arXiv subjects

Cecilia Ceccarelli

Publications and source records attributed to Cecilia Ceccarelli.

At least 73 records · Page 4Linked to original sources

arXiv2019

Reactivity of HCO with CH3 and NH2 on Water Ice Surfaces. A Comprehensive Accurate Quantum Chemistry Study

Interstellar complex organic molecules (iCOMs) can be loosely defined as chemical compounds with at least six atoms in which at least one is carbon. The observations of iCOMs in star-forming regions have shown that they contain an important fraction of carbon in a molecular form, which can be used to synthesize more complex, even biotic molecules. Hence, iCOMs are major actors in the increasing molecular complexity in space and they might have played a role in the origin of terrestrial life. Understand-ing how iCOMs are formed is relevant for predicting the ultimate organic chemistry reached in the interstellar medium. One possibility is that they are synthesized on the interstellar grain icy surfaces, via recombination of previously formed radicals. The present work focuses on the reactivity of HCO with CH3/NH2 on the grain icy sur-faces, investigated by means of quantum chemical simulations. The goal is to carry outa systematic study using different computational approaches and models for the icy surfaces. Specifically, DFT computations have been bench-marked with CASPT2 and CCSD(T) methods, and the ice mantles have been mimicked with cluster models of 1, 2, 18 and 33 H2O molecules, in which different reaction sites have been considered. Our results indicate that the HCO + CH3/NH2 reactions, if they actually occur, have two major competitive channels: the formation of iCOMs CH3CHO/NH2CHO, or the formation of CO + CH4/NH3. These two channels are either barrierless or presentrelatively low ($\leq$ 10 kJ/mol equal to about 1200 K) energy barriers. Finally, we briefly discuss the astrophysical implications of these findings.

astro-ph.SR↗

arXiv2019

Interstellar formamide (NH$_2$CHO), a key prebiotic precursor

Formamide (NH$_2$CHO) has been identified as a potential precursor of a wide variety of organic compounds essential to life, and many biochemical studies propose it likely played a crucial role in the context of the origin of life on our planet. The detection of formamide in comets, which are believed to have --at least partially-- inherited their current chemical composition during the birth of the Solar System, raises the question whether a non-negligible amount of formamide may have been exogenously delivered onto a very young Earth about four billion years ago. A crucial part of the effort to answer this question involves searching for formamide in regions where stars and planets are forming today in our Galaxy, as this can shed light on its formation, survival, and chemical re-processing along the different evolutionary phases leading to a star and planetary system like our own. The present review primarily addresses the chemistry of formamide in the interstellar medium, from the point of view of (i) astronomical observations, (ii) experiments, and (iii) theoretical calculations. While focusing on just one molecule, this review also more generally reflects the importance of joining efforts across multiple scientific disciplines in order to make progress in the highly interdisciplinary science of astrochemistry.

astro-ph.SR↗

arXiv2019

Interferometric observations of warm deuterated methanol in the inner regions of low-mass protostars

Methanol is a key species in astrochemistry since it is the most abundant organic molecule in the ISM and is thought to be the mother molecule of many complex organic species. Estimating the deuteration of methanol around young protostars is of crucial importance because it highly depends on its formation mechanisms and the physical conditions during its moment of formation. We analyse dozens of transitions from deuterated methanol isotopologues coming from various existing observational datasets from the IRAM-PdBI and ALMA sub-mm interferometers to estimate the methanol deuteration surrounding three low-mass protostars on Solar System scales. A population diagram analysis allows us to derive a [CH$_2$DOH]/[CH$_3$OH] abundance ratio of 3-6 % and a [CH$_3$OD]/[CH$_3$OH] ratio of 0.4-1.6 % in the warm inner protostellar regions. These values are ten times lower than those derived with previous single-dish observations towards these sources but they are 10-100 times higher than the methanol deuteration measured in massive hot cores. Dust temperature maps obtained from Herschel and Planck observations show that massive hot cores are located in warmer molecular clouds than low-mass sources, with temperature differences of $\sim$10 K. Comparison with the predictions of the gas-grain astrochemical model GRAINOBLE shows that such a temperature difference is sufficient to explain the different deuteration observed in low- to high-mass sources, suggesting that the physical conditions of the molecular cloud at the origin of the protostars mostly govern the present observed deuteration of methanol. The methanol deuteration measured in this work is higher by a factor of 5 than the upper limit in methanol deuteration estimated in comet Hale-Bopp, implying that an important reprocessing of the organic material would have occurred in the solar nebula during the formation of the Solar System.

