arXiv subjects

H. Linnartz

Publications and source records attributed to H. Linnartz.

At least 55 records · Page 3Linked to original sources

arXiv2019

Confirming interstellar C$_{60}^+$ using the Hubble Space Telescope

Recent advances in laboratory spectroscopy lead to the claim of ionized Buckminsterfullerene (C60+) as the carrier of two diffuse interstellar bands (DIBs) in the near-infrared. However, irrefutable identification of interstellar C60+ requires a match between the wavelengths and the expected strengths of all absorption features detectable in the laboratory and in space. Here we present Hubble Space Telescope (HST) spectra of the region covering the C60+ 9348, 9365, 9428 and 9577 Å absorption bands toward seven heavily-reddened stars. We focus in particular on searching for the weaker laboratory C60+ bands, the very presence of which has been a matter for recent debate. Using the novel STIS-scanning technique to obtain ultra-high signal-to-noise spectra without contamination from telluric absorption that afflicted previous ground-based observations, we obtained reliable detections of the (weak) 9365, 9428 Å and (strong) 9577 Å C60+ bands. The band wavelengths and strength ratios are sufficiently similar to those determined in the latest laboratory experiments that we consider this the first robust identification of the 9428 Å band, and a conclusive confirmation of interstellar C60+.

astro-ph.GA↗

arXiv2018

H2 chemistry in interstellar ices: the case of CO ice hydrogenation in UV irradiated CO:H2 ice mixtures

Context. In dense clouds, hydrogenation reactions on icy dust grains are key in the formation of molecules, like formaldehyde, methanol, and complex organic molecules (COMs). These species form through the sequential hydrogenation of CO ice. Although molecular hydrogen (H2) abundances can be four orders of magnitude higher than those of free H-atoms in dense clouds, H2 surface chemistry has been largely ignored; several laboratory studies show that H2 does not actively participate in non-energetic ice chemistry because of the high activation energies required. Aims. For the example of CO ice hydrogenation, we experimentally investigated the potential role of H2 molecules on the surface chemistry when energetic processing (i.e., UV photolysis) is involved. We test whether additional hydrogenation pathways become available upon UV irradiation of a CO:H2 ice mixture and whether this reaction mechanism also applies to other chemical systems. Methods. Ultra-high vacuum (UHV) experiments were performed at 8~20 K. A pre-deposited solid mixture of CO:H2 was irradiated with UV-photons. Reflection absorption infrared spectroscopy (RAIRS) was used as an in situ diagnostic tool. Single reaction steps and possible isotopic effects were studied by comparing results from CO:H2 and CO:D2 ice mixtures. Results. After UV-irradiation of a CO:H2 ice mixture, two photon-induced products, HCO and H2CO, are unambiguously detected. The proposed reaction mechanism involves electronically excited CO in the following reaction steps: CO + hν->CO*, CO* + H2->HCO + H where newly formed H-atoms are then available for further hydrogenation reactions. The HCO formation yields have a strong temperature dependence for the investigated regime, which is most likely linked to the H2 sticking coefficient. Finally, the astronomical relevance of this photo-induced reaction channel is discussed.

