Grain-surface Reactions Research Articles

Gas-Phase vs. Grain-Surface Formation of Interstellar Complex Organic Molecules: A Comprehensive Quantum-Chemical Study

Several organic chemical compounds (the so-called interstellar complex organic molecules, iCOMs) have been identified in the interstellar medium (ISM). Examples of iCOMs are formamide (HCONH2), acetaldehyde (CH3CHO), methyl formate (CH3OCHO), or formic acid (HCOOH). iCOMs can serve as precursors of other organic molecules of enhanced complexity, and hence they are key species in chemical evolution in the ISM. The formation of iCOMs is still a subject of a vivid debate, in which gas-phase or grain-surface syntheses have been postulated. In this study, we investigate the grain-surface-formation pathways for the four above-mentioned iCOMs by transferring their primary gas-phase synthetic routes onto water ice surfaces. Our objective is twofold: (i) to identify potential grain-surface-reaction mechanisms leading to the formation of these iCOMs, and (ii) to decipher either parallelisms or disparities between the gas-phase and the grain-surface reactions. Results obtained indicate that the presence of the icy surface modifies the energetic features of the reactions compared to the gas-phase scenario, by increasing some of the energy barriers. Therefore, the investigated gas-phase mechanisms seem unlikely to occur on the icy grains, highlighting the distinctiveness between the gas-phase and the grain-surface chemistry.

Quantum mechanical modelling of the grain-surface formation of acetaldehyde on H2O:CO dirty ice surfaces

ABSTRACTAcetaldehyde (CH3CHO) is one of the most detected interstellar complex organic molecules (iCOMs) in the interstellar medium (ISM). These species have a potential biological relevance, as they can be precursors of more complex species from which life could have emerged. The formation of iCOMs in the ISM is a challenge and a matter of debate, whether gas-phase, grain-surface chemistry, or both are needed for their synthesis. In the gas-phase, CH3CHO can be efficiently synthesized from ethanol and/or ethyl radical. On the grain-surfaces, radical–radical recombinations were traditionally invoked. However, several pitfalls have been recently identified, such as the presence of energy barriers and competitive side reactions (i.e. H abstractions). Here, we investigate a new grain-surface reaction pathway for the formation of acetaldehyde, namely the reaction between CH3 and a CO molecule of a dirty water/CO ice followed by hydrogenation of its product, CH3CO. To this end, we carried out ab initio computations of the reaction occurring on an ice composed of 75 per cent water and 25 per cent CO molecules. We found that the CH3 + CO(ice) reaction exhibits barriers difficult to overcome in the ISM, either adopting a Langmuir–Hinshelwood or an Eley–Rideal mechanism. The subsequent hydrogenation step is found to be barrierless, provided that the two reacting species have the correct orientation. Therefore, this pathway seems unlikely to occur in the ISM.

Chemistry of NH2OH and its related species in the ISM

ABSTRACT Hydroxylamine (NH2OH) is a key precursor of both the formation of amino acids and the concurrent synthesis of pyrimidine and purine nucleosides. Recently, NH2OH was detected towards the quiescent molecular cloud G+0.693-0.027, which is located in the Galactic Centre. In this study, we construct the chemical network for NH2OH and its related species via quantum chemical calculations, and simulate their chemistry using the astrochemical code Nautilus in isothermal models and shock models. According to the disagreement distance formula and molecular abundance ratios, we acquire the best-fitting isothermal model T18 and the best-fitting C-shock model S2, respectively. Of these two models, S2 is more suitable for G+0.693-0.027 due to its reproduction of abundances of all considered molecules. From the model, we found that NH2OH and CH3NH2 are mainly formed on grain surfaces, while HNCN and CH2NH, which are the post-shock tracers, are produced by both gas-phase and grain-surface reactions. Our chemical modelling also agrees with the observed abundances or upper limits of NH2OH and its related species towards IRAS 16293-2422 B and Sgr B2(N). Moreover, we predict that NH2OH and the undiscovered species H2NO and HNOH are of high abundance, thus are detectable in cold clouds and pre-stellar cores, and in G+0.693-0.027, respectively.

