Spiers Memorial Lecture: Astrochemistry at high resolution.

Astrochemistry is the science that studies the chemistry in the Universe, namely the combination of two fields: astronomy and chemistry. It started about fifty years ago and it has progressed in leaps and bounds, often triggered by the advent of new telescopes. From the collection of new interstellar molecule detections, astrochemistry has evolved more and more in the quest to understand how they are formed and thrive in the harsh conditions of the interstellar medium. Collaboration between astronomers and chemists has never been more necessary than today, when new powerful astronomical facilities provide us with ever sharper images of the regions where interstellar molecules are present. This review focuses on the special case of interstellar complex organic molecules (iCOMs), one the most debated astrochemical fields and where the astronomers-chemists collaboration and synergy is indispensable. The review will go through the various phases of the formation of planetary system similar to the solar system, providing the most recent observational picture at each step. The current scenarios of the iCOMs formation will be laid down and the critical chemical processes and quantities involved in each of them will be discussed. The major goal of this review is not only to present the progress but, more importantly, to highlight the many areas of uncertainty. A few specific cases will be discussed to give practical examples of why the huge challenge that represents the formation of iCOMs can only be won if chemists and astronomers work together.

Streamers feeding the SVS13-A protobinary system: astrochemistry reveals accretion shocks?

We report Atacama Large Millimeter/submillimeter Array (ALMA) high-angular resolution (∼50 au) observations of the binary system SVS13-A. More specifically, we analyse deuterated water (HDO) and sulfur dioxide (SO2) emission. The molecular emission is associated with both the components of the binary system, VLA4A and VLA4B. The spatial distribution is compared to that of formamide (NH2CHO), previously analysed in the system. Deuterated water shows an additional emitting component spatially coincident with the dust-accretion streamer, at a distance ≥120 au from the protostars, and at blue-shifted velocities (>3 km s-1 from the systemic velocities). We investigate the origin of the molecular emission in the streamer, in light of thermal sublimation temperatures calculated using updated binding energy (BE) distributions. We propose that the observed emission is produced by an accretion shock at the interface between the accretion streamer and the disk of VLA4A. Thermal desorption is not completely excluded in case the source is actively experiencing an accretion burst.

Theoretical Distribution of the Ammonia Binding Energy at Interstellar Icy Grains: A New Computational Framework.

The binding energies (BE) of molecules on the interstellar grains are crucial in the chemical evolution of the interstellar medium (ISM). Both temperature-programmed desorption (TPD) laboratory experiments and quantum chemistry computations have often provided, so far, only single values of the BE for each molecule. This is a severe limitation, as the ices enveloping the grain mantles are structurally amorphous, giving rise to a manifold of possible adsorption sites, each with different BEs. However, the amorphous ice nature prevents the knowledge of structural details, hindering the development of a common accepted atomistic icy model. In this work, we propose a computational framework that closely mimics the formation of the interstellar grain mantle through a water by water accretion. On that grain, an unbiased random (but well reproducible) positioning of the studied molecule is then carried out. Here we present the test case of NH3, a ubiquitous species in the molecular ISM. We provide the BE distribution computed by a hierarchy approach, using the semiempirical xTB-GFN2 as a low-level method to describe the whole icy cluster in combination with the B97D3 DFT functional as a high-level method on the local zone of the NH3 interaction. The final ZPE-corrected BE is computed at the ONIOM(DLPNO-CCSD(T)//B97D3:xTB-GFN2) level, ensuring the best cost/accuracy ratio. The main peak of the predicted NH3 BE distribution is in agreement with experimental TPD and computed data in the literature. A second broad peak at very low BE values is also present, which has never been detected before. It may provide the solution to a longstanding puzzle about the presence of gaseous NH3 also observed in cold ISM objects.

Computer Generated Realistic Interstellar Icy Grain Models: Physicochemical Properties and Interaction with NH3.

