CO$_2$ ice has a phase transition at 35 K when its structure changes from amorphous to crystalline. Using Reflection absorption Infrared Spectroscopy (RAIRS), Öberg et al. observed that the photodesorption yield of CO$_2$ ice deposited at 60 K and irradiated at 18 K is 40% lower than that of CO$_2$ ice deposited and irradiated at 18 K. In this work, CO$_2$ ices were deposited at 16-60 K and UV-irradiated at 16 K to rule out the temperature effect and figure out the relationship between photodesorption yield and ice structure. IR spectroscopy is a common method used for measurement of the photodesorption yield in ices. We found that undetectable C atoms produced in irradiated CO$_2$ ice can account for 33% of the amount of depleted CO$_2$ molecules in the ice. A quantitative calibration of QMS was therefore performed to convert the measured ion current into photodesorption yield. During various irradiation periods, the dominant photodesorbing species were CO, O$_2$, and CO$_2$, and their photodesorption yields in CO$_2$ ices deposited at different temperature configurations were almost the same, indicating that ice morphology has no effect on the photodesorption yield of CO$_2$ ice. In addition, we found that the lower desorption yield reported by Martín-Doménech et al. is due to a linear relationship between the photodesorption yield and the combination of energy distribution of Microwave-Discharge Hydrogen-flow Lamp (MDHL) and UV absorption cross section of ices.
The HDO/H2O ratio in interstellar gas is often used to draw conclusions on the origin of water in star-forming regions and on Earth. In cold cores and in the outer regions of protoplanetary disks, gas-phase water comes from photodesorption of water ice. We present fitting formulae for implementation in astrochemical models using photodesorption efficiencies for all water ice isotopologues obtained using classical molecular dynamics simulations. We investigate if the gas-phase HDO/H2O ratio reflects that present in the ice or whether fractionation can occur during photodesorption. Probabilities…
Pure acetonitrile (CH3CN) and mixed CO:CH3CN and H2O:CH3CN ices have been irradiated at 15K with Vacuum UltraViolet (VUV) photons in the 7-13.6 eV range using synchrotron radiation. VUV photodesorption yields of CH3CN and of photo-products have been derived as a function of the incident photon energy. The coadsorption of CH3CN with CO and H2O molecules, which are expected to be among the main constituents of interstellar ices, is found to have no significant influence on the VUV photodesorption spectra of CH3CN, CHCN, HCN, CN and CH3. Contrary to what has generally been evidenced for most of t…
Vacuum-UV (VUV) photodesorption from water-rich ice mantles coating interstellar grains is known to play an important role in the gas-to-ice ratio in star- and planet-forming regions. Quantitative photodesorption yields from water ice are crucial for astrochemical models. We aim to provide the first quantitative photon-energy dependent photodesorption yields from water ice in the VUV. This information is important to understand the photodesorption mechanisms and to account for the variation of the yields under interstellar irradiation conditions. Experiments have been performed on the DESIRS b…
Ultraviolet photodesorption of molecules from icy interstellar grains can explain observations of cold gas in regions where thermal desorption is negligible. This non-thermal desorption mechanism should be especially important where UV fluxes are high. N2 and O2 are expected to play key roles in astrochemical reaction networks, both in the solid state and in the gas phase. Measurements of the wavelength-dependent photodesorption rates of these two infrared-inactive molecules provide astronomical and physical-chemical insights into the conditions required for their photodesorption. Tunable radi…
UV ice photodesorption is an important non-thermal desorption pathway in many interstellar environments that has been invoked to explain observations of cold molecules in disks, clouds and cloud cores. Systematic laboratory studies of the photodesorption rates, between 7 and 14 eV, from CO:N2 binary ices, have been performed at the DESIRS vacuum UV beamline of the synchrotron facility SOLEIL. The photodesorption spectral analysis demonstrates that the photodesorption process is indirect, i.e. the desorption is induced by a photon absorption in sub-surface molecular layers, while only surface m…