Circumplanetary disk ices

Context. The subsurface oceans of icy satellites are among the most compelling among the potentially habitable environments in our Solar System. The question of whether a liquid subsurface layer can be maintained over geological timescales depends on its chemical composition. The composition of icy satellites is linked to that of the circumplanetary disk (CPD) in which they form. The CPD accretes material from the surrounding circumstellar disk in the vicinity of the planet, however, the degree of chemical inheritance is unclear. Aims. We aim to investigate the composition of ices in chemically reset or inherited circumplanetary disks to inform interior modeling and the interpretation of in situ measurements of icy solar system satellites, with an emphasis on the Galilean moon system. Methods. We used the radiation-thermochemical code ProDiMo to produce circumplanetary disk models and then extract the ice composition from time-dependent chemistry, incorporating gas-phase and grain-surface reactions. Results. The initial sublimation of ices during accretion may result in a CO2 -rich ice composition due to efficient OH formation at high gas densities. In the case of a Jovian CPD, the sublimation of accreted ices results in a CO2 iceline between the present-day orbits of Ganymede and Callisto. Sublimated ammonia ice is destroyed by background radiation while drifting towards the CPD midplane. Liberated nitrogen becomes locked in N2 due to efficient self-shielding, leaving ices depleted of ammonia. A significant ammonia ice component remains only when ices are inherited from the circumstellar disk. Conclusions. The observed composition of the Galilean moons is consistent with the sublimation of ices during accretion onto the CPD. In this scenario, the Galilean moon ices are nitrogen-poor and CO2 on Callisto is endogenous and primordial. The ice composition is significantly altered after an initial reset of accreted circumstellar ice. The chemical history of the Galilean moons stands in contrast to the Saturnian system, where the composition of the moons corresponds more closely with the directly inherited circumstellar disk material.

Grain-Surface Hydrogen-Addition Reactions as a Chemical Link Between Cold Cores and Hot Corinos: The Case of H2CCS and CH3CH2SH.

Recently, searches were made for H2CCS and HCCSH in a variety of interstellar environments─all of them resulted in nondetections of these two species. Recent findings have indicated the importance of destruction pathways, e.g., with atomic hydrogen, in explaining the consistent nondetection of other species, such as the H2C3O family of isomers. We have thus performed ab initio calculations looking at reactions of H2CCS, HCCSH, and related species with atomic hydrogen. Our results show that H2CCS and HCCSH are both destroyed barrierlessly by atomic hydrogen, thus providing a plausible explanation for the nondetections. We further find that subsequent reactions with atomic hydrogen can barrierlessly lead to CH3CH2SH, which has been detected. Astrochemical simulations including these reactions result not only in reproducing the observed abundance of H2CCS in TMC-1 but also show that CH3CH2SH, produced via our H-addition pathways and subsequently trapped on grains, can desorb in warmer sources up to abundances that match previous observations of CH3CH2SH in Orion KL. These results, taken together, point to the importance of grain-surface H-atom addition reactions and highlight the chemical links between cold prestellar cores and their subsequent, warmer evolutionary stages.