astro-ph.GA↗

arXiv2019

Sulfur-Bearing Species Tracing the Disk/Envelope System in the Class I Protostellar Source Elias 29

We have observed the Class I protostellar source Elias 29 with Atacama Large Millimeter/submillimeter Array (ALMA). We have detected CS, SO, $^{34}$SO, SO$_2$, and SiO line emissions in a compact component concentrated near the protostar and a ridge component separated from the protostar by 4\arcsec\ ($\sim 500$ au). The former component is found to be abundant in SO and SO$_2$ but deficient in CS. The abundance ratio SO/CS is as high as $3^{+13}_{-2} \times 10^2$ at the protostar, which is even higher than that in the outflow-shocked region of L1157 B1. However, organic molecules (HCOOCH$_3$, CH$_3$OCH$_3$, CCH, and c-C$_3$H$_2$) are deficient in Elias 29. We attribute the deficiency in organic molecules and richness in SO and SO$_2$ to the evolved nature of the source or the relatively high dust temperature (\protect\raisebox{-0.7ex}{$\:\stackrel{\textstyle >}{\sim}\:$} 20 K) in the parent cloud of Elias 29. The SO and SO$_2$ emissions trace rotation around the protostar. Assuming a highly inclined configuration ($i \geq 65$\degr; 0\degr\ for a face-on configuration) and Keplerian motion for simplicity, the protostellar mass is estimated to be (0.8 -- 1.0) \Msun. The $^{34}$SO and SO$_2$ emissions are asymmetric in their spectra; the blue-shifted components are weaker than the red-shifted ones. Although this may be attributed to the asymmetric molecular distribution, other possibilities are also discussed.

astro-ph.SR↗

arXiv2019

Impact of nonconvergence and various approximations of the partition function on the molecular column densities in the interstellar medium

We emphasize that the completeness of the partition function, that is, the use of a converged partition function at the typical temperature range of the survey, is very important to decrease the uncertainty on this quantity and thus to derive reliable interstellar molecular densities. In that context, we show how the use of different approximations for the rovibrational partition function together with some interpolation and/or extrapolation procedures may affect the estimate of the interstellar molecular column density. For that purpose, we apply the partition function calculations to astronomical observations performed with the IRAM-30m telescope towards the NGC7538-IRS1 source of two N-bearing molecules: isocyanic acid (HNCO, a quasilinear molecule) and methyl cyanide (CH$_3$CN, a symmetric top molecule). The case of methyl formate (HCOOCH$_3$), which is an asymmetric top O-bearing molecule containing an internal rotor is also discussed. Our analysis shows that the use of different partition function approximations leads to relative differences in the resulting column densities in the range 9 to 43\%. Thus, we expect this work to be relevant for surveys of sources with temperatures higher than 300~K and to observations in the infrared.

astro-ph.GA↗

arXiv2019

Sulfur Chemistry in L1157-B1

The main carrier of sulfur in dense clouds, where it is depleted from the gas phase, remains a mystery. Shock waves in young molecular outflows disrupt the ice mantles and allow us to directly probe the material that is ejected into the gas phase. A comprehensive study of sulfur-bearing species towards L1157-B1, a shocked region along a protostellar outflow, has been carried out as part of the IRAM-30m large program ASAI. The dataset contains over 100 lines of CCS, H$_2$CS, OCS, SO, SO$_2$ and isotopologues. The results of these observations are presented, complementing previous studies of sulfur-bearing species in the region. The column densities and fractional abundances of these species are measured and together these species account for 10\% of the cosmic sulfur abundance in the region. The gas properties derived from the observations are also presented, demonstrating that sulfur bearing species trace a wide range of different gas conditions in the region.

