A series of catalytic reactions has been performed in our laboratory using olivine-type silicates (OTS) and SiC as catalysts for the conversion of carbon-containing molecules (such as acetylene, CO and methanol) to small organic molecules (C2H4, C3H3, CH3O) and also polycyclic aromatic hydrocarbons (PAHs). Experimentally, small-to-medium-sized gas-phase compounds such as PAHs, reaction intermediates and hydrocarbon compounds were detected in situ using the time-of-light mass-spectrometry technique. Solid deposition on the catalyst surface was examined by high-resolution transmission electron microscopy and thermo-gravimetric analysis techniques. Our laboratory results show that the conversion of acetylene to PAHs, the CO disproportionation reaction for producing CO2 and carbon deposition (graphitic and carbon nanostructures), and also the transformation of methanol to hydrocarbon compounds can easily be achieved with OTS as a catalyst. Furthermore, the conversion of acetylene to PAHs could also be achieved by SiC as the catalyst. It is proposed that these catalytic reactions mimic similar chemical processes in circumstellar envelopes (CSEs).

The formation of molecules in the interstellar medium is significantly driven by grain chemistry, ranging from simple (e.g. H2) to relatively complex (e.g. CH3OH) products. The movement of atoms and molecules on amorphous ice surfaces is not well constrained, and this is a quintessential component of surface chemistry. We show that ice structure created by utilizing an off-lattice Monte Carlo kinetics model is highly dependent on deposition parameters (i.e. angle, rate, and temperature). The model, thus far, successfully predicts the densities of deposition rate- and temperature-dependent laboratory experiments. The simulations indicate, when angle and deposition rate increase, the density decreases. On the other hand, temperature has the opposite effect and will increase the density. We can make ices with desired densities and monitor how molecules, like CO, percolate through H2O ice pores. The strength of this model lies in the ability to replicate TPD-like experiments by monitoring molecules diffusing on and desorbing from user-defined surfaces.

Gas chemistry is typically characterized comparing integrated intensities of different molecular species. With the advent of ALMA, chemistry is now resolved not only in space but also in velocity. When observed at high spectral resolution, most of the clouds, filaments, and cores in the solar neighbourhood show a complex internal structure with multiple velocity components. This intrinsic complexity should be disentangled in order to correctly interpret their chemical properties. We present the first results of the FIVE+ analysis technique combining both state-of-the-art structure reconstruction (2D), kinematic decomposition (+1D), and chemical analysis (+1D) in large molecular datasets.

We present first results of a new heterodyne spectrometer dedicated to high-resolution spectroscopy of molecules of astrophysical importance. The spectrometer, based on a room-temperature heterodyne receiver, is sensitive to frequencies between 75 and 110 GHz with an instantaneous bandwidth of currently 2.5 GHz in a single sideband. The system performance, in particular the sensitivity and stability, is evaluated. Proof of concept of this spectrometer is demonstrated by recording the emission spectrum of methyl cyanide, CH3CN. Compared to state-of-the-art radio telescope receivers the instrument is less sensitive by about one order of magnitude. Nevertheless, the capability for absolute intensity measurements can be exploited in various experiments, in particular for the interpretation of the ever richer spectra in the ALMA era. The ease of operation at room-temperature allows for long time integration, the fast response time for integration in chirped pulse instruments or for recording time dependent signals. Future prospects as well as limitations of the receiver for the spectroscopy of complex organic molecules (COMs) are discussed.

In this work, one intends to computationally simulate and investigate, via thermochemical calculations, how the chemical environment influences some molecular properties, such as IR spectra and absorption cross section, of individual species embedded in the solid phase employing the Polarized Continuum Model (PCM) approach. The trial molecules used here to check these effects are CO, CO2 and H2O. The solid phase (bulk ice) is simulated using different dielectric constant values representing different types of astrophysical ice at PCM approach. The effect of temperature is also investigated since it is known it affects the dielectric constant of the solvent medium.

