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Mid-infrared emission features probe the properties of ionized gas, and hot or warm molecular gas. The Orion Bar is a frequently studied photodissociation region (PDR) containing large amounts of gas under these conditions, and was observed with the MIRI IFU aboard JWST as part of the "PDRs4All" program. The resulting IR spectroscopic images of high angular resolution (0.2") reveal a rich observational inventory of mid-IR emission lines, and spatially resolve the substructure of the PDR, with a mosaic cutting perpendicularly across the ionization front and three dissociation fronts. We extracted five spectra that represent the ionized, atomic, and molecular gas layers, and measured the most prominent gas emission lines. An initial analysis summarizes the physical conditions of the gas and the potential of these data. We identified around 100 lines, report an additional 18 lines that remain unidentified, and measured the line intensities and central wavelengths. The H I recombination lines originating from the ionized gas layer bordering the PDR, have intensity ratios that are well matched by emissivity coefficients from H recombination theory, but deviate up to 10% due contamination by He I lines. We report the observed emission lines of various ionization stages of Ne, P, S, Cl, Ar, Fe, and Ni, and show how certain line ratios vary between the five regions. We observe the pure-rotational H$_2$ lines in the vibrational ground state from 0-0 S(1) to 0-0 S(8), and in the first vibrationally excited state from 1-1 S(5) to 1-1 S(9). We derive H$_2$ excitation diagrams, and approximate the excitation with one thermal (~700 K) component representative of an average gas temperature, and one non-thermal component (~2700 K) probing the effect of UV pumping. We compare these results to an existing model for the Orion Bar PDR and highlight the differences with the observations., Comment: 26 pages, 12 figures, 3 tables. Submitted to A&A, under review (1st revision)

Reports on the detection of carbonates in planetary nebulae (PNe) and protostars suggested the existence of a mechanism that produce these compounds in stellar winds and outflows. A consecutive laboratory study reported a possible mechanism by observing the non-thermodynamic equilibrium (TE), gas-phase condensation of amorphous silicate grains with amorphous calcium carbonate inclusions. It concluded that water vapor was necessary to the formation of the carbonates. We present a laboratory study with pulsed laser ablation of an MgSi target in O$_2$ and CO$_2$ gases and report, in the absence of water vapor, the non-TE, gas-phase condensation of amorphous carbonated magnesium silicate dust. It consists of amorphous silicate grains with formula MgSiO$_3$ that comprise carbonate groups homogeneously dispersed in their structure. The infrared spectra of the grains show the characteristic bands of amorphous silicates and two bands at $\sim$6.3 and $\sim$7.0 $\mu$m that we assign to the carbonate groups. The silicate bands are not significantly affected at an estimated Si:C ratio of 9:1 to 9:2. Such grains could form in winds and outflows of evolved stars and PNe if C atoms are present during silicate condensation. Additionally, we find that Lyman-$\alpha$ radiation dissociates the carbonate groups at the surface of the carbonated silicate grains and we estimate the corresponding photodissociation cross section of (0.04 $\pm$ 0.02) $\times$ 10$^{-16}$ cm$^2$. Therefore, photodissociation would limit the formation of carbonate groups on grains in winds and outflows of stars emitting VUV photons and the carbonates observed in protostars have not formed by gas-phase condensation., Comment: 19 pages, 16 figures, accepted for publication in The Astrophysical Journal

Most low-mass stars form in stellar clusters that also contain massive stars, which are sources of far-ultraviolet (FUV) radiation. Theoretical models predict that this FUV radiation produces photo-dissociation regions (PDRs) on the surfaces of protoplanetary disks around low-mass stars, impacting planet formation within the disks. We report JWST and Atacama Large Millimetere Array observations of a FUV-irradiated protoplanetary disk in the Orion Nebula. Emission lines are detected from the PDR; modelling their kinematics and excitation allows us to constrain the physical conditions within the gas. We quantify the mass-loss rate induced by the FUV irradiation, finding it is sufficient to remove gas from the disk in less than a million years. This is rapid enough to affect giant planet formation in the disk.