Interstellar grains are composed by a rocky core (usually amorphous silicates) covered by an icy mantle, the most abundant molecule being H2O followed by CO, CO2, NH3, and also radicals in minor quantities. In dense molecular clouds, gas-phase chemical species freeze onto the grain surface, making it an important reservoir of molecular diversity/complexity whose evolution leads to interstellar complex organic molecules (iCOMs). Many different models of water clusters have appeared in the literature, but without a systematic study on the properties of the grain (such as the H-bonds features, the oxygen radial distribution function, the dangling species present on the mantle surface, the surface electrostatic potential, etc.). In this work, we present a computer procedure (ACO-FROST) grounded on the newly developed semiempirical GFN2 tight-binding quantum mechanical method and the GFN-FF force field method to build-up structures of amorphous ice of large size. These methods show a very favorable accuracy/cost ratio as they are ideally designed to take noncovalent interactions into account. ACO-FROST program can be tuned to build grains of different composition mimicking dirty icy grains. These icy grain models allow studying the adsorption features (structure, binding energy, vibrational frequencies, etc.) of relevant species on a large variety of adsorption sites so to obtain a statistically meaningful distribution of the physicochemical properties of interest to be transferred in numerical models. As a test case, we computed the binding energy of ammonia adsorbed at the different sites of the icy grain surface, showing a broad distribution not easily accounted for by other more size limited icy grain models. Our method is also the base for further refinements, adopting the present grain in a more rigorous QM:MM treatment, capable of giving binding energies within the chemical accuracy.

Tracing the Primordial Chemical Life of Glycine: A Review from Quantum Chemical Simulations.

Glycine (Gly), NH2CH2COOH, is the simplest amino acid. Although it has not been directly detected in the interstellar gas-phase medium, it has been identified in comets and meteorites, and its synthesis in these environments has been simulated in terrestrial laboratory experiments. Likewise, condensation of Gly to form peptides in scenarios resembling those present in a primordial Earth has been demonstrated experimentally. Thus, Gly is a paradigmatic system for biomolecular building blocks to investigate how they can be synthesized in astrophysical environments, transported and delivered by fragments of asteroids (meteorites, once they land on Earth) and comets (interplanetary dust particles that land on Earth) to the primitive Earth, and there react to form biopolymers as a step towards the emergence of life. Quantum chemical investigations addressing these Gly-related events have been performed, providing fundamental atomic-scale information and quantitative energetic data. However, they are spread in the literature and difficult to harmonize in a consistent way due to different computational chemistry methodologies and model systems. This review aims to collect the work done so far to characterize, at a quantum mechanical level, the chemical life of Gly, i.e., from its synthesis in the interstellar medium up to its polymerization on Earth.

Non-energetic Formation of Ethanol via CCH Reaction with Interstellar H2O Ices. A Computational Chemistry Study.

Ethanol (CH3CH2OH) is a relatively common molecule, often found in star-forming regions. Recent studies suggest that it could be a parent molecule of several so-called interstellar complex organic molecules (iCOMs). However, the formation route of this species remains under debate. In the present work, we study the formation of ethanol through the reaction of CCH with one H2O molecule belonging to the ice as a test case to investigate the viability of chemical reactions based on a "radical + ice component" scheme as an alternative mechanism for the synthesis of iCOMs, beyond the usual radical-radical coupling. This has been done by means of DFT calculations adopting two clusters of 18 and 33 water molecules as ice models. Results indicate that CH3CH2OH can potentially be formed by this proposed reaction mechanism. The reaction of CCH with H2O on the water ice clusters can be barrierless (because of the help of boundary icy water molecules acting as proton-transfer assistants), leading to the formation of vinyl alcohol precursors (H2CCOH and CHCHOH). Subsequent hydrogenation of vinyl alcohol yielding ethanol is the only step presenting a low activation energy barrier. We finally discuss the astrophysical implications of these findings.

Hydrogen molecular ions and the violent birth of the Solar System.

Many pieces of evidence indicate that the Solar System youth was marked by violent processes: among others, high fluxes of energetic particles (greater than or equal to 10 MeV) are unambiguously recorded in meteoritic material, where an overabundance of the short-lived 10Be products is measured. Several hypotheses have been proposed to explain from where these energetic particles originate, but there is no consensus yet, mostly because of the scarcity of complementary observational constraints. In general, the reconstruction of the past history of the Solar System is best obtained by simultaneously considering what we know of it and of similar systems nowadays in formation. However, when it comes to studying the presence of energetic particles in young forming stars, we encounter the classical problem of the impossibility of directly detecting them toward the emitting source (analogously to what happens to galactic cosmic rays). Yet, exploiting the fact that energetic particles, such as cosmic rays, create [Formula: see text] and that an enhanced abundance of [Formula: see text] causes dramatic changes on the overall gas chemical composition, we can indirectly estimate the flux of energetic particles. This contribution provides an overview of the search for solar-like protostars permeated by energetic particles and the discovery of a protocluster, OMC-2 FIR4, where the phenomenon is presently occurring. This article is part of a discussion meeting issue 'Advances in hydrogen molecular ions: H3+, H5+ and beyond'.