UV-induced photodesorption of ice is a non-thermal evaporation process that can explain the presence of cold molecular gas in a range of interstellar regions. Information on the average UV photodesorption yield of astrophysically important ices exists for broadband UV lamp experiments. UV fields around low-mass pre-main sequence stars, around shocks and in many other astrophysical environments are however often dominated by discrete atomic and molecular emission lines. It is therefore crucial to consider the wavelength dependence of photodesorption yields and mechanisms. In this work, for the …
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…
Wavelength dependent photodesorption rates have been determined using synchrotron radiation, for condensed pure and mixed methanol ice in the 7 -- 14 eV range. The VUV photodesorption of intact methanol molecules from pure methanol ices is found to be of the order of 10$^{-5}$ molecules/photon, that is two orders of magnitude below what is generally used in astrochemical models. This rate gets even lower ($<$ 10$^{-6}$ molecules/photon) when the methanol is mixed with CO molecules in the ices. This is consistent with a picture in which photodissociation and recombination processes are at the o…
Ice mantles detected on the surface of dust grains toward the coldest regions of the interstellar medium can be photoprocessed by the secondary ultraviolet (UV) field present in dense cloud interiors. In this work, we present UV-irradiation experiments under astrophysically relevant conditions of pure NH3 ice samples in an ultra-high vacuum chamber where solid samples were deposited onto a substrate at 8 K. The ice analogs were subsequently photoprocessed with a microwave-discharged hydrogen- flow lamp. The induced radiation and photochemistry led to the production of H2, N2 and N2H4. In addit…
Non-thermal desorption from icy grains containing H$_2$CO has been invoked to explain the observed H$_2$CO gas phase abundances in ProtoPlanetary Disks (PPDs) and Photon Dominated Regions (PDRs). Photodesorption is thought to play a key role, however no absolute measurement of the photodesorption from H$_2$CO ices were performed up to now, so that a default value is used in the current astrophysical models. As photodesorption yields differ from one molecule to the other, it is crucial to experimentally investigate photodesorption from H$_2$CO ices. We measured absolute wavelength-resolved phot…
Water is the main constituent of interstellar ices, and it plays a key role in the evolution of many regions of the interstellar medium, from molecular clouds to planet-forming disks. In cold regions of the ISM, water is expected to be completely frozen out onto the dust grains. Nonetheless, observations indicate the presence of cold water vapor, implying that non-thermal desorption mechanisms are at play. Photodesorption by UV photons has been proposed to explain these observations, with the support of extensive experimental and theoretical work on ice analogues. In contrast, photodesorption …
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 photodesor…
Non-thermal desorption of inter- and circum-stellar ice mantles on dust grains, in particular ultraviolet photon-induced desorption, has gained importance in recent years. These processes may account for the observed gas phase abundances of molecules like CO toward cold interstellar clouds. Ice mantle growth results from gas molecules impinging on the dust from all directions and incidence angles. Nevertheless, the effect of the incident angle for deposition on ice photo-desorption rate has not been studied. This work explores the impact on the accretion and photodesorption rates of the incide…
The VUV absorption cross sections of most molecular solids present in interstellar ice mantles with the exception of H2O, NH3, and CO2 have not been reported yet. Models of ice photoprocessing depend on the VUV absorption cross section of the ice to estimate the penetration depth and radiation dose, and in the past, gas phase cross section values were used as an approximation. We aim to estimate the VUV absorption cross section of molecular ice components. Pure ices composed of CO, H2O, CH3OH, NH3, or H2S were deposited at 8 K. The column density of the ice samples was measured in situ by infr…