The GUAPOS project: G31.41+0.31 Unbiased ALMA sPectral Observational Survey

Context.One of the goals of astrochemistry is to understand the degree of chemical complexity that can be reached in star-forming regions, along with the identification of precursors of the building blocks of life in the interstellar medium. To answer such questions, unbiased spectral surveys with large bandwidth and high spectral resolution are needed, in particular, to resolve line blending in chemically rich sources and identify each molecule (especially for complex organic molecules). These kinds of observations have already been successfully carried out, primarily towards the Galactic Center, a region that shows peculiar environmental conditions.Aims.We present an unbiased spectral survey of one of the most chemically rich hot molecular cores located outside the Galactic Center, in the high-mass star-forming region G31.41+0.31. The aim of this 3mm spectral survey is to identify and characterize the physical parameters of the gas emission in different molecular species, focusing on complex organic molecules. In this first paper, we present the survey and discuss the detection and relative abundances of the three isomers of C2H4O2: methyl formate, glycolaldehyde, and acetic acid.Methods.Observations were carried out with the ALMA interferometer, covering all of band 3 from 84 to 116 GHz (~32 GHz bandwidth) with an angular resolution of 1.2′′ × 1.2′′ (~ 4400 au × 4400 au) and a spectral resolution of ~0.488 MHz (~1.3−1.7 km s−1). The transitions of the three molecules have been analyzed with the software XCLASS to determine the physical parameters of the emitted gas.Results.All three isomers were detected with abundances of (2 ± 0.6) × 10−7, (4.3−8) × 10−8, and (5.0 ± 1.4) × 10−9for methyl formate, acetic acid, and glycolaldehyde, respectively. Methyl formate and acetic acid abundances are the highest detected up to now, if compared to sources in the literature. The size of the emission varies among the three isomers with acetic acid showing the most compact emission while methyl formate exhibits the most extended emission. Different chemical pathways, involving both grain-surface chemistry and cold or hot gas-phase reactions, have been proposed for the formation of these molecules, but the small number of detections, especially of acetic acid and glycolaldehyde, have made it very difficult to confirm or discard the predictions of the models. The comparison with chemical models in literature suggests the necessity of grain-surface routes for the formation of methyl formate in G31, while for glycolaldehyde both scenarios could be feasible. The proposed grain-surface reaction for acetic acid is not capable of reproducing the observed abundance in this work, while the gas-phase scenario should be further tested, given the large uncertainties involved.

Mapping observations of complex organic molecules around Sagittarius B2 with the ARO 12 m telescope

ABSTRACT We have performed high-sensitivity mapping observations of several complex organic molecules around Sagittarius B2 with the ARO 12 m telescope at 3 mm wavelength. Based on their spatial distribution, molecules can be classified as either ‘extended’, those detected not only in Sgr B2(N) and Sgr B2(M), or ‘compact’, those only detected toward or near Sgr B2(N) and Sgr B2(M). The ‘extended’ molecules include glycolaldehyde (CH2OHCHO), methyl formate (CH3OCHO), formic acid (t-HCOOH), ethanol (C2H5OH) and methyl amine (CH3NH2), while the ‘compact’ molecules include dimethyl ether (CH3OCH3), ethyl cyanide (C2H5CN), and amino acetonitrile (H2NCH2CN). These ‘compact’ molecules are likely produced under strong UV radiation, while the ‘extended’ molecules are likely formed at low temperatures, via gas-phase or grain-surface reactions. The spatial distribution of ‘warm’ CH2OHCHO at 89 GHz differs from the spatial distribution of ‘cold’ CH2OHCHO observed at 13 GHz. We found evidence for an overabundance of CH2OHCHO compared to that expected from the gas-phase model, which indicates that grain-surface reactions are necessary to explain the origin of CH2OHCHO in Sagittarius B2. Grain-surface reactions are also needed to explain the correlation between the abundances of ‘cold’ CH2OHCHO and C2H5OH. These results demonstrate the importance of grain-surface chemistry in the production of complex organic molecules.

The ALMA-PILS survey: propyne (CH3CCH) in IRAS 16293–2422

Context. Propyne (CH3CCH), also known as methyl acetylene, has been detected in a variety of environments, from Galactic star-forming regions to extragalactic sources. These molecules are excellent tracers of the physical conditions in star-forming regions, allowing the temperature and density conditions surrounding a forming star to be determined. Aims. This study explores the emission of CH3CCH in the low-mass protostellar binary, IRAS 16293–2422, and examines the spatial scales traced by this molecule, as well as its formation and destruction pathways. Methods. Atacama Large Millimeter/submillimeter Array (ALMA) observations from the Protostellar Interferometric Line Survey (PILS) were used to determine the abundances and excitation temperatures of CH3CCH towards both protostars. This data allows us to explore spatial scales from 70 to 2400 au. This data is also compared with the three-phase chemical kinetics model MAGICKAL, to explore the chemical reactions of this molecule. Results. CH3CCH is detected towards both IRAS 16293A and IRAS 16293B, and is found the hot corino components, one around each source, in the PILS dataset. Eighteen transitions above 3σ are detected, enabling robust excitation temperatures and column densities to be determined in each source. In IRAS 16293A, an excitation temperature of 90 K and a column density of 7.8 × 1015 cm−2 best fits the spectra. In IRAS 16293B, an excitation temperature of 100 K and 6.8 × 1015 cm−2 best fits the spectra. The chemical modelling finds that in order to reproduce the observed abundances, both gas-phase and grain-surface reactions are needed. The gas-phase reactions are particularly sensitive to the temperature at which CH4 desorbs from the grains. Conclusions. CH3CCH is a molecule whose brightness and abundance in many different regions can be utilised to provide a benchmark of molecular variation with the physical properties of star-forming regions. It is essential when making such comparisons, that the abundances are determined with a good understanding of the spatial scale of the emitting region, to ensure that accurate abundances are derived.

