Indirect x-ray photodesorption of N215 and CO13 from mixed and layered ices.

X-ray photodesorption yields of N215 and CO13 are derived as a function of the incident photon energy near the N (∼400 eV) and O K-edge (∼500 eV) for pure N215 ice and mixed CO13:N215 ices. The photodesorption spectra from the mixed ices reveal an indirect desorption mechanism for which the desorption of N215 and CO13 is triggered by the photoabsorption of CO13 and N215, respectively. This mechanism is confirmed by the x-ray photodesorption of CO13 from a layered CO13/N215 ice irradiated at 401 eV on the N 1s → π* transition of N215. This latter experiment enables us to quantify the relevant depth involved in the indirect desorption process, which is found to be 30-40 monolayers in that case. This value is further related to the energy transport of Auger electrons emitted from the photoabsorbing N215 molecules that scatter toward the ice surface, inducing the desorption of CO13. The photodesorption yields corrected from the energy that can participate in the desorption process (expressed in molecules desorbed by eV deposited) do not depend on the photon energy; hence, they depend neither on the photoabsorbing molecule nor on its state after Auger decay. This demonstrates that x-ray induced electron stimulated desorption, mediated by Auger scattering, is the dominant process explaining the desorption of N215 and CO13 from the ices studied in this work.

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.

Mechanism of Indirect Photon-Induced Desorption at the Water Ice Surface.

Electronic excitations near the surface of water ice lead to the desorption of adsorbed molecules, through a so far debated mechanism. A systematic study of photon-induced indirect desorption, revealed by the spectral dependence of the desorption (7-13 eV), is conducted for Ar, Kr, N_{2}, and CO adsorbed on H_{2}O or D_{2}O amorphous ices. The mass and isotopic dependence and the increase of intrinsic desorption efficiency with photon energy all point to a mechanism of desorption induced by collisions between adsorbates and energetic H/D atoms, produced by photodissociation of water. This constitutes a direct and unambiguous experimental demonstration of the mechanism of indirect desorption of weakly adsorbed species on water ice, and sheds new light on the possibility of this mechanism in other systems. It also has implications for the description of photon-induced desorption in astrochemical models.

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.

XUV photodesorption of carbon cluster ions and ionic photofragments from a mixed methane-water ice.

The photochemical processing of a CH4 : D2O 1 : 3.3 ice mixture adsorbed on an HOPG surface in the XUV regime was investigated using pulses obtained from the Free-electron LASer in Hamburg (FLASH) facility. Ice films were exposed to femtosecond pulses with a photon energy of hν = 40.8 eV, consistent with the HeII resonance line. Cationic species desorbing directly from the ice films were detected using time-of-flight (ToF) mass spectrometry. Simple ions formed through the fragmentation of the parent molecules and subsequent recombination reactions were detected and are consistent with efficient D+ and H+ ejection from the parent species, similar to the case for low energy electron irradiation. The FEL fluence dependencies of these ions are linear or exhibit a non-linear order of up to 3. In addition, a series of Cn+ cluster ions (with n up to 12) were also identified. These ions display a highly non-linear desorption yield with respect to the FEL fluence, having an order of 6-10, suggesting a complex multi-step process involving the primary products of CH4 fragmentation. Two-pulse correlation measurements were performed to gain further insight into the underlying reaction dynamics of the photo-chemical reactions. The yield of the D2O derived products displayed a different temporal behaviour with respect to the Cn+ ions, indicating the presence of very different reaction pathways to the two families of ionic products.

Adsorption energies and prefactor determination for CH3OH adsorption on graphite.

In this paper, we have studied adsorption and thermal desorption of methanol CH3OH on graphite surface, with the specific aim to derive from experimental data quantitative parameters that govern the desorption, namely, adsorption energy Eads and prefactor ν of the Polanyi-Wigner law. In low coverage regime, these two values are interconnected and usually the experiments can be reproduced with any couple (Eads, ν), which makes intercomparison between studies difficult since the results depend on the extraction method. Here, we use a method for determining independently the average adsorption energy and a prefactor value that works over a large range of incident methanol coverage, from a limited set of desorption curves performed at different heating rates. In the low coverage regime the procedure is based on a first order kinetic law, and considers an adsorption energy distribution which is not expected to vary with the applied heating rate. In the case of CH3OH multilayers, Eads is determined as 430 meV with a prefactor of 5 × 10(14) s(-1). For CH3OH submonolayers on graphite, adsorption energy of 470 ± 30 meV and a prefactor of (8 ± 3) × 10(16) s(-1) have been found. These last values, which do not change between 0.09 ML and 1 ML initial coverage, suggest that the methanol molecules form island-like structure on the graphite even at low coverage.

Wavelength resolved UV photodesorption and photochemistry of CO2 ice.

Over the last four years we have illustrated the potential of a novel wavelength-dependent approach in determining molecular processes at work in the photodesorption of interstellar ice analogs. This method, utilizing the unique beam characteristics of the vacuum UV beamline DESIRS at the French synchrotron facility SOLEIL has revealed an efficient indirect desorption mechanism that scales with the electronic excitations in molecular solids. This process, known as DIET--desorption induced by electronic transition--occurs efficiently in ices composed of very volatile species (CO, N2), for which photochemical processes can be neglected. In the present study, we investigate the photodesorption energy dependence of pure and pre-irradiated CO2 ices at 10-40 K and between 7 and 14 eV. The photodesorption from pure CO2 is limited to photon energies above 10.5 eV and is clearly initiated by CO2 excitation and by the contribution of dissociative and recombination channels. The photodesorption from "pre-irradiated" ices is shown to present an efficient additional desorption pathway below 10 eV, dominating the desorption depending on the UV-processing history of the ice film. This effect is identified as an indirect DIET process mediated by photoproduced CO, observed for the first time in the case of less volatile species. The results presented here pinpoint the importance of the interconnection between photodesorption and photochemical processes in interstellar ices driven by UV photons having different energies.

Nuclear spin conversion of molecular hydrogen on amorphous solid water in the presence of O2 traces.

Nuclear spin conversion (NSC) of ortho- to para-H(2) and para- to ortho-D(2) has been investigated on an amorphous solid water (ASW) surface at 10 K, in the presence of co-adsorbed O(2). The dynamics of the nuclear spin conversion could be revealed by combination of resonance enhanced multiphoton ionization spectroscopy (REMPI) with temperature programmed desorption (TPD) experiments. The conversion rates are consistent with a diffusion of molecular hydrogen inducing a nuclear spin conversion enhanced in the vicinity of molecular oxygen. The conversion times were found to increase with decreasing O(2) and H(2) coverage. Finally, on oxygen free ASW surface, the extremely long conversion characteristic times measured showed that such surface is not an efficient catalyst for NSC, in contradiction with hypothesis commonly made for interstellar medium.