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CO 2 is a major component of the icy mantles surrounding dust grains in planet and star formation regions. Understanding its photodesorption is crucial for explaining gas phase abundances in the coldest environments of the interstellar medium irradiated by vacuum-UV (VUV) photons. Photodesorption yields determined experimentally from CO 2 samples grown at low temperatures ( T = 15 K) have been found to be very sensitive to experimental methods and conditions. Several mechanisms have been suggested for explaining the desorption of CO 2 , O 2 and CO from CO 2 ices. In the present study, the cross-sections characterizing the dynamics of photodesorption as a function of photon fluence (determined from released molecules in the gas phase) and of ice composition modification (determined in situ in the solid phase) are compared for the first time for different photon flux conditions (from 7.3 × 10 12 photon per s cm -2 to 2.2× 10 14 photon per s cm -2 ) using monochromatic synchrotron radiation in the VUV range (on the DESIRS beamline at SOLEIL). This approach reveals that CO and O 2 desorptions are decorrelated from that of CO 2 . CO and O 2 photodesorption yields depend on photon flux conditions and can be linked to surface chemistry. In contrast, the photodesorption yield of CO 2 is independent of the photon flux conditions and can be linked to bulk ice chemical modification, consistently with indirect desorption induced by an electronic transition (DIET) process.

Being a potential process that could explain gas phase abundances of so-called complex organic molecules (COMs) in the cold interstellar medium (ISM), the UV photon-induced desorption from organics-containing molecular ices has been experimentally studied. In this work, we focused on the observation of the photodesorbed products and the measurement of the associated photodesorption yields from pure and mixed molecular ices, each containing organic molecules whose detection has been achieved in the gas phase of the cold ISM, namely formic acid HCOOH and methyl formate HCOOCH 3 . Each molecule, in pure ice or in ice mixed with CO or water, was irradiated at 15 K with monochromatic vacuum UV photons in the 7-14 eV range using synchrotron radiation from the SOLEIL synchrotron facility, DESIRS beamline. Photodesorption yields of the intact molecules and of the photoproducts were derived as a function of the incident photon energy. Experiments have revealed that the desorbing species match the photodissociation pattern of each isolated molecule, with little influence of the kind of ice (pure or mixed in CO or H 2 O-rich environment). For both species, the photodesorption of the intact organics is found to be negligible in our experimental conditions, resulting in yields typically below 10 -5 ejected molecules per incident photon. The results obtained on HCOOH and HCOOCH 3 -containing ices are similar to what has already been found for methanol-containing ices, but contrast with the case of another complex molecule, CH 3 CN, photodesorption of which has been recently studied. Such experimental results may be linked to the observation of COMs in protoplanetary disks, in which CH 3 CN is commonly observed whereas HCOOH or methanol are detected only in some sources, HCOOCH 3 not being detected at all.

X-Ray irradiation of interstellar ice analogues has recently been proven to induce desorption of molecules, thus being a potential source for the still-unexplained presence of gaseous organics in the coldest regions of the interstellar medium, especially in protoplanetary disks. The proposed desorption mechanism involves the Auger decay of excited molecules following soft X-ray absorption, known as X-ray induced electron-stimulated desorption (XESD). Aiming to quantify electron induced desorption in XESD, we irradiated pure methanol (CH 3 OH) ices at 23 K with 505 eV electrons, to simulate the Auger electrons originating from the O 1s core absorption. Desorption yields of neutral fragments and the effective methanol depletion cross-section were quantitatively determined by mass spectrometry. We derived desorption yields in molecules per incident electron for CO, CO 2 , CH 3 OH, CH 4 /O, H 2 O, H 2 CO, C 2 H 6 and other less abundant but more complex organic products. We obtained desorption yields remarkably similar to XESD values., (© 2023 The Authors. ChemPhysChem published by Wiley-VCH GmbH.)

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.

Confinement effects on the ro-translational (RT) dynamics of water, trapped in rare gas matrices or within endofullerenes (i.e., H 2 O@C 60 ), can be experimentally assessed using rotationally resolved far-infrared, or mid-infrared, spectroscopy [Putaud et al., J. Chem. Phys. 156, 074305 (2022) (Paper II)]. The confined rotor model is used here to reveal how the quantized rotational and frustrated translational energy levels of confined water interact and mix by way of the confinement-induced rotation-translation coupling (RTC). An eccentric but otherwise isotropic 3D harmonic effective potential is used to account for confinement effects, thereby allowing the dependence of the magnitude of the RTC on the topology of the model confinement potential, the resulting intricate mixing schemes, and their impact on the RT energy levels to be examined in detail. The confined rotor model thus provides a convenient framework to investigate the matrix and isotope effects on the RT dynamics of water under extreme confinement probed spectroscopically, thereby potentially providing insight into the mechanisms and rates for ortho-H 2 O ↔ para-H 2 O nuclear spin isomer interconversion in confined water.

