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X-rays emitted from pre-main-sequence stars at the center of protoplanetary disks can induce nonthermal desorption from interstellar ices populating the cold regions. This X-ray photodesorption needs to be quantified for complex organic molecules (COMs), including acetonitrile CH3CN, which has been detected in several disks. We experimentally estimate the X-ray photodesorption yields of neutral species from pure CH3CN ices and from interstellar ice analogs for which CH3CN is mixed either in a CO- or H2O-dominated ice. The ices were irradiated at 15 K by soft X-rays (400-600 eV) from synchrotron light (SOLEIL synchrotron). X-ray photodesorption was probed in the gas phase via quadrupole mass spectrometry. X-ray photodesorption yields were derived from the mass signals and were extrapolated to higher X-ray energies for astrochemical models. X-ray photodesorption of the intact CH3CN is detected from pure CH3CN ices and from mixed 13CO:CH3CN ices, with a yield of about 5x10^(-4) molecules/photon at 560 eV. When mixed in H2O-dominated ices, X-ray photodesorption of the intact CH3CN at 560 eV is below its detection limit, which is 10^(-4) molecules/photon. Yields associated with the desorption of HCN, CH4 , and CH3 are also provided. The derived astrophysical yields significantly depend on the local conditions expected in protoplanetary disks. They vary from 10^(-4) to 10(-6) molecules/photon for the X-ray photodesorption of intact CH3CN from CO-dominated ices. Only upper limits varying from 5x10^(-5) to 5x10^(-7) molecules/photon could be derived for the X-ray photodesorption of intact CH3CN from H2O-dominated ices. X-ray photodesorption of intact CH3CN from interstellar ices might in part explain the abundances of CH3CN observed in protoplanetary disks. The desorption efficiency is expected to vary with the local physical conditions, hence with the disk region.

X-ray photodesorption yields of $^{15}$N$_2$ and $^{13}$CO are derived as a function of the incident photon energy near the N ($\sim$400 eV) and O K-edge ($\sim$500 eV) for pure $^{15}$N$_2$ ice and mixed $^{13}$CO:$^{15}$N$_2$ ices. The photodesorption spectra from the mixed ices reveal an indirect desorption mechanism for which the desorption of $^{15}$N$_2$ and $^{13}$CO is triggered by the photo-absorption of respectively $^{13}$CO and $^{15}$N$_2$. This mechanism is confirmed by the X-ray photodesorption of $^{13}$CO from a layered $^{13}$CO/$^{15}$N$_2$ ice irradiated at 401 eV, on the N 1s$\rightarrow \pi^*$ transition of $^{15}$N$_2$. This latter experiment enables to quantify the relevant depth involved in the indirect desorption process, which is found to be 30 - 40 ML in that case. This value is further related to the energy transport of Auger electrons emitted from the photo-absorbing $^{15}$N$_2$ molecules that scatter towards the ice surface, inducing the desorption of $^{13}$CO. The photodesorption yields corrected from the energy that can participate to the desorption process (expressed in molecules desorbed by eV deposited) do not depend on the photon energy hence neither on the photo-absorbing molecule nor on its state after Auger decay. This demonstrates that X-ray induced electron stimulated desorption (XESD), mediated by Auger scattering, is the dominant process explaining the desorption of $^{15}$N$_2$ and $^{13}$CO from the ices studied in this work.

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, are 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., Comment: Accepted in PCCP

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 to 13 eV), is conducted for Ar, Kr, N2, and CO adsorbed on H2O or D2O 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 or 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., Comment: Supplemental Material available freely at https://journals.aps.org/prl/supplemental/10.1103/PhysRevLett.126.156001

Astrophysical observations show complex organic molecules (COMs) in the gas phase of protoplanetary disks. X-rays emitted from the central young stellar object (YSO) that irradiate interstellar ices in the disk, followed by the ejection of molecules in the gas phase, are a possible route to explain the abundances observed in the cold regions. This process, known as X-ray photodesorption, needs to be quantified for methanol-containing ices. We aim at experimentally measuring X-ray photodesorption yields of methanol and its photo-products from binary mixed ices: $^{13}$CO:CH$_3$OH ice and H$_2$O:CH$_3$OH ice. We irradiated these ices at 15 K with X-rays in the 525 - 570 eV range. The release of species in the gas phase was monitored by quadrupole mass spectrometry, and photodesorption yields were derived. For $^{13}$CO:CH$_3$OH ice, CH$_3$OH X-ray photodesorption yield is estimated to be 10$^{-2}$ molecule/photon at 564 eV. X-ray photodesorption of larger COMs, which can be attributed to either ethanol, dimethyl ether, and/or formic acid, is detected with a yield of 10$^{-3}$ molecule/photon. When methanol is mixed with water, X-ray photodesorption of methanol and of the previous COMs is not detected. X-ray induced chemistry, dominated by low-energy secondary electrons, is found to be the main mechanism that explains these results. We also provide desorption yields that are applicable to protoplanetary disk environments for astrochemical models. The X-ray emission from YSOs should participate in the enrichment of the protoplanetary disk gas phase with COMs such as methanol in the cold and X-ray dominated regions because of X-ray photodesorption from methanol-containing ices., Comment: arXiv admin note: text overlap with arXiv:2101.06179