CO destruction in protoplanetary disk midplanes: Inside versus outside the CO snow surface

Context. The total gas mass is one of the most fundamental properties of disks around young stars, because it controls their evolution and their potential to form planets. To measure disk gas masses, CO has long been thought to be the best tracer as it is readily detected at (sub)mm wavelengths in many disks. However, inferred gas masses from CO in recent ALMA observations of large samples of disks in the 1–5 Myr age range seem inconsistent with their inferred dust masses. The derived gas-to-dust mass ratios from CO are between one and two orders of magnitude lower than the ISM value of ~100 even if photodissociation and freeze-out are included. In contrast, Herschel measurements of hydrogen deuteride line emission of a few disks imply gas masses in line with gas-to-dust mass ratios of 100. This suggests that at least one additional mechanism is removing CO from the gas phase. Aims. Here we test the suggestion that the bulk of the CO is chemically processed and that the carbon is sequestered into less volatile species such as CO2, CH3OH, and CH4 in the dense, shielded midplane regions of the disk. This study therefore also addresses the carbon reservoir of the material which ultimately becomes incorporated into planetesimals. Methods. Using our gas-grain chemical code, we performed a parameter exploration and follow the CO abundance evolution over a range of conditions representative of shielded disk midplanes. Results. Consistent with previous studies, we find that no chemical processing of CO takes place on 1–3 Myr timescales for low cosmic-ray ionisation rates, <5 × 10−18 s−1. Assuming an ionisation rate of 10−17 s−1, more than 90% of the CO is converted into other species, but only in the cold parts of the disk below 30 K. This order of magnitude destruction of CO is robust against the choice of grain-surface reaction rate parameters, such as the tunnelling efficiency and diffusion barrier height, for temperatures between 20 and 30 K. Below 20 K there is a strong dependence on the assumed efficiency of H tunnelling. Conclusions. The low temperatures needed for CO chemical processing indicate that the exact disk temperature structure is important, with warm disks around luminous Herbig stars expected to have little to no CO conversion. In contrast, for cold disks around sun-like T Tauri stars, a large fraction of the emitting CO layer is affected unless the disks are young (<1 Myr). This can lead to inferred gas masses that are up to two orders of magnitude lower. Moreover, unless CO is locked up early in large grains, the volatile carbon composition of the icy pebbles and planetesimals forming in the midplane and drifting to the inner disk will be dominated by CH3OH, CO2 and/or hydrocarbons.

The Distribution and Excitation of CH3CN in a Solar Nebula Analog

Abstract Cometary studies suggest that the organic composition of the early Solar Nebula was rich in complex nitrile species such CH3CN. Recent ALMA detections in protoplanetary disks suggest that these species may be common during planet and comet formation, but connecting gas-phase measurements to cometary abundances first requires constraints on formation chemistry and distributions of these species. We present here the detection of seven spatially resolved transitions of CH3CN in the protoplanetary disk around the T-Tauri star TW Hya. Using a rotational diagram analysis, we find a disk-averaged column density of cm−2 and a rotational temperature of K. A radially resolved rotational diagram shows the rotational temperature to be constant across the disk, suggesting that the CH3CN emission originates from a layer at z/r ∼ 0.3. Through comparison of the observations with predictions from a disk chemistry model, we find that grain-surface reactions likely dominate CH3CN formation and that in situ disk chemistry is sufficient to explain the observed CH3CN column density profile without invoking inheritance from the protostellar phase. However, the same model fails to reproduce a solar system cometary abundance of CH3CN relative to H2O in the midplane, suggesting that either vigorous vertical mixing or some degree of inheritance from interstellar ices occurred in the Solar Nebula.