A new experimental set-up INterStellar Ice-Dust Experiment (INSIDE), was designed for studying cosmic grain analogues represented by ice-coated carbon- and silicate-based dust grains. In the new instrument, we can simulate physical and chemical conditions prevailing in interstellar and circumstellar environments. The set-up combines ultrahigh vacuum and low temperature conditions with infrared spectroscopy and mass spectrometry. Using INSIDE, we plan to investigate physical and chemical processes, such as adsorption, desorption, and formation of molecules, on the surface of dust/ice samples. F…
Methanol is a common component of interstellar and circumstellar ice mantles and is often used as an evolution indicator in star-forming regions. The observations of gas-phase methanol in the interiors of dense molecular clouds at temperatures as low as 10 K suggests that a non-thermal ice desorption must be active. Ice photodesorption was proposed to explain the abundances of gas-phase molecules toward the coldest regions. Laboratory experiments were performed to investigate the potential photodesorption of methanol toward the coldest regions. Solid methanol was deposited at 8 K and UV-irradi…
Context. Methane is among the main components of the ice mantles of insterstellar dust grains, where it is at the start of a rich solid-phase chemical network. Quantification of the photon-induced desorption yield of these frozen molecules and understanding of the underlying processes is necessary to accurately model the observations and the chemical evolution of various regions of the interstellar medium. Aims. This study aims at experimentally determining absolute photodesorption yields for the CH4 molecule as a function of photon energy. The influence of the ice composition is also investig…
In dense clouds of the interstellar medium, dust grains are covered by ice mantles, dominated by H$_2$O. CO and CO$_2$ are common ice components observed in infrared spectra, while infrared inactive N$_2$ is expected to be present in the ice. Molecules in the ice can be dissociated, react or desorb by exposure to secondary ultraviolet photons. Thus, different physical scenarios lead to different ice mantle compositions. This work aims to understand the behaviour of $^{13}$CO : N$_2$ and $^{13}$CO$_2$ : N$_2$ ice mixtures submitted to ultraviolet radiation in the laboratory. Photochemical proce…
This paper reports the first measurements of solid-phase vacuum-ultraviolet (VUV) absorption cross-sections of heavy isotopologues present in icy dust grain mantles of dense interstellar clouds and cold circumstellar environments. Pure ices composed of D2O, CD3OD, 13CO2, and 15N15N were deposited at 8 K, a value similar to the coldest dust temperatures in space. The column density of the ice samples was measured in situ by infrared spectroscopy in transmittance. VUV spectra of the ice samples were collected in the 120-160 nm (10.33-7.74 eV) range using a commercial microwave discharged hydroge…
The astrochemistry of CO2 ice analogues has been a topic of intensive investigation due to the prevalence of CO2 throughout the interstellar medium and the Solar System, as well as the possibility of it acting as a carbon feedstock for the synthesis of larger, more complex organic molecules. In order to accurately discern the physico-chemical processes in which CO2 plays a role, it is necessary to have laboratory-generated spectra to compare against observational data acquired by ground- and space-based telescopes. A key factor which is known to influence the appearance of such spectra is temp…
Carbonic acid (H2CO3) is a weak acid relevant to astrobiology which, to date, remains undetected in space. Experimental work has shown that the beta-polymorph of H2CO3 forms under space relevant conditions through energetic (UV photon, electron, and cosmic ray) processing of CO2- and H2O-rich ices. We present a systematic set of VUV photoabsorption spectra of pure and mixed CO2 and H2O ices exposed to 1 keV electrons at 20 and 80 K to simulate different interstellar and Solar System environments. Ices were then annealed to obtain a layer of pure H2CO3 which was further exposed to 1 keV electro…
The astronomical detection of formamide (NH$_2$CHO) toward various star-forming regions and in cometary material implies that the simplest amide might have an early origin in dark molecular clouds at low temperatures. Laboratory studies have proven the efficient NH$_2$CHO formation in interstellar CO:NH$_3$ ice analogs upon energetic processing. However, it is still under debate, whether the proposed radical-radical recombination reactions forming complex organic molecules remain valid in an abundant H$_2$O environment. The aim of this work was to investigate the formation of NH$_2$CHO in H$_2…