Existence of strongly bound water molecules on silicate surfaces, above the desorption temperature of water ice, has been first predicted by computational studies and recently demonstrated by laboratory experiments. Such trapped water may be present in various astrophysical environments and there is now evidence for its presence in the diffuse interstellar medium and in extraterrestrial particles. We present here new results of a laboratory study of the phenomenon of trapping (strong bonding) of water molecules by silicates. We show that the efficiency of trapping is strongly dependent on the properties and composition of the surface. Our results point out that the presence of trapped water should be due to the hydrophilic properties of the silicate surface and that the nature of trapping is physical (physisorption rather than chemisorption). We demonstrate that water can be trapped on silicates up to the temperatures of about 470 K, which speaks for the presence of wet silicate grains in the terrestrial planet formation zone in planet-forming disks. Studying the thermal and UV stability of trapped water, we conclude that the detection of trapped water in the diffuse ISM speaks for its efficient continuous formation. We discuss our results as relevant to fundamental scientific questions, such as the oxygen depletion problem, the origin of water on Earth, and the formation of rocky planets., Comment: Accepted for publication in ApJ

The diffusion of water molecules through mesoporous dust of amorphous carbon (a-C) is a key process in the evolution of prestellar, protostellar, and protoplanetary dust, as well as in that of comets. It also plays a role in the formation of planets. Given the absence of data on this process, we experimentally studied the isothermal diffusion of water molecules desorbing from water ice buried at the bottom of a mesoporous layer of aggregated a-C nanoparticles, a material analogous to protostellar and cometary dust. We used infrared spectroscopy to monitor diffusion in low temperature (160 to 170 K) and pressure (6 $\times$ 10$^{-5}$ to 8 $\times$ 10$^{-4}$ Pa) conditions. Fick's first law of diffusion allowed us to derive diffusivity values on the order of 10$^{-2}$ cm$^2$ s$^{-1}$, which we linked to Knudsen diffusion. Water vapor molecular fluxes ranged from 5 $\times$ 10$^{12}$ to 3 $\times$ 10$^{14}$ cm$^{-2}$ s$^{-1}$ for thicknesses of the ice-free porous layer ranging from 60 to 1900 nm. Assimilating the layers of nanoparticles to assemblies of spheres, we attributed to this cosmic dust analog of porosity 0.80-0.90 a geometry correction factor, similar to the tortuosity factor of tubular pore systems, between 0.94 and 2.85. Applying the method to ices and refractory particles of other compositions will provides us with other useful data.

The JWST has captured the most detailed and sharpest infrared images ever taken of the inner region of the Orion Nebula, the nearest massive star formation region, and a prototypical highly irradiated dense photo-dissociation region (PDR). We investigate the fundamental interaction of far-ultraviolet photons with molecular clouds. The transitions across the ionization front (IF), dissociation front (DF), and the molecular cloud are studied at high-angular resolution. These transitions are relevant to understanding the effects of radiative feedback from massive stars and the dominant physical and chemical processes that lead to the IR emission that JWST will detect in many Galactic and extragalactic environments. Due to the proximity of the Orion Nebula and the unprecedented angular resolution of JWST, these data reveal that the molecular cloud borders are hyper structured at small angular scales of 0.1-1" (0.0002-0.002 pc or 40-400 au at 414 pc). A diverse set of features are observed such as ridges, waves, globules and photoevaporated protoplanetary disks. At the PDR atomic to molecular transition, several bright features are detected that are associated with the highly irradiated surroundings of the dense molecular condensations and embedded young star. Toward the Orion Bar PDR, a highly sculpted interface is detected with sharp edges and density increases near the IF and DF. This was predicted by previous modeling studies, but the fronts were unresolved in most tracers. A complex, structured, and folded DF surface was traced by the H2 lines. This dataset was used to revisit the commonly adopted 2D PDR structure of the Orion Bar. JWST provides us with a complete view of the PDR, all the way from the PDR edge to the substructured dense region, and this allowed us to determine, in detail, where the emission of the atomic and molecular lines, aromatic bands, and dust originate.