Modelling the molecular composition and nuclear-spin chemistryof collapsing pre-stellar sources★

We study the gravitational collapse of prestellar sources and the associated evolution of their chemical composition. We use the University of Grenoble Alpes Astrochemical Network (UGAN), which includes reactions involving the different nuclear--spin states of H2, H3+, and of the hydrides of carbon, nitrogen, oxygen, and sulfur, for reactions involving up to seven protons. In addition, species-to-species rate coefficients are provided for the ortho/para interconversion of the H3+ + H2 system and isotopic variants. The composition of the medium is followed from an initial steady state through the early phase of isothermal gravitational collapse. Both the freeze--out of the molecules on to grains and the coagulation of the grains were incorporated in the model. The predicted abundances and column densities of the spin isomers of ammonia and its deuterated forms are compared with those measured recently towards the prestellar cores H-MM1, L16293E, and Barnard B1. We find that gas--phase processes alone account satisfactorily for the observations, without recourse to grain-surface reactions. In particular, our model reproduces both the isotopologue abundance ratios and the ortho:para ratios of NH2D and NHD2 within observational uncertainties. More accurate observations are necessary to distinguish between full scrambling processes---as assumed in our gas-phase network---and direct nucleus- or atom-exchange reactions.

Kinetic Monte Carlo Simulations of the Grain-surface Back-diffusion Effect

Abstract Rate-equation models are a widely used and inexpensive tool for the simulation of interstellar chemistry under a range of physical conditions. However, their application to grain-surface chemical systems necessitates a number of simplifying assumptions, due to the requirement to treat only the total population of each species, using averaged rates, rather than treating each surface particle as an independent entity. While the outputs from rate-equation models are strictly limited to such population information, the inputs—in the form of the averaged rates that control the time-evolution of chemical populations—can be guided by the results from more exact simulation methods. Here, we examine the effects of back-diffusion, wherein particles diffusing on a surface revisit binding sites on the lattice, slowing the total reaction rate. While this effect has been studied for two-particle systems, its influence at greater surface coverage of reactants has not been explored. Results from two Monte Carlo kinetics models (one a 2D periodic lattice, the other the surface of a three-dimensionally realized grain) were used to develop a means to incorporate the grain-surface back-diffusion effect into rate-equation methods. The effects of grain size, grain morphology, and surface coverage on the magnitude of the back-diffusion effect were studied for the simple H+H reaction system. The results were fit with expressions that can be easily incorporated into astrochemical rate-equation models to accurately reproduce the effects of back-diffusion on grain-surface reaction rates. Back-diffusion reduces reaction rates by a maximum factor of around 5 for the canonical grain of ∼106 surface sites, but this falls to unity at close to full surface coverage.

Chemical evolution in planet-forming regions. Impact on volatile abundances and C/O ratios of planet-building material

AbstractConnecting the observed composition of exoplanets to their formation sites often involves comparing the atmospheric C/O ratio to a disk midplane model with a fixed chemical composition. In this scenario chemistry during the planet formation era is not considered. However, kinetic chemical evolution during the lifetime of the gaseous disk can change the relative abundances of volatile species, thus altering the C/O ratios of planetary building blocks. In our chemical evolition models we utilize a large network of gas-phase, grain-surface and gas-grain interaction reactions, thus providing a comprehensive treatment of chemistry. The results show that, if sufficient ionisation is present, then chemistry does alter the C/O ratios of gas and ice during the epoch of planet(esimal) formation. This modifies the picture of C/O ratios in disk midplanes defined simply by volatile ice lines in a midplane of fixed chemical composition. Chemical evolution thus needs to be addressed when predicting the makeup of planets and their atmospheres.