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arXiv2018

The formation of peptide-like molecules on interstellar dust grains

Molecules with an amide functional group resemble peptide bonds, the molecular bridges that connect amino acids, and may thus be relevant in processes that lead to the formation of life. In this study, the solid state formation of some of the smallest amides is investigated in the laboratory. To this end, CH$_{4}$:HNCO ice mixtures at 20 K are irradiated with far-UV photons, where the radiation is used as a tool to produce the radicals required for the formation of the amides. Products are identified and investigated with infrared spectroscopy and temperature programmed desorption mass spectrometry. The laboratory data show that NH$_{2}$CHO, CH$_{3}$NCO, NH$_{2}$C(O)NH$_{2}$, CH$_{3}$C(O)NH$_{2}$ and CH$_{3}$NH$_{2}$ can simultaneously be formed. The NH$_{2}$CO radical is found to be key in the formation of larger amides. In parallel, ALMA observations towards the low-mass protostar IRAS 16293-2422B are analysed in search of CH$_{3}$NHCHO (N-methylformamide) and CH$_{3}$C(O)NH$_{2}$ (acetamide). CH$_{3}$C(O)NH$_{2}$ is tentatively detected towards IRAS 16293-2422B at an abundance comparable with those found towards high-mass sources. The combined laboratory and observational data indicates that NH$_{2}$CHO and CH$_{3}$C(O)NH$_{2}$ are chemically linked and form in the ice mantles of interstellar dust grains. A solid-state reaction network for the formation of these amides is proposed.

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arXiv2018

Photoinduced polycyclic aromatic hydrocarbon dehydrogenation: The competition between H- and H2-loss

PAHs constitute a major component of the interstellar medium carbon budget, locking up to 10--20% of the elemental carbon. Sequential fragmentation induced by energetic photons leads to the formation of new species, including fullerenes. However, the exact chemical routes involved in this process remain largely unexplored. In this work, we focus on the first photofragmentation steps, which involve the dehydrogenation of these molecules. For this, we consider a multidisciplinary approach, taking into account the results from experiments, DFT calculations, and modeling using dedicated Monte-Carlo simulations. By considering the simplest isomerization pathways --- i.e., hydrogen roaming along the edges of the molecule --- we are able to characterize the most likely photodissociation pathways for the molecules studied here. These comprise nine PAHs with clearly different structural properties. The formation of aliphatic-like side groups is found to be critical in the first fragmentation step and, furthermore, sets the balance of the competition between H- and H2-loss. We show that the presence of trio hydrogens, especially in combination with bay regions in small PAHs plays an important part in the experimentally established variations in the odd-to-even H-atom loss ratios. In addition, we find that, as PAH size increases, H2 formation becomes dominant, and sequential hydrogen loss only plays a marginal role. We also find disagreements between experiments and calculations for large, solo containing PAHs, which need to be accounted for. In order to match theoretical and experimental results, we have modified the energy barriers and restricted the H-hopping to tertiary atoms. The formation of H2 in large PAHs upon irradiation appears to be the dominant fragmentation channel, suggesting an efficient formation path for molecular hydrogen in PDRs.

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arXiv2018

The EDIBLES survey III. C2-DIBs and their profiles

The so-called C2-DIBs are a class of very weak bands that fall in the blue part of the optical spectrum and are associated with high column densities of the C2 molecule. DIB profile structures constrain potential molecular carriers, but their measurement requires high S/N and spectra and the use of sightlines without Doppler splitting, as typical for a single-cloud situation. Spectra from the ESO Diffuse Interstellar Bands Large Exploration Survey (EDIBLES) conducted at the VLT (ESO/Paranal) were explored to identify single-cloud and high C2 column sightlines, extract the corresponding C2-DIBs and study their strengths and profiles, and to investigate in detail any sub-structures. The target selection was made based on profile-fitting of the Sodium doublets and the detection of C2 lines. The C2 (2-0) Phillips system was fitted using a physical model of the host cloud. C2 column densities, temperatures as well as gas densities were derived for each sightline. 18 known C2-DIBs and 8 strong non-C2 DIBs were extracted towards 8 targets, comprising 7 single-cloud and one multi-cloud line-of-sights. Correlational studies revealed a tight association of the former group with the C2 columns, whereas the non-C2 DIBs are primarily correlated with reddening. We report three new weak diffuse band candidates. We show for the first time that at least 14 C2-DIBs exhibit spectral sub-structures which are consistent with unresolved rotational branches of molecular carriers. The variability of their peak separations among the bands for a given sightline implies that their carriers are different molecules with quite different sizes. We also illustrate how profiles of the same DIB vary among targets and as a function of physical parameters and provide tables defining the sub-structures to be compared with future models and experimental results.

