Chemical modeling of Infrared Dark Clouds: the Role of Surface Chemistry

We simulate the chemistry of infrared dark clouds (IRDCs) with a model in which the physical conditions are homogeneous and time-independent. The chemistry is solved as a function of time with three networks: one purely gas-phase, one that includes accretion and desorption, and one, the complete gas-grain network, that includes surface chemistry in addition. We compare our results with observed molecular abundances for two representative IRDCs -- IRDC013.90-1 and IRDC321.73-1 -- using the molecular species N$_2$H$^+$, HC$_3$N, HNC, HCO$^+$, HCN, C$_2$H, NH$_3$ and CS. IRDC013.90-1 is a cold IRDC, with a temperature below 20 K, while IRDC321.73-1 is somewhat warmer, in the range 20 - 30 K. We find that the complete gas-grain model fits the data very well, but that the goodness-of-fit is not sharply peaked at a particular temperature. Surface processes are important for the explanation of the high gas-phase abundance of N$_2$H$^+$ in IRDC321.73-1. The general success of the 0-D model in reproducing single-dish observations of our limited sample of 8 species shows that it is probably sufficient for an explanation of this type of data. To build and justify more complicated models, including spatial temperature and density structure, contraction, and heating, we require high-resolution interferometric data.Comment: accepted for publication in Ap

O2 signature in thin and thick O2-H2O ices

Aims. In this paper we investigate the detectability of the molecular oxygen in icy dust grain mantles towards astronomical objects. Methods. We present a systematic set of experiments with O2-H2O ice mixtures designed to disentangle how the molecular ratio affects the O2 signature in the mid- and near-infrared spectral regions. All the experiments were conducted in a closed-cycle helium cryostat coupled to a Fourier transform infrared spectrometer. The ice mixtures comprise varying thicknesses from 8 $\times$ 10$^{-3}$ to 3 $\mu$m. The absorption spectra of the O2-H2O mixtures are also compared to the one of pure water. In addition, the possibility to detect the O2 in icy bodies and in the interstellar medium is discussed. Results. We are able to see the O2 feature at 1551 cm$^{-1}$ even for the most diluted mixture of H2O : O2 = 9 : 1, comparable to a ratio of O2/H2O = 10 % which has already been detected in situ in the coma of the comet 67P/Churyumov-Gerasimenko. We provide an estimate for the detection of O2 with the future mission of the James Webb Space Telescope (JWST).Comment: 11 pages, 10 figures, article in press, to appear in A&A 201

A Unified Monte Carlo Treatment of Gas-Grain Chemistry for Large Reaction Networks. I. Testing Validity of Rate Equations in Molecular Clouds

In this study we demonstrate for the first time that the unified Monte Carlo approach can be applied to model gas-grain chemistry in large reaction networks. Specifically, we build a time-dependent gas-grain chemical model of the interstellar medium, involving about 6000 gas-phase and 200 grain surface reactions. This model is used to test the validity of the standard and modified rate equation methods in models of dense and translucent molecular clouds and to specify under which conditions the use of the stochastic approach is desirable. We found that at temperatures 25--30 K gas-phase abundances of H$_2$O, NH$_3$, CO and many other gas-phase and surface species in the stochastic model differ from those in the deterministic models by more than an order of magnitude, at least, when tunneling is accounted for and/or diffusion energies are 3x lower than the binding energies. In this case, surface reactions, involving light species, proceed faster than accretion of the same species. In contrast, in the model without tunneling and with high binding energies, when the typical timescale of a surface recombination is greater than the timescale of accretion onto the grain, we obtain almost perfect agreement between results of Monte Carlo and deterministic calculations in the same temperature range. At lower temperatures ($\sim10$ K) gaseous and, in particular, surface abundances of most important molecules are not much affected by stochastic processes.Comment: 33 pages, 9 figures, 1 table. Accepted for publication in Ap