(Abridged) Mid-infrared observations of photodissociation regions (PDRs) are dominated by strong emission features called aromatic infrared bands (AIBs). The most prominent AIBs are found at 3.3, 6.2, 7.7, 8.6, and 11.2 $\mu$m. The most sensitive, highest-resolution infrared spectral imaging data ever taken of the prototypical PDR, the Orion Bar, have been captured by JWST. We provide an inventory of the AIBs found in the Orion Bar, along with mid-IR template spectra from five distinct regions in the Bar: the molecular PDR, the atomic PDR, and the HII region. We use JWST NIRSpec IFU and MIRI MRS observations of the Orion Bar from the JWST Early Release Science Program, PDRs4All (ID: 1288). We extract five template spectra to represent the morphology and environment of the Orion Bar PDR. The superb sensitivity and the spectral and spatial resolution of these JWST observations reveal many details of the AIB emission and enable an improved characterization of their detailed profile shapes and sub-components. While the spectra are dominated by the well-known AIBs at 3.3, 6.2, 7.7, 8.6, 11.2, and 12.7 $\mu$m, a wealth of weaker features and sub-components are present. We report trends in the widths and relative strengths of AIBs across the five template spectra. These trends yield valuable insight into the photochemical evolution of PAHs, such as the evolution responsible for the shift of 11.2 $\mu$m AIB emission from class B$_{11.2}$ in the molecular PDR to class A$_{11.2}$ in the PDR surface layers. This photochemical evolution is driven by the increased importance of FUV processing in the PDR surface layers, resulting in a "weeding out" of the weakest links of the PAH family in these layers. For now, these JWST observations are consistent with a model in which the underlying PAH family is composed of a few species: the so-called 'grandPAHs'., Comment: 25 pages, 10 figures, to appear in A&A

The origin of organic compounds detected in meteorites and comets, some of which could serve as precursors of life on Earth, still remains an open question. The aim of the present study is to make one more step in revealing the nature and composition of organic materials of extraterrestrial particles by comparing infrared spectra of laboratory-made refractory organic residues to the spectra of cometary particles returned by the Stardust mission, interplanetary dust particles, and meteorites. Our results reinforce the idea of a pathway for the formation of refractory organics through energetic and thermal processing of molecular ices in the solar nebula. There is also the possibility that some of the organic material formed already in the parental molecular cloud before it entered the solar nebula. The majority of the IR "organic" bands of the studied extraterrestrial particles can be reproduced in the spectra of the laboratory organic residues. We confirm the detection of water, nitriles, hydrocarbons, and carbonates in extraterrestrial particles and link it to the formation location of the particles in the outer regions of the solar nebula. To clarify the genesis of the species, high-sensitivity observations in combination with laboratory measurements like those presented in this paper are needed. Thus, this study presents one more piece of the puzzle of the origin of water and organic compounds on Earth and motivation for future collaborative laboratory and observational projects., Comment: accepted for publication in ApJ

Massive stars disrupt their natal molecular cloud material through radiative and mechanical feedback processes. These processes have profound effects on the evolution of interstellar matter in our Galaxy and throughout the Universe, from the era of vigorous star formation at redshifts of 1-3 to the present day. The dominant feedback processes can be probed by observations of the Photo-Dissociation Regions (PDRs) where the far-ultraviolet photons of massive stars create warm regions of gas and dust in the neutral atomic and molecular gas. PDR emission provides a unique tool to study in detail the physical and chemical processes that are relevant for most of the mass in inter- and circumstellar media including diffuse clouds, proto-planetary disks and molecular cloud surfaces, globules, planetary nebulae, and star-forming regions. PDR emission dominates the infrared (IR) spectra of star-forming galaxies. Most of the Galactic and extragalactic observations obtained with the James Webb Space Telescope (JWST) will therefore arise in PDR emission. In this paper we present an Early Release Science program using the MIRI, NIRSpec, and NIRCam instruments dedicated to the observations of an emblematic and nearby PDR: the Orion Bar. These early JWST observations will provide template datasets designed to identify key PDR characteristics in JWST observations. These data will serve to benchmark PDR models and extend them into the JWST era. We also present the Science-Enabling products that we will provide to the community. These template datasets and Science-Enabling products will guide the preparation of future proposals on star-forming regions in our Galaxy and beyond and will facilitate data analysis and interpretation of forthcoming JWST observations., Comment: Submitted to PASP

The solid-state reaction C + H$_2$O $\rightarrow$ H$_2$CO was studied experimentally following the codeposition of C atoms and H$_2$O molecules at low temperatures. In spite of the reaction barrier and absence of energetic triggering, the reaction proceeds fast on the experimental timescale pointing to its quantum tunneling mechanism. This route to formaldehyde shows a new "non-energetic" pathway to complex organic and prebiotic molecules in astrophysical environments. Energetic processing of the produced ice by UV irradiation leads mainly to the destruction of H$_2$CO and the formation of CO$_2$ challenging the role of energetic processing in the synthesis of complex organic molecules under astrophysically relevant conditions., Comment: to appear in APJ