astro-ph.GA↗

arXiv2019

Destruction of dimethyl ether and methyl formate by collisions with He$^+$

To correctly model the abundances of interstellar complex organic molecules (iCOMS) in different environments, both formation and destruction routes should be appropriately accounted for. While several scenarios have been explored for the formation of iCOMs via grain and gas-phase processes, much less work has been devoted to understanding the relevant destruction pathways, with special reference to (dissociative) charge exchange or proton transfer reactions with abundant atomic and molecular ions such as He$^+$, H$_3^+$ and HCO$^+$. By using a combined experimental and theoretical methodology we provide new values for the rate coefficients and branching ratios (BRs) of the reactions of He$^+$ ions with two important iCOMs, namely dimethyl ether (DME) and methyl formate (MF). We also review the destruction routes of DME and MF by other two abundant ions, namely H$_3^+$ and HCO$^+$. Based on our recent laboratory measurements of cross sections and BRs for the DME/MF + He$^+$ reactions over a wide collision energy range, we extend our theoretical insights on the selectivity of the microscopic dynamics to calculate the rate coefficients $k(T)$ in the temperature range from 10 to 298 K. We implement these new and revised kinetic data in a general model of cold and warm gas, simulating environments where DME and MF have been detected. Due to stereodynamical effects present at low collision energies, the rate coefficients, BRs and temperature dependences here proposed differ substantially from those reported in KIDA and UDfA, two of the most widely used astrochemical databases. These revised rates impact the predicted abundances of DME and MF, with variations up to 40% in cold gases and physical conditions similar to those present in prestellar cores

astro-ph.SR↗

arXiv2018

A theoretical investigation of the reaction between the amidogen, NH, and the ethyl, C2H5, radicals: a possible gas-phase formation route of interstellar and planetary ethanimine

The reaction between the amidogen, NH, radical and the ethyl, C2H5, radical has been investigated by performing electronic structure calculations of the underlying doublet potential energy surface. Rate coefficients and product branching ratios have also been estimated by combining capture and RRKM calculations. According to our results, the reaction is very fast, close to the gas-kinetics limit. However, the main product channel, with a yield of ca. 86-88% in the range of temperatures investigated, is the one leading to methanimine and the methyl radical. The channels leading to the two E-, Z- stereoisomers of ethanimine account only for ca. 5-7% each. The resulting ratio [E-CH3CHNH]/[Z-CH3CHNH] is ca. 1.2, that is a value rather lower than that determined in the Green Bank Telescope PRIMOS radio astronomy survey spectra of Sagittarius B2 North (ca. 3). Considering that ice chemistry would produce essentially only the most stable isomer, a possible conclusion is that the observed [E-CH3CHNH]/[Z-CH3CHNH] ratio is compatible with a combination of gas-phase and grain chemistry. More observational and laboratory data are needed to definitely address this issue.

astro-ph.EP↗

arXiv2018

Interstellar dimethyl ether gas-phase formation: a quantum chemistry and kinetics study

Dimethyl ether is one of the most abundant interstellar complex organic molecules. Yet its formation route remains elusive. In this work, we have performed electronic structure and kinetics calculations to derive the rate coefficients for two ion-molecule reactions recently proposed as a gas-phase formation route of dimethyl ether in interstellar objects, namely CH$_3$OH + CH$_3$OH$_2^+$ $\rightarrow$ (CH$_3$)$_2$OH$^+$ + H$_2$O followed by (CH$_3$)$_2$OH$^+$ + NH$_3$ $\rightarrow$ CH$_3$OCH$_3$ + NH$_4^+$. A comparison with previous experimental rate coefficients for the reaction CH$_3$OH + CH$_3$OH$_2^+$ sustains the accuracy of the present calculations and allow a more reliable extrapolation at the low temperatures of interest in interstellar objects (10-100 K). The rate coefficient for the reaction (CH$_3$)$_2$OH$^+$ + NH$_3$ is, instead, provided for the first time ever. The rate coefficients derived in this work essentially confirm the prediction by Taquet et al. (2016) concerning dimethyl ether formation in hot cores/corinos. Nevertheless, this formation route cannot be efficient in cold objects (like prestellar cores) where dimethyl ether is also detected, because ammonia has a very low abundance in those environments.