Silicate-mediated interstellar water formation: A theoretical study.

Water is one of the most abundant molecules in the form of solid ice phase in the different regions of the interstellar medium (ISM). This large abundance cannot be properly explained by using only traditional low temperature gas-phase reactions. Thus, surface chemical reactions are believed to be major synthetic channels for the formation of interstellar water ice. Among the different proposals, hydrogenation of atomic O (i.e., 2H + O → H2O) is a chemically "simple" and plausible reaction toward water formation occurring on the surfaces of interstellar grains. Here, novel theoretical results concerning the formation of water adopting this mechanism on the crystalline (010) Mg2SiO4 surface (a unequivocally identified interstellar silicate) are presented. The investigated reaction aims to simulate the formation of the first water ice layer covering the silicate core of dust grains. Adsorption of the atomic O as a first step of the reaction has been computed, results indicating that a peroxo ( O 2 2 - ) group is formed. The following steps involve the adsorption, diffusion and reaction of two successive H atoms with the adsorbed O atom. Results indicate that H diffusion on the surface has barriers of 4-6 kcal mol-1, while actual formation of OH and H2O present energy barriers of 22-23 kcal mol-1. Kinetic study results show that tunneling is crucial for the occurrence of the reactions and that formation of OH and H2O are the bottlenecks of the overall process. Several astrophysical implications derived from the theoretical results are provided as concluding remarks.

Change in the chemical composition of infalling gas forming a disk around a protostar.

IRAS 04368+2557 is a solar-type (low-mass) protostar embedded in a protostellar core (L1527) in the Taurus molecular cloud, which is only 140 parsecs away from Earth, making it the closest large star-forming region. The protostellar envelope has a flattened shape with a diameter of a thousand astronomical units (1 AU is the distance from Earth to the Sun), and is infalling and rotating. It also has a protostellar disk with a radius of 90 AU (ref. 6), from which a planetary system is expected to form. The interstellar gas, mainly consisting of hydrogen molecules, undergoes a change in density of about three orders of magnitude as it collapses from the envelope into the disk, while being heated from 10 kelvin to over 100 kelvin in the mid-plane, but it has hitherto not been possible to explore changes in chemical composition associated with this collapse. Here we report that the unsaturated hydrocarbon molecule cyclic-C3H2 resides in the infalling rotating envelope, whereas sulphur monoxide (SO) is enhanced in the transition zone at the radius of the centrifugal barrier (100 ± 20 AU), which is the radius at which the kinetic energy of the infalling gas is converted to rotational energy. Such a drastic change in chemistry at the centrifugal barrier was not anticipated, but is probably caused by the discontinuous infalling motion at the centrifugal barrier and local heating processes there.

Theoretical investigation of the isomerization of trans-HCOH to H2CO: an example of a water-catalyzed reaction.

A concerted hydrogen atom transfer mechanism has been elucidated for the isomerization of trans-HCOH to H(2)CO using a variety of ab initio and density functional theory methods. This work places specific emphasis on the role water molecules can play as a catalyst for this reaction and the mechanism by which this is achieved. This is of particular importance in the context of molecular ices in the interstellar medium because the presence of water in this reaction reduces the activation energy by at least 80%, which is accompanied by a significant enhancement of the reaction rate, at ≤300 K.

Observations and models of deuterated H3+ in proto-planetary disks.

Young, gas-rich proto-planetary disks orbiting around solar-type young stars represent a crucial phase in disk evolution and planetary formation. Of particular relevance is to observationally track the evolution of the gas, which governs the overall evolution of the disk and is eventually dispersed. However, the bulk of the mass resides in the plane, which is so cold and dense that virtually all heavy-element-bearing molecules freeze out onto the dust grains and disappear from the gas phase. In this paper, we show that the ground-state ortho-H2D+ transition is the best, if not the only, tracer of the disk-plane gas. We report the theoretical models of the chemical structure of the plane of the disk, where the deuterated forms of H3+, including H2D+, play a major role. We also compare the theoretical predictions with the observations obtained towards the disk of the young star DM Tau and show that the ionization rate is probably enhanced there, perhaps owing to the penetration of X-rays from the central object through the disk plane. We conclude by remarking that the ground-state ortho-H2D+ transition is such a powerful diagnostic that it may also reveal the matter in the dark halos of external galaxies, if it is hidden in cold, dense and small clouds, as several theories predict.