Whether ice in cold cosmic environments is physically separated from the silicate dust or mixed with individual silicate moieties is not known. However, different grain models give very different compositions and temperatures of grains. The aim of the present study is a comparison of the mid-IR spectra of laboratory silicate-grains/water-ice mixtures with astronomical observations to evaluate the presence of dust/ice mixtures in interstellar and circumstellar environments. The laboratory data can explain the observations assuming reasonable mass-averaged temperatures for the protostellar envelopes and protoplanetary disks demonstrating that a substantial fraction of water ice may be mixed with silicate grains. Based on the combination of laboratory data and infrared observations, we provide evidence of the presence of solid-state water in the diffuse interstellar medium. Our results have implications for future laboratory studies trying to investigate cosmic dust grain analogues and for future observations trying to identify the structure, composition, and temperature of grains in different astrophysical environments., Comment: Accepted for publication in Nature Astronomy

Surface processes on cosmic solids in cold astrophysical environments lead to gas phase depletion and molecular complexity. Most astrophysical models assume that the molecular ice forms a thick multilayer substrate, not interacting with the dust surface. In contrast, we present experimental results demonstrating the importance of the surface for porous grains. We show that cosmic dust grains may be covered by a few monolayers of ice only. This implies that the role of dust surface structure, composition, and reactivity in models describing surface processes in cold interstellar, protostellar, and protoplanetary environments has to be reevaluated., Comment: Accepted for publication in Physical Review Letters

The catalytic role of dust grain surfaces in the thermal reaction CO2 + 2NH3 $\rightarrow$ NH4+NH2COO was recently demonstrated by our group. The rate coefficients for the reaction at 80 K on the surface of nanometre-sized carbon and silicate grains were measured to be up to three times higher compared to the reaction rate coefficients measured on KBr. In this study, the reaction was performed on carbon grains and on KBr in the extended temperature range of 50 - 80 K and with the addition of water ice. The reaction activation energy was found to be about 3 times lower on grains compared to the corresponding ice layer on KBr. Thus, the catalytic role of the dust grain surface in the studied reaction can be related to a reduction of the reaction barrier. Addition of water to NH3:CO2 ice on grains slowed the reaction down. At the H2O:CO2 ratio of 5:1, the reaction was not detected on the experimental timescale. This result calls into question the thermal formation of ammonium carbamate in dense molecular clouds and outer regions of protostellar and protoplanetary environments with dominating water ice mantle chemistry. However, it can still happen in inner regions of protostellar and protoplanetary environments in crystalline ices.

The feasibility of contemporary gas-grain astrochemical models depends on the availability of accurate kinetics data, in particular, for surface processes. We study the sensitivity of gas-grain chemical models to the energy barrier Ea of the important surface reaction between some of the most abundant species: C and H2 (surface C + surface H2 = surface CH2). We used the gas-grain code ALCHEMIC to model the time-dependent chemical evolution over a 2D grid of densities (nH: 10^{3} - 10^{12}cm^{-3}) and temperatures (T: 10 - 300 K), assuming UV-dark (Av = 20 mag) and partly UV-irradiated (Av = 3 mag) conditions that are typical of the dense interstellar medium. We considered two values for the energy barrier of the surface reaction, Ea = 2500 K (as originally implemented in the networks) and Ea = 0 K (as measured in the laboratory and computed by quantum chemistry simulations). We find that if the C + H2 = CH2 surface reaction is barrierless, a more rapid conversion of the surface carbon atoms into methane ice occurs. Overproduction of the CHn hydrocarbon ices affects the surface formation of more complex hydrocarbons, cyanides and nitriles, and CS-bearing species at low temperatures < 10-15 K. The surface hydrogenation of CO and hence the synthesis of complex (organic) molecules become affected as well. As a result, important species whose abundances may change by more than a factor of two at 1 Myr include atomic carbon, small mono-carbonic (C1) and di-carbonic (C2) hydrocarbons, CO2, CN, HCN, HNC, HNCO, CS, H2CO, H2CS, CH2CO, and CH3OH (in either gas and/or ice). The abundances of key species, CO, H2O, and N2 as well as O, HCO+, N2H+, NH3, NO, and most of the S-bearing molecules, remain almost unaffected. Further accurate laboratory measurements and quantum chemical calculations of the surface reaction barriers will be crucial to improve the accuracy of astrochemical models., Comment: Submitted to Astronomy & Astrophysics (A&A), 9 pages