Hydrogen–deuterium substitution in solid ethanol by surface reactions at low temperatures

Ethanol (CH3CH2OH) is one of the most abundant complex organic molecules in star-forming regions. Despite its detection in the gas phase only, ethanol is believed to be formed by low-temperature grain-surface reactions. Methanol, the simplest alcohol, has been a target for observational, experimental, and theoretical studies in view of its deuterium enrichment in the interstellar medium; however, the deuterium chemistry of ethanol has not yet been an area of focus. Recently, deuterated dimethyl ether, a structural isomer of ethanol, was found in star-forming regions, indicating that deuterated ethanol can also be present in those environments. In this study, we performed laboratory experiments on the deuterium fractionation of solid ethanol at low temperatures through a reaction with deuterium (D) atoms at 10 K. Hydrogen (H)–D substitution, which increases the deuteration level, was found to occur on the ethyl group but not on the hydroxyl group. In addition, when deuterated ethanol (e.g. CD3CD2OD) solid was exposed to H atoms at 10 K, D–H substitution that reduced the deuteration level occurred on the ethyl group. Based on the results, it is likely that deuterated ethanol is present even under H-atom-dominant conditions in the interstellar medium.

Cometary ices in forming protoplanetary disc midplanes

Low-mass protostars are the extrasolar analogues of the natal Solar System. Sophisticated physicochemical models are used to simulate the formation of two protoplanetary discs from the initial prestellar phase, one dominated by viscous spreading and the other by pure infall. The results show that the volatile prestellar fingerprint is modified by the chemistry en route into the disc. This holds relatively independent of initial abundances and chemical parameters: physical conditions are more important. The amount of CO2 increases via the grain-surface reaction of OH with CO, which is enhanced by photodissociation of H2O ice. Complex organic molecules are produced during transport through the envelope at the expense of CH3OH ice. Their abundances can be comparable to that of methanol ice (few % of water ice) at large disc radii (R > 30 AU). Current Class II disc models may be underestimating the complex organic content. Planet population synthesis models may underestimate the amount of CO2 and overestimate CH3OH ices in planetesimals by disregarding chemical processing between the cloud and disc phases. The overall C/O and C/N ratios differ between the gas and solid phases. The two ice ratios show little variation beyond the inner 10 AU and both are nearly solar in the case of pure infall, but both are sub-solar when viscous spreading dominates. Chemistry in the protostellar envelope en route to the protoplanetary disc sets the initial volatile and prebiotically-significant content of icy planetesimals and cometary bodies. Comets are thus potentially reflecting the provenances of the midplane ices in the Solar Nebula.

Ethyl alcohol and sugar in comet C/2014 Q2 (Lovejoy).

The presence of numerous complex organic molecules (COMs; defined as those containing six or more atoms) around protostars shows that star formation is accompanied by an increase of molecular complexity. These COMs may be part of the material from which planetesimals and, ultimately, planets formed. Comets represent some of the oldest and most primitive material in the solar system, including ices, and are thus our best window into the volatile composition of the solar protoplanetary disk. Molecules identified to be present in cometary ices include water, simple hydrocarbons, oxygen, sulfur, and nitrogen-bearing species, as well as a few COMs, such as ethylene glycol and glycine. We report the detection of 21 molecules in comet C/2014 Q2 (Lovejoy), including the first identification of ethyl alcohol (ethanol, C2H5OH) and the simplest monosaccharide sugar glycolaldehyde (CH2OHCHO) in a comet. The abundances of ethanol and glycolaldehyde, respectively 5 and 0.8% relative to methanol (0.12 and 0.02% relative to water), are somewhat higher than the values measured in solar-type protostars. Overall, the high abundance of COMs in cometary ices supports the formation through grain-surface reactions in the solar system protoplanetary disk.