astro-ph.GA↗

arXiv2018

Can Formamide Be Formed on Interstellar Ice? An Atomistic Perspective

Interstellar formamide (NH2CHO) has recently attracted significant attention due to its potential role as a molecular building block in the formation of precursor biomolecules relevant for the origin of life. Its formation, whether on the surfaces of the interstellar grains or in the gas phase, is currently debated. The present article presents new theoretical quantum chemical computations on possible NH2CHO formation routes in water-rich amorphous ices, simulated by a 33-H2O-molecule cluster. We have considered three possible routes. The first one refers to a scenario used in several current astrochemical models, that is, the radical-radical association reaction between NH2 and HCO. Our calculations show that formamide can indeed be formed, but in competition with formation of NH3 and CO through a direct H transfer process. The final outcome of the NH2 + HCO reactivity depends on the relative orientation of the two radicals on the ice surface. We then analyzed two other possibilities, suggested here for the first time: reaction of either HCN or CN with water molecules of the ice mantle. The reaction with HCN has been found to be characterized by large energy barriers and, therefore, cannot occur under the interstellar ice conditions. On the contrary, the reaction with the CN radical can occur, possibly leading through multiple steps to the formation of NH2CHO. For this reaction, water molecules of the ice act as catalytic active sites since they help the H transfers involved in the process, thus reducing the energy barriers (compared to the gas-phase analogous reaction). Additionally, we apply a statistical model to estimate the reaction rate coefficient when considering the cluster of 33-H2O-molecules as an isolated moiety with respect to the surrounding environment, i.e., the rest of the ice.

astro-ph.EP↗

arXiv2018

Rotation in the NGC 1333 IRAS 4C Outflow

We report molecular line observations of the NGC 1333 IRAS 4C outflow in the Perseus Molecular Cloud with the Atacama Large Millimeter/Submillimeter Array. The CCH and CS emission reveal an outflow cavity structure with clear signatures of rotation with respect to the outflow axis. The rotation is detected from about 120 au up to about 1400 au above the envelope/disk mid-plane. As the distance to the central source increases, the rotation velocity of the outflow decreases while the outflow radius increases, which gives a flat specific angular momentum distribution along the outflow. The mean specific angular momentum of the outflow is about 100 au km/s. Based on reasonable assumptions on the outward velocity of the outflow and the protostar mass, we estimate the range of outflow launching radii to be 5-15 au. Such a launching radius rules out that this outflow is launched as an X-wind, but rather, it is more consistent to be a slow disk wind launched from relatively large radii on the disk. The radius of the centrifugal barrier is roughly estimated, and the role of the centrifugal barrier in the outflow launching is discussed.

astro-ph.GA↗

arXiv2018

IR Spectral Fingerprint of Carbon Monoxide in Interstellar Water Ice Models

Carbon monoxide (CO) is the second most abundant molecule in the gas-phase of the interstellar medium. In dense molecular clouds, it is also present in the solid-phase as a constituent of the mixed water-dominated ices covering dust grains. Its presence in the solid-phase is inferred from its infrared (IR) signals. In experimental observations of solid CO/water mixed samples, its IR frequency splits into two components, giving rise to a blue- and a redshifted band. However, in astronomical observations, the former has never been observed. Several attempts have been carried out to explain this peculiar behaviour, but the question still remains open. In this work, we resorted to pure quantum mechanical simulations in order to shed some light on this problem. We adopted different periodic models simulating the CO/H$_2$O ice system, such as single and multiple CO adsorption on water ice surfaces, CO entrapped into water cages and proper CO:H$_2$O mixed ices. We also simulated pure solid CO. The detailed analysis of our data revealed how the quadrupolar character of CO and the dispersive forces with water ice determine the energetic of the CO/H$_2$O ice interaction, as well as the CO spectroscopic behaviour. Our data suggest that the blueshifted peak can be assigned to CO interacting {\it via} the C atom with dangling H atoms of the water ice, while the redshifted one can actually be the result of CO involved in different reciprocal interactions with the water matrix. We also provide a possible explanation for the lack of the blueshifted peak in astronomical spectra. Our aim is not to provide a full account of the various interstellar ices, but rather to elucidate the sensitivity of the CO spectral features to different water ice environments.