The formation and growth of refractory matter on pre-existing interstellar dust grain surfaces was studied experimentally by annealing neon-ice matrices in which potential precursors of silicate grains (Mg and Fe atoms, SiO and SiO$_2$ molecules) and of solid carbon (C$_n$ molecules, $n$ = 2-10) were initially isolated. Other molecules, mainly O$_3$, CO, CO$_2$, C$_3$O, and H$_2$O, were embedded at the same time in the matrices. The annealing procedure caused the cold dopants to diffuse and interact in the neon ice. Monitoring the procedure in situ with infrared spectroscopy revealed the disappearance of the silicon oxide and carbon molecules at temperatures lower than 13 K, and the rise of the Si-O stretching band of silicates. Ex situ electron microscopy confirmed the formation of silicate grains and showed that their structure was amorphous. It also showed that amorphous carbon matter was formed simultaneously next to the silicate grains, the two materials being chemically separated. The results of the experiments support the hypothesis that grains of complex silicates and of carbonaceous materials are re-formed in the cold ISM, as suggested by astronomical observations and evolution models of cosmic dust masses. Moreover, they show that the potential precursors of one material do not combine with those of the other at cryogenic temperatures, providing us with a clue as to the separation of silicates and carbon in interstellar grains., Comment: 20 pages, 9 figures, accepted for publication in The Astrophysical Journal

Photoelectron photoion coincidence spectroscopy has been used to measure the threshold photoelectron spectrum of 1-ethynylpyrene and to obtain the breakdown graph describing the dissociation of the 1-ethynylpyrene cation. The threshold photoelectron measurement has allowed us to improve the determination of the ionization energy of 1-ethynylpyrene at 7.391 $\pm$ 0.005 eV. Concerning the main dissociation channels, the analysis of the breakdown graph has given 3.70 $\pm$ 0.60 eV as the activation energy for the loss of one H atom and 2.98 $\pm$ 1.80 eV for the loss of a second independent H atom. The corresponding entropies of activation are affected by large errors as observed in similar studies of other polycyclic aromatic hydrocarbon cations. Minor dissociation channels were also detected and identified as the loss of the C$_2$H group and the loss of a C$_2$H$_2$ unit and/or that of an H atom plus the C$_2$H group. The activation energies and the entropies of activation of these minor pathways could not be derived from the measurements. It is found that the cation of 1-ethynylpyrene behaves like the cation of pyrene and is consequently more photostable than the cation of 1-methylpyrene. We conclude that photodissociation is not the leading cause of the low abundance, if not the absence, of ethynyl-substituted polycyclic aromatic hydrocarbon species in the interstellar medium., Comment: 13 pages, 9 figures, accepted for publication in The Astrophysical Journal

Water ice is important for the evolution and preservation of life. Identifying the distribution of water ice in debris disks is therefore of great interest in the field of astrobiology. Furthermore, icy dust grains are expected to play important roles throughout the entire planet formation process. However, currently available observations only allow deriving weak conclusions about the existence of water ice in debris disks. We investigate whether it is feasible to detect water ice in typical debris disk systems. We take the following ice destruction mechanisms into account: sublimation of ice, dust production through planetesimal collisions, and photosputtering by UV-bright central stars. We consider icy dust mixture particles with various shapes consisting of amorphous ice, crystalline ice, astrosilicate, and vacuum inclusions. We calculated optical properties of inhomogeneous icy dust mixtures using effective medium theories, that is, Maxwell-Garnett rules. Subsequently, we generated synthetic debris disk observables, such as spectral energy distributions and spatially resolved thermal reemission and scattered light intensity and polarization maps with our code DMS. We find that the prominent $\sim$ 3 $\mu\rm{m}$ and 44 $\mu\rm{m}$ water ice features can be potentially detected in future observations of debris disks with the James Webb Space Telescope and the Space Infrared telescope for Cosmology and Astrophysics. We show that the sublimation of ice, collisions between planetesimals, and photosputtering caused by UV sources clearly affect the observational appearance of debris disk systems. In addition, highly porous ice tends to produce highly polarized radiation at around 3 $\mu\rm{m}$. Finally, the location of the ice survival line is determined by various dust properties such as a fractional ratio of ice versus dust, physical states of ice, and the porosity of icy grains., Comment: Accepted for publication in A&A, 17 pages, 20 figures (including 3 figures in the appendix)