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arXiv2018

EDIBLES II. On the detectability of C60+ bands

Gas phase spectroscopic laboratory experiments for the buckminsterfullerene cation C60+ resulted in accurate rest wavelengths for five C60+ transitions that have been compared with diffuse interstellar bands (DIBs) in the near infra-red. Detecting these in astronomical spectra is difficult due to the strong contamination of ground-based spectra by atmospheric water vapor, to the presence of weak and shallow stellar lines and/or blending with other weak DIBs. The detection of the two strong bands has been claimed by several teams, and the three additional and weaker bands have been detected in a few sources. Certain recent papers have argued against the identification of C60+ based on spectral analyses claiming (i) a large variation in the ratio between the equivalent widths of the 9632 and 9577Å\: bands, (ii) a large redshift of the 9632Å\: band for the Orion star HD 37022, and (iii) the non-detection of the weaker 9428Å~DIB. Here we address these three points. (i) We show that the model stellar line correction for the 9632Å~DIB overestimates the difference between the strengths of the lines in giant and dwarf star spectra, casting doubts on the conclusions about the ratio variability. (ii) Using high quality stellar spectra from the ESO Diffuse Interstellar Bands Large Exploration Survey (EDIBLES), recorded with the ESO/Paranal Ultraviolet Echelle Spectrograph (UVES) in about the same atmospheric conditions, we find no wavelength shift in the 9632Å band towards HD 37022. (iii) Using EDIBLES spectra and data from the Echelle SpectroPolarimetric Device for the Observation of Stars (ESPaDOnS) at CFHT we show that the presence of a weak 9428Å band cannot be ruled out, even in the same observations that a previous study claimed it was not present.

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arXiv2018

Formation of interstellar methanol ice prior to the heavy CO freeze-out stage

The formation of methanol (CH3OH) on icy grain mantles during the star formation cycle is mainly associated with the CO freeze-out stage. Yet there are reasons to believe that CH3OH also can form at an earlier period of interstellar ice evolution in CO-poor and H2O-rich ices. This work focuses on CH3OH formation in a H2O-rich interstellar ice environment following the OH-mediated H-abstraction in the reaction, CH4 + OH. Experimental conditions are systematically varied to constrain the CH3OH formation yield at astronomically relevant temperatures. CH4, O2, and hydrogen atoms are co-deposited in an ultrahigh vacuum chamber at 10-20 K. OH radicals are generated by the H + O2 surface reaction. Temperature programmed desorption - quadrupole mass spectrometry (TPD-QMS) is used to characterize CH3OH formation, and is complemented with reflection absorption infrared spectroscopy (RAIRS) for CH3OH characterization and quantitation. CH3OH formation is shown to be possible by the sequential surface reaction chain, CH4 + OH -> CH3 + H2O and CH3 + OH -> CH3OH at 10-20 K. This reaction is enhanced by tunneling, as noted in a recent theoretical investigation (Lamberts et al. 2017). The CH3OH formation yield via the CH4 + OH route versus the CO + H route is approximately 20 times smaller for the laboratory settings studied. The astronomical relevance of the new formation channel investigated here is discussed.

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arXiv2018

Methanol ice co-desorption as a mechanism to explain cold methanol in the gas-phase