A systematic study, using ion trap time-of-flight mass spectrometry, is presented for the photo-dissociation processes of Bisanthenquinone (Bq) cations, C28H12O2+, a ketone substituted Polycyclic Aromatic Hydrocarbon (PAH). The Bq cation fragments through sequential loss of the two neutral carbonyl (CO) units upon laser (626nm) irradiation, resulting in a PAH-like derivative C26H12+. Upon further irradiation, C26H12+ exhibits both stepwise dehydrogenation and C2/C2H2 loss fragmentation channels. Quantum chemistry calculations reveal a detailed picture for the first CO-loss, which involves a transition state with a barrier of ∼ 3.4 eV, which is lower than the energy required for the lowest H-loss pathway (∼ 5.0 eV). The barrier for the second CO-loss is higher (∼ 4.9 eV). The subsequent loss of this unit changes the Bq geometry from a planar to a bent one. It is concluded that the photodissociation mechanism of the substituted PAH cations studied here is site selective in the substituted subunit. This work also shows that an acetone substituted PAH cation is not photo-stable upon irradiation.

Methyl isocyanate (CH3NCO) belongs to a select group of peptide-like prebiotic molecules. In this paper we present its first detection toward the solar type low-mass protostar IRAS16293-2422 (hereafter IRAS16293). CH3NCO is detected towards IRAS16293 as a warm component with Tex > 100 K and HNCO/CH3NCO ∼4-12. Also, its grain surface formation route is investigated in the laboratory. VUV processing of CH4:HNCO mixtures, investigated by IR spectroscopy and mass spectrometry, revealed that it can be formed by reactions of CH3 and with (H)NCO. Observations and experiments strongly hint that methyl isocyanate is formed on interstellar dust grains.

We describe the characteristics and the capabilities of the laboratory facility, COSmIC, that was developed at NASA Ames to generate, process and analyze interstellar, circumstellar and planetary analogs in the laboratory. COSmIC stands for ’Cosmic Simulation Chamber’ and is dedicated to the study of neutral and ionized molecules and nanoparticles under the low temperature and high vacuum conditions that are required to simulate various space environments such as diffuse interstellar clouds, circumstellar outflows and planetary atmospheres. Recent results obtained using COSmIC will be highlighted. In particular, the progress that has been achieved in the domain of the diffuse interstellar bands (DIBs) and in monitoring, in the laboratory, the formation of circumstellar dust grains and planetary atmosphere aerosols from their gas-phase molecular precursors. Plans for future laboratory experiments on interstellar and planetary molecules and grains will also be addressed, as well as the implications of the studies underway for astronomical observations and past and future space mission data analysis.

Back-diffusion is the phenomenon by which random walkers revisit binding sites on a lattice. This phenomenon must occur on interstellar dust particles, slowing down dust-grain reactions, but it is not accounted for by standard rate-equation models. Microscopic kinetic Monte Carlo models have been used to investigate the effect of back-diffusion on reaction rates on interstellar dust grains. Grain morphology, size, and grain-surface coverage were varied and the effects of these variations on the magnitude of the back-diffusion effect were studied for the simple H+H reaction system. This back-diffusion effect is seen to reduce reaction rates by a maximum factor of ∼5 for the canonical grain of 106 binding sites. The resulting data were fit to logarithmic functions that can be used to reproduce the effects of back-diffusion in rate-equation models.

The diffusion and photoprocessing of molecules within interstellar ices has been verified experimentally but often not fully included in astrochemical models. With models that consider photodissociation, binary reactions, and diffusion for molecules on the surface and in bulk ice, we explored the chemistry of interstellar and circumstellar ices in gravitationally contracting low-mass starless and prestellar cores, and a protostellar envelope.

Results. Photoprocessing gradually converts mixed H2O and CO ices into CO2 and allows for a late synthesis of icy organic species. Different layers within a single icy mantle favor the synthesis different species. Deuterium-rich molecules are concentrated on the outer surface of ice. Formation of organic molecules in bulk ice lowers their average deuterium content. The abundances of major icy species can be changed by about 25-50 % because of ice photoprocessing. Inter-layer diffusion of icy species allows sequential evaporation in protostellar envelopes, which occurs over a prolonged period.