Surface chemistry on cosmic dust grains plays an important role in the formation of molecules at low temperatures in the interstellar and circumstellar environments. For the first time, we experimentally put in evidence the catalytic role of dust surfaces using the thermal reaction CO2 + 2NH3 = NH4+NH2COO-, which is also a proxy of radical-radical reactions. Nanometre-sized amorphous silicate and carbon grains produced in our laboratory were used as grain analogues. Surface catalysis on grains accelerates the kinetics of the reaction studied at a temperature of 80 K by a factor of up to 3 compared to the reaction occurring in the molecular solid. The evidence of the catalytic effect of grain surfaces opens a door for experiments and calculations on the surface formation of interstellar and circumstellar molecules on dust. Ammonium carbamate on the surface of grains or released intact into protostellar or protoplanetary disk phases can give start to a network of prebiotic reactions. Therefore, there should be a great interest to search for ammonium carbamate and its daughter molecule, carbamic acid, in interstellar clouds, protostellar envelopes, and protoplanetary disks.

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. First experiments on the photodesorption of water ice molecules from the surface of silicate and carbon grains by UV photons revealed a strong influence of the surface properties on the desorption yield, in particular in the monolayer regime. In the second experiment, the thermal desorption of cometary ice analogues composed of six molecular components was studied for the first time. Co-desorption of CO2 and CH3OH with O2 indicates that at high O2 concentrations in cometary or interstellar ices "heavy" ice molecules can be partly trapped in O2 and release to the gas phase much earlier than expected. This effect could explain astronomical detections of complex organic molecules in cold dense interstellar clouds.

Understanding the history and evolution of small bodies, such as dust grains and comets, in planet-forming disks is very important to reveal the architectural laws responsible for the creation of planetary systems. These small bodies in cold regions of the disks are typically considered as mixtures of dust particles with molecular ices, where ices cover the surface of a dust core or are actually physically mixed with dust. Whilst the first case, ice-on-dust, has been intensively studied in the laboratory in recent decades, the second case, ice-mixed-with-dust, present uncharted territory. This work is the first laboratory study of the temperature-programmed desorption (TPD) of water ice mixed with amorphous carbon and silicate grains. We show that the kinetics of desorption of H2O ice depends strongly on the dust/ice mass ratio, probably, due to the desorption of water molecules from a large surface of fractal clusters composed of carbon or silicate grains. In addition, it is shown that water ice molecules are differently bound to silicate grains in contrast to carbon. The results provide a link between the structure and morphology of small cosmic bodies and the kinetics of desorption of water ice included in them., Comment: Submitted to the Astrophysical Journal

Two different silicate/water ice mixtures representing laboratory analogues of interstellar and circumstellar icy grains were produced in the laboratory. For the first time, optical constants, the real and imaginary parts of the complex refractive index, of such silicate/water ice mixtures were experimentally determined in the mid-infrared spectral region at low temperatures. In addition, optical constants of pure water ice and pure silicates were derived in the laboratory. Two sets of constants were compared, namely, measured constants calculated from the transmission spectra of silicate/water ice samples and effective constants calculated from the optical constants of pure silicates and pure water ice samples using different mixing rules (effective medium approaches). Differences between measured and effective constants show that a mixing (averaging) of optical constants of water ice and silicates for the determination of the optical properties of silicate/ice mixtures can lead to incorrect results. Also, it is shown that a part of water ice molecules is trapped in/on silicate grains and does not desorb up to 200 K. Our unique data are just in time with respect to the new challenging space mission, James Webb Space Telescope, which will be able to bring novel detailed information on interstellar and circumstellar grains, and suitable laboratory data are extremely important for the decoding of astronomical spectra., Comment: The Astrophysical Journal, accepted for publication

This is an editorial to the special issue on Cosmic Dust IX., Comment: Planetary and Space Science, 149, 1-4, December 2017

The life-cycle of cosmic dust grains is far from being understood and the origin and evolution of interstellar medium (ISM) grains is still under debate. In the ISM, the cosmic dust destruction rate is faster than the production rate by stellar sources. However, observations of ISM refractory matter suggest that to maintain a steady amount of cosmic grains, some supplementary production mechanism takes place. In this context, we aimed to study possible re-formation mechanisms of cosmic grains taking place at low temperature directly in the ISM. The low temperature condensation of carbonaceous materials has been investigated in experiments mimicking the ISM conditions. Gas-phase carbonaceous precursors created by laser ablation of graphite were forced to accrete on cold substrates (T about 10 K) representing surviving dust grains. The growing and evolution of the condensing carbonaceous precursors have been monitored by MIR and UV spectroscopy under a number of experimental scenarios. It is demonstrated, for the first time, the possibility to form ISM carbonaceous grains in "situ". The condensation process is governed by carbon chains that first condense into small carbon clusters and finally into more stable carbonaceous materials, which structural characteristics are comparable to the material formed in gas-phase condensation experiments at very high temperature. We also show that the so-formed fullerene-like carbonaceous material is transformed into a more ordered material under VUV processing. The cold condensation mechanisms here discussed can give fundamental clues to fully understand the balance between the timescale for dust injection, destruction and re-formation in the ISM., Comment: 15 pages, 12 figures - accepted for publication in ApJS