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 H 2 16 O, H 2 17 O, and H 2 18 O, 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.

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.

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.

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 + , H 2 O + , 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 H 2 O 2 .

The infrared gas-phase absorption spectrum of methane was used to determine its Clapeyron solid-gas equilibrium curve in the 40-77 K temperature range. For comparative purposes and to obtain more reliable results, two different optical experimental setups were used. At higher temperatures (53-77 K), a single pass cryogenically cooled cell was coupled to a standard low-resolution Fourier transform infrared spectrometer. The second system was a state-of-the-art vertical-external-cavity surface-emitting laser tunable source operating at around 2.3 μm, combined with a 7 m path Herriott cell, to record methane absorption features down to 40 K. From the measurements, the vapor pressure curve ln( p/Pa) = -(1191.92 ± 8.92)/( T/K) + (22.49 ± 0.16) was derived in the range 40-77 K. This corresponds to a value of 9910 ± 75 J mol -1 for the sublimation enthalpy. The relation was validated down to 40 K, increasing our knowledge of the saturation pressure by 2 orders of magnitude. Data were compared with available pressure measurements from the literature, obtained by manometric or mass spectrometry techniques, and the sublimation enthalpy was compared with a thermodynamic approach based on heat capacity measurements in the solid and gas phases.

The photochemical processing of a CH 4  : D 2 O 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 C n + 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 CH 4 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 D 2 O derived products displayed a different temporal behaviour with respect to the C n + ions, indicating the presence of very different reaction pathways to the two families of ionic products.

We report the results of an experimental study related to the relaxation of the nuclear spin isomers of the water molecule in a supersonic expansion. Rovibrational lines of both ortho and para spin isomers were recorded in the spectral range of H 2 O stretching vibrations at around 3700 cm -1 using FTIR direct absorption. Water vapor seeded in argon, helium, or oxygen or in a mixture of oxygen and argon was expanded into vacuum through a slit nozzle. The water vapor partial pressure in the mixture varied over a wide range from 1.5 to 102.7 hPa, corresponding to a water molar fraction varying between 0.2 and 6.5%. Depending on expansion conditions, the effect of water vapor clustering was clearly seen in some of our measured spectra. The Boltzmann plot of the line intensities allowed the H 2 O rotational temperatures in the isentropic core and in the lateral shear layer probed zones of the planar expansion to be determined. The study of the OPR, i.e., the ratio of the ortho to para absorption line intensities as a function of T rot , did not reveal any signs of the OPR being relaxed to the sample temperature. In contrast, the OPR was always conserved according to the stagnation reservoir equilibrium temperature. The conservation of the OPR was found irrespective of whether water molecule clustering was pronounced or not. Also, no effect of the paramagnetic oxygen admixture enhancing OPR relaxation was observed.

The mechanism for interconversion between the nuclear spin isomers (NSI) of H 2 O remains shrouded in uncertainties. The temperature dependence displayed by NSI interconversion rates for H 2 O isolated in an argon matrix provides evidence that confinement effects are responsible for the dramatic increase in their kinetics with respect to the gas phase, providing new pathways for o-H 2 O↔p-H 2 O conversion in endohedral compounds. This reveals intramolecular aspects of the interconversion mechanism which may improve methodologies for the separation and storage of NSI en route to applications ranging from magnetic resonance spectroscopy and imaging to interpretations of spin temperatures in the interstellar medium.

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.

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.

Carbon monoxide is after H(2) the most abundant molecule identified in the interstellar medium (ISM), and is used as a major tracer for the gas phase physical conditions. Accreted at the surface of water-rich icy grains, CO is considered to be the starting point of a complex organic--presumably prebiotic--chemistry. Non-thermal desorption processes, and especially photodesorption by UV photons, are seen as the main cause that drives the gas-to-ice CO balance in the colder parts of the ISM. The process is known to be efficient and wavelength-dependent, but, the underlying mechanism and the physical-chemical parameters governing the photodesorption are still largely unknown. Using monochromatized photons from a synchrotron beamline, we reveal that the molecular mechanism responsible for CO photoejection is an indirect, (sub)surface-located process. The local environment of the molecules plays a key role in the photodesorption efficiency, and is quenched by at least an order of magnitude for CO interacting with a water ice surface.

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.