Compact dusty clouds and efficient H2_2 formation in diffuse ISM

The formation of compact dusty clouds in diffuse interstellar medium (ISM) has been recently proposed and studied by Tsytovich et al. (2014). In the present paper, an effect of the clouds on the rate of H$\to$H$_2$ transition in the ISM is examined. We discuss the mechanisms leading to the formation of the clouds and the creation of gaseous clumps around them, analyze the main processes determining the efficiency of the recombination of atomic hydrogen on dust grains, and estimate the expected enhancement of the global H$_2$ formation due to the presence of the clouds. In conclusion, we argue that the compact dusty clouds provide optimum conditions for the atomic recombination in diffuse ISM, and point out some astrophysical implications of the resulting H$_2$ formation enhancement.Comment: 5 pages, 2 figures, accepted to The Astrophysical Journa

Rotational spectroscopy of the HCCO and DCCO radicals in the millimeter and submillimeter range

The ketenyl radical, HCCO, has recently been detected in the ISM for the first time. Further astronomical detections of HCCO will help us understand its gas-grain chemistry, and subsequently revise the oxygen-bearing chemistry towards dark clouds. Moreover, its deuterated counterpart, DCCO, has never been observed in the ISM. HCCO and DCCO still lack a broad spectroscopic investigation, although they exhibit a significant astrophysical relevance. In this work we aim to measure the pure rotational spectra of the ground state of HCCO and DCCO in the millimeter and submillimeter region, considerably extending the frequency range covered by previous studies. The spectral acquisition was performed using a frequency-modulation absorption spectrometer between 170 and 650 GHz. The radicals were produced in a low-density plasma generated from a select mixture of gaseous precursors. For each isotopologue we were able to detect and assign more than 100 rotational lines. The new lines have significantly enhanced the previous data set allowing the determination of highly precise rotational and centrifugal distortion parameters. In our analysis we have taken into account the interaction between the ground electronic state and a low-lying excited state (Renner-Teller pair) which enables the prediction and assignment of rotational transitions with $K_a$ up to 4. The present set of spectroscopic parameters provides highly accurate, millimeter and submillimeter rest-frequencies of HCCO and DCCO for future astronomical observations. We also show that towards the pre-stellar core L1544, ketenyl peaks in the region where $c$-$\mathrm{C_3H_2}$ peaks, suggesting that HCCO follows a predominant hydrocarbon chemistry, as already proposed by recent gas-grain chemical models

First ALMA maps of HCO, an important precursor of complex organic molecules, towards IRAS 16293-2422

The formyl radical HCO has been proposed as the basic precursor of many complex organic molecules such as methanol (CH$_3$OH) or glycolaldehyde (CH$_2$OHCHO). Using ALMA, we have mapped, for the first time at high angular resolution ($\sim$1$^{\prime\prime}$, $\sim$140 au), HCO towards the Solar-type protostellar binary IRAS 16293$-$2422, where numerous complex organic molecules have been previously detected. We also detected several lines of the chemically related species H$_2$CO, CH$_3$OH and CH$_2$OHCHO. The observations revealed compact HCO emission arising from the two protostars. The line profiles also show redshifted absorption produced by foreground material of the circumbinary envelope that is infalling towards the protostars. Additionally, IRAM 30m single-dish data revealed a more extended HCO component arising from the common circumbinary envelope. The comparison between the observed molecular abundances and our chemical model suggests that whereas the extended HCO from the envelope can be formed via gas-phase reactions during the cold collapse of the natal core, the HCO in the hot corinos surrounding the protostars is predominantly formed by the hydrogenation of CO on the surface of dust grains and subsequent thermal desorption during the protostellar phase. The derived abundance of HCO in the dust grains is high enough to produce efficiently more complex species such as H$_2$CO, CH$_3$OH, and CH$_2$OHCHO by surface chemistry. We found that the main formation route of CH$_2$OHCHO is the reaction between HCO and CH$_2$OH.Comment: Accepted in Monthly Notices of the Royal Astronomical Society; 19 pages, 12 figures, 7 table