Methanol is formed via surface reactions on icy dust grains. Methanol is also detected in the gas-phase at temperatures below its thermal desorption temperature and at levels higher than can be explained by pure gas-phase chemistry. The process that controls the transition from solid state to gas-phase methanol in cold environments is not understood. The goal of this work is to investigate whether thermal CO desorption provides an indirect pathway for methanol to co-desorb at low temperatures. Mixed CH$_{3}$OH:CO/CH$_{4}$ ices were heated under UHV (ultra-high vacuum) conditions and ice contents are traced using RAIRS (reflection absorption IR spectroscopy), while desorbing species were detected mass spectrometrically. An updated gas-grain chemical network was used to test the impact of the results of these experiments. The physical model used is applicable for TW Hya, a protoplanetary disk in which cold gas-phase methanol has recently been detected. Methanol release together with thermal CO desorption is found to be an ineffective process in the experiments, resulting in an upper limit of $\leq$ 7.3 $\times$ 10$^{-7}$ CH3OH molecules per CO molecule over all ice mixtures considered. Chemical modelling based on the upper limits shows that co-desorption rates as low as 10$^{-6}$ CH$_{3}$OH molecules per CO molecule are high enough to release substantial amounts of methanol to the gas-phase at and around the location of the CO thermal desorption front in a protoplanetary disk. The impact of thermal co-desorption of CH3OH with CO as a grain-gas bridge mechanism is compared with that of UV induced photodesorption and chemisorption.

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arXiv2017

Infrared spectra of complex organic molecules in astronomically relevant ice matrices. I. Acetaldehyde, ethanol, and dimethyl ether

Context. The number of identified complex organic molecules (COMs) in inter- and circumstellar gas-phase environments is steadily increasing. Recent laboratory studies show that many such species form on icy dust grains. At present only smaller molecular species have been directly identified in space in the solid state. Accurate spectroscopic laboratory data of frozen COMs, embedded in ice matrices containing ingredients related to their formation scheme, are still largely lacking. Aims. This work provides infrared reference spectra of acetaldehyde (CH$_3$CHO), ethanol (CH$_3$CH$_2$OH), and dimethyl ether (CH$_3$OCH$_3$) recorded in a variety of ice environments and for astronomically relevant temperatures, as needed to guide or interpret astronomical observations, specifically for upcoming James Webb Space Telescope observations. Methods. Fourier transform transmission spectroscopy (500-4000 cm$^{-1}$ / 20-2.5 $μ$m, 1.0 cm$^{-1}$ resolution) was used to investigate solid acetaldehyde, ethanol and dimethyl ether, pure or mixed with water, CO, methanol, or CO:methanol. These species were deposited on a cryogenically cooled infrared transmissive window at 15~K. A heating ramp was applied, during which IR spectra were recorded until all ice constituents were thermally desorbed. Results. We present a large number of reference spectra that can be compared with astronomical data. Accurate band positions and band widths are provided for the studied ice mixtures and temperatures. Special efforts have been put into those bands of each molecule that are best suited for identification. For acetaldehyde the 7.427 and 5.803 $μ$m bands are recommended, for ethanol the 11.36 and 7.240 $μ$m bands are good candidates, and for dimethyl ether bands at 9.141 and 8.011 $μ$m can be used. All spectra are publicly available in the Leiden Database for Ice.

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arXiv2017

Searching for interstellar C60+ using a new method for high signal-to-noise HST/STIS spectroscopy

Due to recent advances in laboratory spectroscopy, the first optical detection of a very large molecule has been claimed in the diffuse interstellar medium (ISM): C60+ (ionized Buckminsterfullerene). Confirming the presence of this molecule would have significant implications regarding the carbon budget and chemical complexity of the ISM. Here we present results from a new method for ultra-high signal-to-noise (S/N) spectroscopy of background stars in the near infrared (at wavelengths 0.9-1 micron), using the Hubble Space Telescope Imaging Spectrograph (STIS) in a previously untested `STIS scan' mode. The use of HST provides the crucial benefit of eliminating the need for error-prone telluric correction methods in the part of the spectrum where the C60+ bands lie, and terrestrial water vapor contamination is severe. Our STIS spectrum of the heavily-reddened B0 star BD63\,1964 reaches an unprecedented S/N for this instrument ($\sim600-800$), allowing the detection of the diffuse interstellar band (DIB) at 9577 Å attributed to C60+ as well as new DIBs in the near-IR. Unfortunately, the presence of overlapping stellar lines, and the unexpected weakness of the C60+ bands in this sightline, prevents conclusive detection of the weaker C60+ bands. A probable correlation between the 9577 Å DIB strength and interstellar radiation field is identified, which suggests that more strongly-irradiated interstellar sightlines will provide the optimal targets for future C60+ searches.