The C60 molecule has been recently detected in a wide range of astrophysical environments through its four active intramolecular vibrational modes (T1u) near 18.9, 17.4, 8.5, and 7.0 microns. The strengths of the mid-infrared emission bands have been used to infer astrophysical conditions in the fullerene-rich regions. Widely varying values of the relative intrinsic strengths (RIS) of these four bands are reported in laboratory and theoretical papers, which impedes the derivation of the excitation mechanism of C60 in the astrophysical sources. The spectroscopic analysis of the C60 samples produced with our method delivers highly reproducible RIS values of 100, 25 +- 1, 26 +- 1, and 40 +- 4. A comparison of the inferred C60 emission band strengths with the astrophysical data shows that the observed strengths cannot be explained in terms of fluorescent or thermal emission alone. The large range in the observed 17.4/18.9 emission ratios indicates that either the emission bands contain significant contributions from emitters other than C60, or that the population distribution among the C60 vibrational modes is affected by physical processes other than thermal or UV excitation, such as chemo-luminescence from nascent C60 or possibly, Poincare fluorescence resulting from an inverse internal energy conversion. We have carefully analyzed the effect of the weakly-active fundamental modes and second order modes in the mid-infrared spectrum of C60 and propose that neutral C60 is the carrier of the unidentified emission band at 6.49 microns which has been observed in fullerene-rich environments., Comment: Accepted for publication in The Astrophysical Journal

This is an editorial to the special issue on Cosmic Dust VII.

The life cycle of the population of interstellar polycyclic aromatic hydrocarbon (PAH) molecules depends partly on the photostability of the individual species. We have studied the dissociative photoionization of two ethynyl-substituted PAH species, namely, 9-ethynylphenanthrene and 1-ethynylpyrene. Their adiabatic ionization energy and the appearance energy of fragment ions have been measured with the photoelectron photoion coincidence (PEPICO) spectroscopy technique. The adiabatic ionization energy has been found at 7.84 +/- 0.02 eV for 9-ethynylphenanthrene and at 7.41 +/- 0.02 eV for 1-ethynylpyrene. These values are similar to those determined for the corresponding non-substituted PAH molecules phenanthrene and pyrene. The appearance energy of the fragment ion indicative of the loss of a H atom following photoionization is also similar for either ethynyl-substituted PAH molecule and its non-substituted counterpart. The measurements are used to estimate the critical energy for the loss of a H atom by the PAH cations and the stability of ethynyl-substituted PAH molecules upon photoionization. We conclude that these PAH derivatives are as photostable as the non-substituted species in HI regions. If present in the interstellar medium, they may play an important role in the growth of interstellar PAH molecules., Comment: Accepted for publication in Astrophys. J. on 1 August 2015, 19 pages, 6 figures, 1 table

The condensation of complex silicates with pyroxene and olivine composition at conditions prevailing in molecular clouds has been experimentally studied. For this purpose, molecular species comprising refractory elements were forced to accrete on cold substrates representing the cold surfaces of surviving dust grains in the interstellar medium. The efficient formation of amorphous and homogeneous magnesium iron silicates at temperatures of about 12 K has been monitored by IR spectroscopy. The gaseous precursors of such condensation processes in the interstellar medium are formed by erosion of dust grains in supernova shock waves. In the laboratory, we have evaporated glassy silicate dust analogs and embedded the released species in neon ice matrices that have been studied spectroscopically to identify the molecular precursors of the condensing solid silicates. A sound coincidence between the 10 micron band of the interstellar silicates and the 10 micron band of the low-temperature siliceous condensates can be noted., Comment: 12 pages, 7 figures, Faraday Discussions meeting 168, submitted on 12 Feb 2014, accepted on 13 Feb 2014