Astrophysical observations show complex organic molecules (COMs) in the gas phase of protoplanetary disks. X-rays emitted from the central young stellar object (YSO) that irradiate interstellar ices in the disk, followed by the ejection of molecules in the gas phase, are a possible route to explain the abundances observed in the cold regions. This process, known as X-ray photodesorption, needs to be quantified for methanol-containing ices. This paper I focuses on the case of X-ray photodesorption from pure methanol ices. We aim at experimentally measuring X-ray photodesorption yields of methanol and its photo-products from pure CH$_3$OH ices, and to shed light on the mechanisms responsible for the desorption process. We irradiated methanol ices at 15 K with X-rays in the 525 - 570 eV range. The release of species in the gas phase was monitored by quadrupole mass spectrometry, and photodesorption yields were derived. Under our experimental conditions, the CH$_3$OH X-ray photodesorption yield from pure methanol ice is 10$^{-2}$ molecule/photon at 564 eV. Photo-products such as CH$_4$, H$_2$CO, H$_2$O, CO$_2$ , and CO also desorb at increasing efficiency. X-ray photodesorption of larger COMs, which can be attributed to either ethanol, dimethyl ether, and/or formic acid, is also detected. The physical mechanisms at play are discussed and must likely involve the thermalization of Auger electrons in the ice, thus indicating that its composition plays an important role. Finally, we provide desorption yields applicable to protoplanetary disk environments for astrochemical models. The X-rays are shown to be a potential candidate to explain gas-phase abundances of methanol in disks. However, more relevant desorption yields derived from experiments on mixed ices are mandatory to properly support the role played by X-rays in nonthermal desorption of methanol (see paper II).

Core-excitation of water ice releases many different molecules and ions in the gas phase. Studying these desorbed species and the underlying 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 (\rev{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$^-$, OH$^-$) give a new perspective on their previously reported very low desorption yields for most types of irradiation of water, showing that they mostly originate from the dissociation of photoproducts such as H$_2$O$_2$., Comment: Accepted in Journal of Chemical Physics

A very low ortho-to-para ratio (OPR) of 0.1-0.5 was previously reported in the Orion Bar photon-dominated region (PDR), based on observations of two optically thin $\mathrm{H_2^{18}O}$ lines which were analyzed by using a single-slab large velocity gradient model. The corresponding spin temperature does not coincide with the kinetic temperature of the molecular gas in this UV-illuminated region. This was interpreted as an indication of water molecules being formed on cold icy grains which were subsequently released by UV photodesorption. A more complete set of water observations in the Orion Bar, including seven $\mathrm{H_2^{16}O}$ lines and one $\mathrm{H_2^{18}O}$ line, carried out using Herschel/HIFI instrument, was reanalyzed using the Meudon PDR code to derive gas-phase water abundance and the OPR, taking into account the steep density and temperature gradients present in the region. The model line intensities are in good agreement with the observations assuming that water molecules formed with an OPR corresponding to thermal equilibrium conditions at the local kinetic temperature of the gas and when solely considering gas-phase chemistry and water gas-grain exchanges through adsorption and desorption. Gas-phase water is predicted to arise from a region deep into the cloud, corresponding to a visual extinction of $A_{\mathrm{V}} \sim 9$, with a $\mathrm{H_2^{16}O}$ fractional abundance of $\sim 2\times 10^{-7}$ and column density of $(1.4 \pm 0.8) \times 10^{15}$ cm$^{-2}$ for a total cloud depth of $A_{\mathrm{V}}=15$. A line-of-sight average ortho-to-para ratio of $2.8 \pm 0.2$ is derived. The observational data are consistent with a nuclear spin isomer repartition corresponding to the thermal equilibrium at a temperature of $36 \pm 2$ K, much higher than the spin temperature previously reported for this region and close to the gas kinetic temperature in the water-emitting gas.

The study and quantification of UV photon-induced desorption of frozen molecules furthers our understanding of the chemical evolution of cold interstellar regions. Nitric oxide (NO) is an important intermediate species in both gas-phase and solid-phase chemical networks. In this work, we present quantitative measurements of the photodesorption of a pure NO ice.We used the tunable monochromatic synchrotron light of the DESIRS beamline of the SOLEIL facility near Paris to irradiate NO ices in the 6 - 13.6 eV range and measured desorption by quadrupole mass spectrometry.We find that NO photodesorption is very efficient, its yield being around 1e-2 molecule per incident photon for UV fields relevant to the diffuse and dense interstellar medium. We discuss the extrapolation of our results to an astrophysical context and we compare photodesorption of NO to previously studied molecules., Comment: A&A, Accepted

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