The search for complex organic molecules (COMs) in the ISM has revealed chemical species of ever greater complexity. This search relies heavily on the progress made in the laboratory to characterize the rotational spectra of these molecules. Observationally, the advent of ALMA with its high angular resolution and sensitivity has allowed to reduce the spectral confusion and detect low-abundance molecules that could not be probed before. We present results of the EMoCA survey conducted with ALMA toward the star-forming region Sgr B2(N). This spectral line survey aims at deciphering the molecular content of Sgr B2(N) in order to test the predictions of astrochemical models and gain insight into the chemical processes at work in the ISM. We report on the tentative detection of N-methylformamide, on deuterated COMs, and on the detection of a branched alkyl molecule. Prospects for probing molecular complexity in the ISM even further are discussed at the end.

Gas-phase methanol was recently detected in a protoplanetary disk for the first time with ALMA. The peak abundance and distribution of methanol observed in TW Hya differed from that predicted by chemical models. Here, the chemistry of methanol gas and ice is calculated using a physical model tailored for TW Hya with the aim to contrast the results with the recent detection in this source. New pathways for the formation of larger complex molecules (e.g., ethylene glycol) are included in an updated chemical model, as well as the fragmentation of methanol ice upon photodesorption. It is found that including fragmentation upon photodesorption improves the agreement between the peak abundance reached in the chemical models with that observed in TW Hya (∼10−11 with respect to H2); however, the model predicts that the peak in emission resides a factor of 2 − 3 farther out in the disk than the ALMA images. Reasons for the persistent differences in the gas-phase methanol distribution between models and the observations of TW Hya are discussed. These include the location of the ice reservoir which may coincide with the compact mm-dust disk (≲ 60 au) and sources of gas-phase methanol which have not yet been considered in models. The possibility of detecting larger molecules with ALMA is also explored. Calculations of the rotational spectra of complex molecules other than methanol using a parametric model constrained by the TW Hya observations suggest that the detection of individual emission lines of complex molecules with ALMA remains challenging. However, the signal-to-noise ratio can be enhanced via stacking of multiple transitions which have similar upper energy levels.

The detection of iso-propyl cyanide (i-C3H7CN) toward the Galactic Center hot-core source Sgr B2(N) (by Belloche et al. 2014) marked the first interstellar detection of an aliphatic molecule with a branched carbon-chain structure. Surprisingly, this branched form was found to have an almost equal abundance with its straight-chain homologue, normal-propyl cyanide (i:n = 0.40 ± 0.06). The detection of this first example of an interstellar molecule with a side-chain raises the question as to how prominent such structures may be in interstellar chemistry, and whether the large branched-to-straight chain ratio is maintained for even larger molecules.

Here are presented recently published models that simulate the chemistry occurring in Sgr B2(N) using a chemical network that explicitly includes the straight-chain and branched forms of propyl cyanide (normal/iso) and butyl cyanide (normal/iso/sec/tert), as well as butane (n/i) and pentane (n/i/neo). Formation is assumed to occur on dust-grain surfaces, but a full complement of destruction mechanisms is included both on the grains and in the gas phase.

The models suggest that branched structures become increasingly dominant as molecular sizes increase. In the case of butyl cyanide, the sec form is at least ∼2 times more abundant than the straight-chain normal form, and together the branched forms dominate normal-butyl cyanide by a factor of at least 3. The results for the larger alkanes suggest similarly large ratios of branched to straight-chain molecules. A key set of reactions in the surface/ice chemistry of interstellar nitriles is found to be the addition of the CN radical to unsaturated hydrocarbons, especially acetylene and ethene. The models also predict that the dominant, sec form of butyl cyanide reaches a peak abundance equal to that of n-propyl cyanide, albeit with a smaller emission radius. This makes s-C4H9CN a good candidate for detection. New ALMA observations to search for this molecule are ongoing.