astro-ph.GA↗

arXiv2017

Production of complex organic molecules: H-atom addition versus UV irradiation

Complex organic molecules (COMs) have been identified in different environments in star- forming regions. Laboratory studies show that COMs form in the solid state, on icy grains, typically following a non-energetic (atom-addition) or energetic (UV-photon absorption) trigger. So far, such studies have been largely performed for single processes. Here, we present the first work that quantitatively investigates both the relative importance and the cumulative effect of (non-)energetic processing. We focus on astronomically relevant CO:CH3OH = 4:1 ice analogues exposed to doses relevant for the collapse stage of dense clouds. Hydrogenation experiments result in the formation of methyl formate (MF HC(O)OCH3), glycolaldehyde (GA HC(O)CH2OH) and ethylene glycol (EG H2C(OH)CH2OH) at 14 K. The absolute abundances and the abundance fractions are found to be dependent on the H-atom/CO-CH3OH molecule ratios and on the overall deposition rate. In the case that ices are exposed to UV photons only, several different COMs are found. Typically, the abundance fractions are 0.2 for MF, 0.3 for GA and 0.5 for EG as opposed to the values found in pure hydrogenation experiments without UV in which MF is largely absent: 0.0, 0.2-0.6 and 0.8-0.4, respectively. In experiments where both are applied, overall COM abundances drop to about half of those found in the pure UV irradiation experiments, but the composition fractions are very similar. This implies COM ratios can be used as a diagnostic tool to derive the processing history of an ice. Solid-state branching ratios derived here for GA and EG compare well with observations, while the MF case cannot be explained by solid-state conditions investigated here.

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arXiv2017

The ALMA-PILS survey: Detection of CH$_{3}$NCO toward the low-mass protostar IRAS 16293-2422 and laboratory constraints on its formation

Methyl isocyanate (CH$_{3}$NCO) belongs to a select group of interstellar molecules considered to be relevant precursors in the formation of larger organic compounds, including those with peptide bonds. The molecule has only been detected in a couple of high-mass protostars and potentially on comets. A formation route on icy grains has been postulated for this molecule but experimental evidence is lacking. Here we extend the range of environments where methyl isocyanate is found, and unambiguously identify CH$_{3}$NCO through the detection of 43 unblended transitions in the ALMA Protostellar Interferometric Line Survey (PILS) of the low mass solar-type protostellar binary IRAS 16293-2422. The molecule is detected toward both components of the binary with a ratio HNCO/CH$_3$NCO $\sim$4--12. The isomers CH$_{3}$CNO and CH$_3$OCN are not identified, resulting in upper abundance ratios of CH$_{3}$NCO/CH$_{3}$CNO > 100 and CH$_{3}$NCO/CH$_3$OCN > 10. The resulting abundance ratios compare well with those found for related N-containing species toward high-mass protostars. To constrain its formation, a set of cryogenic UHV experiments is performed. VUV irradiation of CH$_{4}$:HNCO mixtures at 20 K strongly indicate that methyl isocyanate can be formed in the solid-state through CH$_{3}$ and (H)NCO recombinations. Combined with gas-grain models that include this reaction, the solid-state route is found to be a plausible scenario to explain the methyl isocyanate abundances found in IRAS 16293-2422.

