FIR), rotranslational spectral features compared with the corresponding transitions observed in the gas phase. These confinement-induced perturbations have been related not only to the quantization of translational motion but also to the coupling between the orientational and positional degrees of freedom: the rotation-translation coupling (RTC). As the propensity displayed by the nuclear spin isomers (NSI) of water to undergo interconversion in confinement is intimately related to how its nuclear spin degrees of freedom are coupled with those for intra- and intermolecular motions, confinement-induced RTC should also strongly impact the NSI interconversion mechanisms and rates. Insight into the rotranslational dynamics for H2 16O, H2 17O, and H2 18O, confined in argon and krypton matrices, is provided here based on the evolution of rotranslational spectra induced by NSI interconversion while a definitive assignment is provided from the transition energies and intensities calculated using the confined rotor model [Paper I, Wespiser et al., J. Chem. Phys. 156, 074304 (2021)]. In order to build a complete rotranslational energy diagram of confined water, which is fundamental to understand the NSI interconversion rates, the energy difference between the ground ortho and para rotranslational states is derived from the temperature dependence of the intensity ratio of mid-infrared lines emerging from these states. These investigations should provide deeper insight of the factors that control NSI interconversion of water isotopologues under extreme confinement.

X-Ray induced desorption and photochemistry in CO ice.

We report an investigation of X-ray induced desorption of neutrals, cations and anions from CO ice. The desorption of neutral CO, by far the most abundant, is quantified and discussed within the context of its application to astrochemistry. The desorption of many different cations, including large cations up to the mass limit of the spectrometer, is observed. In contrast, the only desorbing anions detected are O- and C-. The desorption mechanisms of all these species are discussed with the aid of their photodesorption spectrum. The evolution of the X-ray absorption spectrum shows significant chemical modifications of the ice upon irradiation, which along with the desorption of large cations gives a new insight into X-ray induced photochemistry in CO ice.

Desorption of neutrals, cations, and anions from core-excited amorphous solid water.

Core-excitation of water ice releases many different molecules and ions in the gas phase. Studying these desorbed species and the underlying desorption mechanisms can provide useful information on the effects of x-ray irradiation in ice. We report a detailed study of the x-ray induced desorption of a number of neutral, cationic, and anionic species from amorphous solid water. We discuss the desorption mechanisms and the relative contributions of Auger and secondary electrons (x-ray induced electron stimulated desorption) and initial excitation (direct desorption) as well as the role of photochemistry. Anions are shown to desorb not just through processes linked with secondary electrons but also through direct dissociation of the core-excited molecule. The desorption spectra of oxygen ions (O+, OH+, H2O+, O-, and OH-) give a new perspective on their previously reported very low desorption yields for most types of irradiations of water, showing that they mostly originate from the dissociation of photoproducts such as H2O2.