THE DISTRIBUTION AND CHEMISTRY OF H 2 CO IN THE DM TAU PROTOPLANETARY DISK

H$_2$CO ice on dust grains is an important precursor of complex organic molecules (COMs). H$_2$CO gas can be readily observed in protoplanetary disks and may be used to trace COM chemistry. However, its utility as a COM probe is currently limited by a lack of constraints on the relative contributions of two different formation pathways: on icy grain-surfaces and in the gas-phase. We use archival ALMA observations of the resolved distribution of H$_2$CO emission in the disk around the young low-mass star DM Tau to assess the relative importance of these formation routes. The observed H$_2$CO emission has a centrally peaked and radially broad brightness profile (extending out to 500 AU). We compare these observations with disk chemistry models with and without grain-surface formation reactions, and find that both gas and grain-surface chemistry are necessary to explain the spatial distribution of the emission. Gas-phase H$_2$CO production is responsible for the observed central peak, while grain-surface chemistry is required to reproduce the emission exterior to the CO snowline (where H$_2$CO mainly forms through the hydrogenation of CO ice before being non-thermally desorbed). These observations demonstrate that both gas and grain-surface pathways contribute to the observed H$_2$CO in disks, and that their relative contributions depend strongly on distance from the host star.

Interstellar processes: Ortho/para conversion, radiative association, and dissociative recombination

The study of the ortho-to-para ratio of assorted gas-phase interstellar molecules such as H2 ,H 2O, NH3 ,a nd H2O + has gained interest in recent years, based partially on new spectral observations of light hydrides by the Herschel Space Observatory. Although these ratios can yield valuable information about the thermal history of the interstellar cloud where the molecules are found, an understanding of how the ratios are determined involves a number of often poorly studied processes, which can include both gas-phase and grain-surface reactions. In this article, we consider the processes that determine the ortho-to-para ratio of the molecular ion H2O + in diffuse interstellar clouds and attempt to reproduce an unusual observed ratio for this ion. In addition to the study of ortho-to- para ratios, we look carefully at current uncertainties in the gas-phase formation of large neutral molecules in cold dense interstellar clouds via ion-neutral radiative association and dissociative recombination, among other processes.

Grain-surface reactions in molecular clouds: the effect of cosmic rays and quantum tunnelling

Grain-surface reactions play an essential role in interstellar chemistry, since dust grain catalyses reactions at its surface allowing for the formation of molecules. We used a chemical model in which both gas-phase and grain-surface reactions occur and studied particularly the diffusion mechanisms on the surface of the grains. Surface reactions can occur via thermal hopping when species cross over a potential barrier or via quantum tunneling when species cross through this barrier. We show that the thermal diffusion (hopping) can be much more efficient after a cosmic ray particle collides with a dust grain, heating it to a peak temperature of 70K. We present here the results of numerical simulations after including the quantum tunneling mechanism for species H, H2 and O and considering the effect of cosmic ray particle collision on the surface reactions. As a consequence, the gas-phase and grain-surface abundances are affected and we show that more complex molecules can be formed in molecular clouds.

Complex organic molecules in protoplanetary disks

(Abridged) Protoplanetary disks are vital objects in star and planet formation, possessing all the material which may form a planetary system orbiting the new star. We investigate the synthesis of complex organic molecules (COMs) in disks to constrain the achievable chemical complexity and predict species and transitions which may be observable with ALMA. We have coupled a 2D model of a protoplanetary disk around a T Tauri star with a gas-grain chemical network including COMs. We compare compare synthesised line intensities and calculated column densities with observations and determine those COMs which may be observable in future. COMs are efficiently formed in the disk midplane via grain-surface chemical reactions, reaching peak grain-surface fractional abundances 1e-6 - 1e-4 that of the H nuclei number density. COMs formed on grain surfaces are returned to the gas phase via non-thermal desorption; however, gas-phase species reach lower fractional abundances than their grain-surface equivalents, 1e-12 - 1e-7. Including the irradiation of grain mantle material helps build further complexity in the ice through the replenishment of grain-surface radicals which take part in further grain-surface reactions. There is reasonable agreement with several line transitions of H2CO observed towards several T Tauri star-disk systems. The synthesised line intensities for CH3OH are consistent with upper limits determined towards all sources. Our models suggest CH3OH should be readily observable in nearby protoplanetary disks with ALMA; however, detection of more complex species may prove challenging. Our grain-surface abundances are consistent with those derived from cometary comae observations providing additional evidence for the hypothesis that comets (and other planetesimals) formed via the coagulation of icy grains in the Sun's natal disk.