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arXiv2016

H-atom addition and abstraction reactions in mixed CO, H2CO and CH3OH ices: an extended view on complex organic molecule formation

Complex organic molecules (COMs) have been observed not only in the hot cores surrounding low- and high- mass protostars, but also in cold dark clouds. Therefore, it is interesting to understand how such species can be formed without the presence of embedded energy sources. We present new laboratory experiments on the low-temperature solid state formation of three complex molecules: methyl formate (HC(O)OCH3), glycolaldehyde (HC(O)CH2OH) and ethylene glycol (H2C(OH)CH2OH), through recombination of free radicals formed via H-atom addition and abstraction reactions at different stages in the CO-H2CO-CH3OH hydrogenation network at 15 K. The experiments extend previous CO hydrogenation studies and aim at resembling the physical&chemical conditions typical of the CO freeze-out stage in dark molecular clouds, when H2CO and CH3OH form by recombination of accreting CO molecules and H-atoms on ice grains. We confirm that H2CO, once formed through CO hydrogenation, not only yields CH3OH through ongoing H-atom addition reactions, but is also subject to H-atom-induced abstraction reactions, yielding CO again. In a similar way, H2CO is also formed in abstraction reactions involving CH3OH. The dominant methanol H-atom abstraction product is expected to be CH2OH, while H-atom additions to H2CO should at least partially proceed through CH3O intermediate radicals. The occurrence of H-atom abstraction reactions in ice mantles leads to more reactive intermediates (HCO, CH3O and CH2OH) than previously thought, when assuming sequential H-atom addition reactions only. This enhances the probability to form COMs through radical-radical recombination without the need of UV photolysis or cosmic rays as external triggers.

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arXiv2015

Low-temperature chemistry between water and hydroxyl radicals: H/D isotopic effects

Sets of systematic laboratory experiments are presented -- combining Ultra High Vacuum cryogenic and plasma-line deposition techniques -- that allow us to compare H/D isotopic effects in the reaction of H2O (D2O) ice with the hydroxyl radical OD (OH). The latter is known to play a key role as intermediate species in the solid-state formation of water on icy grains in space. The main finding of our work is that the reaction H2O + OD --> OH + HDO occurs and that this may affect the HDO/H2O abundances in space. The opposite reaction D2O + OH --> OD + HDO is much less effective, and also given the lower D2O abundances in space not expected to be of astronomical relevance. The experimental results are extended to the other four possible reactions between hydroxyl and water isotopes and are subsequently used as input for Kinetic Monte Carlo simulations. This way we interpret our findings in an astronomical context, qualitatively testing the influence of the reaction rates.

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arXiv2014

Pore evolution in interstellar ice analogues: simulating the effects of temperature increase

Context. The level of porosity of interstellar ices - largely comprised of amorphous solid water (ASW) - contains clues on the trapping capacity of other volatile species and determines the surface accessibility that is needed for solid state reactions to take place. Aims. Our goal is to simulate the growth of amorphous water ice at low temperature (10 K) and to characterize the evolution of the porosity (and the specific surface area) as a function of temperature (from 10 to 120 K). Methods. Kinetic Monte Carlo simulations are used to mimic the formation and the thermal evolution of pores in amorphous water ice. We follow the accretion of gas-phase water molecules as well as their migration on surfaces with different grid sizes, both at the top growing layer and within the bulk. Results. We show that the porosity characteristics change substantially in water ice as the temperature increases. The total surface of the pores decreases strongly while the total volume decreases only slightly for higher temperatures. This will decrease the overall reaction efficiency, but in parallel, small pores connect and merge, allowing trapped molecules to meet and react within the pores network, providing a pathway to increase the reaction efficiency. We introduce pore coalescence as a new solid state process that may boost the solid state formation of new molecules in space and has not been considered so far.