Polycyclic aromatic hydrocarbon (PAH) molecules have been long considered promising candidates for the carriers of the diffuse interstellar bands (DIBs). The PAH-DIB hypothesis, however, raises two major issues. First, the number of interstellar PAH species is potentially orders of magnitude larger than the number of DIBs. Second, the absorption spectrum of a PAH is in general dominated by bands found at UV wavelengths while, conversely, DIBs are absent from the UV wavelength domain and arise at visible and near IR wavelengths. These issues do not necessarily weaken the PAH-DIB hypothesis and can actually allow us to refine it. In that context, we analyze the UV/vis absorption spectra of PAH molecules isolated in Ne matrices and propose that polyynyl-substituted PAHs, or similar species, are valid candidates for the carriers of the DIBs. Finally, a possible lifecycle for DIB-carrying PAHs is presented., Comment: 5 pages, 1 figure, submitted to Proceedings of the International Astronomical Union (IAU) Symposium 297: The Diffuse Interstellar Bands, edited by J. Cami and N. Cox

Infrared (IR) absorption spectra of individual polycyclic aromatic hydrocarbons (PAHs) containing methyl (-CH3), methylene (>CH2), or diamond-like *CH groups and IR spectra of mixtures of methylated and hydrogenated PAHs prepared by gas phase condensation were measured at room temperature (as grains in pellets) and at low temperature (isolated in Ne matrices). In addition, the PAH blends were subjected to an in-depth molecular structure analysis by means of high-performance liquid chromatography, nuclear magnetic resonance spectroscopy, and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry. Supported by calculations at the density functional theory level, the laboratory results were applied to analyze in detail the aliphatic absorption complex of the diffuse interstellar medium at 3.4 mu-m and to determine the abundances of hydrocarbon functional groups. Assuming that the PAHs are mainly locked in grains, aliphatic CHx groups (x = 1,2,3) would contribute approximately in equal quantities to the 3.4 mu-m feature (N_{CHx} / N_{H} approx 10^{-5} - 2 * 10^{-5}). The abundances, however, may be two to four times lower if a major contribution to the 3.4 mu-m feature comes from molecules in the gas phase. Aromatic =CH groups seem to be almost absent from some lines of sight, but can be nearly as abundant as each of the aliphatic components in other directions (N_{=CH} / N_{H} < 2 * 10^{-5}; upper value for grains). Due to comparatively low binding energies, astronomical IR emission sources do not display such heavy excess hydrogenation. At best, especially in proto-planetary nebulae, >CH2 groups bound to aromatic molecules, i.e., excess hydrogens on the molecular periphery only, can survive the presence of a nearby star., Comment: 34 pages, 19 figures, ApJS, 208, 26

Context. As revealed by high-resolution spectral investigations in the wavelength range between 300 and 400 nm, the interstellar extinction curve does not display any of the sharp electronic absorption bands that are characteristic for large polyatomic molecules, such as polycyclic aromatic hydrocarbons (PAHs), which belong to the most abundant interstellar molecules. Aims. We aim to verify whether the absorption curves of mixtures of medium-sized PAHs produced in the laboratory can explain the astronomical observations. Methods. The PAH mixtures were synthesized by infrared laser pyrolysis and subsequent chemical extraction and size separation. The matrix isolation technique was used to study the absorption spectra of isolated molecules at low temperature. Results. Our experimental results demonstrate that the UV-visible absorption curves of PAH mixtures can be very smooth, displaying no sharp bands, if the molecular diversity is sufficiently high. Conclusions. In view of the absence of sharp electronic features on the interstellar extinction curve for 300 < {\lambda} < 400 nm, we conclude from our experimental findings that the interstellar PAH population must be very diverse. The low fractional abundances of individual species prevent their detection on the basis of spectral fingerprints in the UV., Comment: 6 pages, 5 figures

Solid state spectroscopy continues to be an important source of information on the mineralogical composition and physical properties of dust grains both in space and on planetary surfaces. With only a few exceptions, artificially produced or natural terrestrial analog materials, rather than 'real' cosmic dust grains, are the subject of solid state astrophysics. The Jena laboratory has provided a large number of data sets characterizing the UV, optical and infrared properties of such cosmic dust analogs. The present paper highlights recent developments and results achieved in this context, focussing on 'non-standard conditions' such as very low temperatures, very high temperatures and very long wavelengths., Comment: 15 pages, 10 figures. Contribution to an IAU Conference "The Molecular Universe" held in Toledo in June 2011