Phosphorus is a crucial element in prebiotic chemistry, especially the P−O bond, which is key for the formation of the backbone of the deoxyribonucleic acid. So far, PO had only been detected towards the envelope of evolved stars, and never towards star-forming regions. We report the first detection of PO towards two massive star-forming regions, W51 e1/e2 and W3(OH), using data from the IRAM 30m telescope. PN has also been detected towards the two regions. The abundance ratio PO/PN is 1.8 and 3 for W51 and W3(OH), respectively. Our chemical model indicates that the two molecules are chemically related and are formed via gas-phase ion-molecule and neutral-neutral reactions during the cold collapse. The molecules freeze out onto grains at the end of the collapse and desorb during the warm-up phase once the temperature reaches ~35 K. The observed molecular abundances of 10−10 are predicted by the model if a relatively high initial abundance of 5× 10−9 of initial phosphorus is assumed.

The study of complex organic molecules, and more specifically those of prebiotic interest, is important to understand the chemical richness of star-forming regions. The chemistry of nitrogen bearing molecules such as formamide or methyl isocyanate is poorly constrained. We study different chemical pathways to form and destroy these molecules from both the gas phase and grain surface chemistry. From comparison with observations of four different relevant astrophysical regions, we show that both the gas phase and grain surface chemistry are required to explain the observed abundances of these species.

C2H4O2 isomers, methyl formate (HCOOCH3), acetic acid (CH3COOH) and glycoaldehyde (HOCH2CHO), have been detected in a lot of sources in ISM. However, their abundances are very different, with methyl formate much more abundant than the other two isomers. This fact may be related to the different destruction by ionizing radiation of these molecules. The goal of this work is experimentally study the photodissociation processes of methyl formate and acetic acid ices when exposed to broadband soft X-ray from 6 up to 2000 eV. The experiments were performed coupled to the SGM beamline in the Brazilian Synchrotron Light Source (LNLS/CNPEM) at Campinas, Brazil. The simulated astrophysical ices (12K) were monitored throughout the experiment using infrared vibrational spectroscopy. The analysis of processed ices allowed the determination of the effective destruction cross sections of the parent molecules as well as the effective formation cross section of daughter molecular species. The relative abundance between acetic acid and methyl formate (NCH3COOH/NHCOOCH3) in different astronomical scenarios and their column density evolution in the presence of X-rays were calculated and our results suggests that such radiation field can be one of the factors that explain the difference in the isomers C2H4O2 abundances. We also quantified the daugther species after the establishment of a chemical equilibrium in the samples.

Nitrogen, one of the most abundant elements in the Universe is a fundamental element of molecules which are crucial for life. We present here the modelling of the emission of two of the simplest nitrogen-bearing molecules, CN and NO, with a non-LTE radiative transfer code in IRAS16293-2422, a class 0 low-mass protostar. In this model, we assumed IRAS16293-2422 is formed by 2 compact, hot and dense sources embedded in a three layers of envelope.

Complex organic molecules (COMs) have been observed in comets, hot cores and cold dense regions of the interstellar medium. It is generally accepted that these COMs form on icy dust grain through the recombination reaction of radicals triggered by either energetic UV-photon or non-energetic H-atom addition processing. In this work, we present for the first time laboratory studies that allow for quantitative comparison of hydrogenation and UV-induced reactions as well as their cumulative effect in astronomically relevant CO:CH3OH=4:1 ice analogues. The formation of glycolaldehyde (GA) and ethylene glycol (EG) is confirmed in pure hydrogenation experiments at 14 K, except methyl formate (MF), which is only clearly observed in photolysis. The fractions for MF:GA:EG are 0 : (0.2-0.4) : (0.8-0.6) for pure hydrogenation, and 0.2 : 0.3 : 0.5 for UV involving experiments and can offer a diagnostic tool to derive the chemical origin of these species. The GA/EG ratios in the laboratory (0.3-1.5) compare well with observations toward different objects.

Isocyanic acid (HNCO) is a simple molecule containing the four main atoms essential for life and can be considered as a prebiotic molecule. To model the HNCO emission in the IRAS16293-2422 class 0 low-mass protostar, we used a new set of HNCO collisional coefficients with ortho-H2 and para-H2, computed from a set of rotational excitation quenching rates between HNCO and H2 based on a novel potential energy surface for the rigid molecules interactions. We present here the HNCO Potential Energy Surface used to compute this new set of collisional coefficients and the result of the IRAS16293-2422 HNCO spectrum modelling using them.