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arXiv2014

Detection of vibronic bands of C$_3$ in a translucent cloud towards HD 169454

We report the detection of eight vibronic bands of C$_3$, seven of which have been hitherto unobserved in astrophysical objects, in the translucent cloud towards HD~169454. Four of these bands are also found towards two additional objects: HD~73882 and HD~154368. Very high signal-to-noise ratio ($\sim$1000 and higher) and high resolving power ($R=80,000$) UVES-VLT spectra (Paranal, Chile) allow for detecting novel spectral features of C$_3$, even revealing weak perturbed features in the strongest bands. The work presented here provides the most complete spectroscopic survey of the so far largest carbon chain detected in translucent interstellar clouds. High-quality laboratory spectra of C$_3$ are measured using cavity ring-down absorption spectroscopy in a supersonically expanding hydrocarbon plasma, to support the analysis of the identified bands towards HD~169454. A column density of N(C$_3$) = $(6.6 \pm 0.2) \times 10^{12}$ cm$^{-2}$ is inferred and the excitation of the molecule exhibits two temperature components; $T_{exc}= 22 \pm 1$ K for the low-$J$ states and $T_{exc}= 187 \pm 25$ K for the high-$J$ tail. The rotational excitation of C$_3$ is reasonably well explained by models involving a mechanism including inelastic collisions, formation and destruction of the molecule, and radiative pumping in the far-infrared. These models yield gas kinetic temperatures comparable to those found for $T_{exc}$. The assignment of spectral features in the UV-blue range 3793-4054 Å may be of relevance for future studies aiming at unravelling spectra to identify interstellar molecules associated with the diffuse interstellar bands (DIBs).

astro-ph.GA↗

arXiv2013

Porosity measurements of interstellar ice mixtures using optical laser interference and extended effective medium approximations

Aims. This article aims to provide an alternative method of measuring the porosity of multi-phase composite ices from their refractive indices and of characterising how the abundance of a premixed contaminant (e.g., CO2) affects the porosity of water-rich ice mixtures during omni-directional deposition. Methods. We combine optical laser interference and extended effective medium approximations (EMAs) to measure the porosity of three astrophysically relevant ice mixtures: H2O:CO2=10:1, 4:1, and 2:1. Infrared spectroscopy is used as a benchmarking test of this new laboratory-based method. Results. By independently monitoring the O-H dangling modes of the different water-rich ice mixtures, we confirm the porosities predicted by the extended EMAs. We also demonstrate that CO2 premixed with water in the gas phase does not significantly affect the ice morphology during omni-directional deposition, as long as the physical conditions favourable to segregation are not reached. We propose a mechanism in which CO2 molecules diffuse on the surface of the growing ice sample prior to being incorporated into the bulk and then fill the pores partly or completely, depending on the relative abundance and the growth temperature.

astro-ph.IM↗

arXiv2010

Reaction Networks For Interstellar Chemical Modelling: Improvements and Challenges

We survey the current situation regarding chemical modelling of the synthesis of molecules in the interstellar medium. The present state of knowledge concerning the rate coefficients and their uncertainties for the major gas-phase processes -- ion-neutral reactions, neutral-neutral reactions, radiative association, and dissociative recombination -- is reviewed. Emphasis is placed on those reactions that have been identified, by sensitivity analyses, as 'crucial' in determining the predicted abundances of the species observed in the interstellar medium. These sensitivity analyses have been carried out for gas-phase models of three representative, molecule-rich, astronomical sources: the cold dense molecular clouds TMC-1 and L134N, and the expanding circumstellar envelope IRC +10216. Our review has led to the proposal of new values and uncertainties for the rate coefficients of many of the key reactions. The impact of these new data on the predicted abundances in TMC-1 and L134N is reported. Interstellar dust particles also influence the observed abundances of molecules in the interstellar medium. Their role is included in gas-grain, as distinct from gas-phase only, models. We review the methods for incorporating both accretion onto, and reactions on, the surfaces of grains in such models, as well as describing some recent experimental efforts to simulate and examine relevant processes in the laboratory. These efforts include experiments on the surface-catalysed recombination of hydrogen atoms, on chemical processing on and in the ices that are known to exist on the surface of interstellar grains, and on desorption processes, which may enable species formed on grains to return to the gas-phase.

astro-ph.GA↗