Major components of ices on interstellar grains in molecular clouds - water and carbon oxides - occur at various optical depths. This implies that selective desorption mechanisms are at work. An astrochemical model of a contracting low-mass molecular cloud core is presented. Ice was treated as consisting of the surface and three subsurface layers (sublayers). Photodesorption, reactive desorption, and indirect reactive desorption were investigated. The latter manifests itself through desorption from H+H reaction on grains. Desorption of shallow subsurface species was included. Modeling results …
We investigate nitrogen isotope fractionation in forming and evolving molecular clouds using gas-ice astrochemical simulations. We find that the bulk gas can become depleted in heavy nitrogen (15N) due to the formation of 15N-enriched ices. Around the chemical transition from atomic nitrogen to N2, N15N is selectively photodissociated, which results in the enrichment of 15N in atomic nitrogen. As 15N-enriched atomic nitrogen is converted to ammonia ice via grain surface reactions, the bulk gas is depleted in 15N. The level of 15N depletion in the bulk gas can be up to a factor of two compared …
[Abridged] Observations of protoplanetary disks suggest that they are depleted in gas-phase CO. It has been posed that gas-phase CO is chemically consumed and converted into less volatile species through gas-grain processes. Observations of interstellar ices reveal a CO$_2$ component within H$_2$O ice suggesting co-formation. The aim of this work is to experimentally verify the interaction of gas-phase CO with solid-state OH radicals above the sublimation temperature of CO. Amorphous solid water (ASW) is deposited at 15 K and followed by vacuum-UV (VUV) irradiation to dissociate H$_2$O and cre…
Interstellar grain mantles present in dense interstellar clouds are in constant exchange with the gas phase via accretion and desorption mechanisms such as UV, X-ray photodesorption, cosmic ray induced sputtering, grain thermal fluctuations, and chemical reaction energy release. The relative importance of the various desorption mechanisms is of uttermost importance for astrophysical models to constrain the chemical evolution in such high density dense cloud regions. In this experimental work we investigated the sputtering yield as a function of ice mantle thickness, exposed to Xe ions at 95MeV…
In molecular clouds at temperatures as low as 10 K, all species except hydrogen and helium should be locked in the heterogeneous ice on dust grain surfaces. Nevertheless, astronomical observations have detected over 150 different species in the gas phase in these clouds. The mechanism by which molecules are released from the dust surface below thermal desorption temperatures to be detectable in the gas phase is crucial for understanding the chemical evolution in such cold clouds. Chemical desorption, caused by the excess energy of an exothermic reaction, was first proposed as a key molecular r…
The laboratory work presented here, simulates the chemistry on icy dust grains as typical for the 'CO freeze-out stage' in dark molecular clouds. It differs from previous studies in that solid-state hydrogenation and vacuum UV-photoprocessing are applied simultaneously to co-depositing molecules. In parallel, the reactions at play are described for fully characterized laboratory conditions. The focus is on the formation of molecules containing both carbon and nitrogen atoms, starting with NO in CO-, H2CO-, and CH3OH-rich ices at 13 K. The experiments yield three important conclusions. 1. Witho…
Modeling the UV-photon irradiation of CS$_2$-bearing ices in the laboratory with the pyRate gas-grain astrochemical code. New insights into the missing sulfur problem
Max-Planck-Institut für Extraterrestrische Physik (MPE)（马克斯·普朗克地外物理研究所）；Centro de Astrobiología (CSIC-INTA)（天体生物学中心（西班牙国家科学技术研究委员会-国家航空航天技术研究所））
(Abridged) Mid- and far-infrared observations of the environment around embedded protostars reveal a plethora of high excitation molecular and atomic emission lines. In this work we present spectro-imaging observations of the HH211 system with Herschel/PACS that record emission from major molecular (CO, H2O and OH) and atomic coolants (e.g. [OI]). Molecular lines are mainly exited at the terminal bowshocks of the outflow and around the position of the protostar. All lines show maxima at the southeast bowshock with the exception of water emission that peaks around the central source. Excitation…