astro-ph.GA↗

arXiv2018

First Detection of the Simplest Organic Acid in a Protoplanetary Disk

The formation of asteroids, comets and planets occurs in the interior of protoplanetary disks during the early phase of star formation. Consequently, the chemical composition of the disk might shape the properties of the emerging planetary system. In this context, it is crucial to understand whether and what organic molecules are synthesized in the disk. In this Letter, we report the first detection of formic acid (HCOOH) towards the TW Hydrae protoplanetary disk. The observations of the trans-HCOOH 6$_{(1,6)-5(1,5)}$ transition were carried out at 129~GHz with ALMA. We measured a disk-averaged gas-phase t-HCOOH column density of $\sim$ (2-4)$\times$10$^{12}$~cm$^{-2}$, namely as large as that of methanol. HCOOH is the first organic molecules containing two oxygen atoms detected in a protoplanetary disk, a proof that organic chemistry is very active even though difficult to observe in these objects. Specifically, this simplest acid stands as the basis for synthesis of more complex carboxylic acids used by life on Earth.

astro-ph.SR↗

arXiv2018

Sub-arcsecond Kinematic Structure of the Outflow in the Vicinity of the Protostar in L483

The bipolar outflow associated with the Class 0 low-mass protostellar source (IRAS 18148-0440) in L483 has been studied in the CCH and CS line emission at 245 and 262 GHz, respectively. Sub-arcsecond resolution observations of these lines have been conducted with ALMA. Structures and kinematics of the outflow cavity wall are investigated in the CS line, and are analyzed by using a parabolic model of an outflow. We constrain the inclination angle of the outflow to be from 75 degree to 90 degree, i.e. the outflow is blowing almost perpendicular to the line of sight. Comparing the outflow parameters derived from the model analysis with those of other sources, we confirm that the opening angle of the outflow and the gas velocity on its cavity wall correlate with the dynamical timescale of the outflows. Moreover, a hint of a rotating motion of the outflow cavity wall is found. Although the rotation motion is marginal, the specific angular momentum of the gas on the outflow cavity wall is evaluated to be comparable to or twice that of the infalling-rotating envelope of L483.

astro-ph.SR↗

arXiv2018

Sulphur chemistry in the L1544 pre-stellar core

The L1544 pre-stellar core has been observed as part of the ASAI IRAM 30m Large Program as well as follow-up programs. These observations have revealed the chemical richness of the earliest phases of low-mass star-forming regions. In this paper we focus on the twenty-one sulphur bearing species (ions, isotopomers and deuteration) that have been detected in this spectral-survey through fifty one transitions: CS, CCS, C3S, SO, SO2, H2CS, OCS, HSCN, NS, HCS+, NS+ and H2S. We also report the tentative detection (4 σ level) for methyl mercaptan (CH3SH). LTE and non-LTE radiative transfer modelling have been performed and we used the nautilus chemical code updated with the most recent chemical network for sulphur to explain our observations. From the chemical modelling we expect a strong radial variation for the abundances of these species, which mostly are emitted in the external layer where non thermal desorption of other species has previously been observed. We show that the chemical study cannot be compared to what has been done for the TMC-1 dark cloud, where the abundance is supposed constant along the line of sight, and conclude that a strong sulphur depletion is necessary to fully reproduce our observations of the prototypical pre-stellar core L1544.

astro-ph.GA↗

arXiv2018

Chemical survey toward young stellar objects in the Perseus molecular cloud complex

Chemical diversity of the gas in low-mass protostellar cores is widely recognized. In order to explore its origin, a survey of chemical composition toward 36 Class 0/I protostars in the Perseus molecular cloud complex, which are selected in an unbiased way under certain physical conditions, has been conducted with IRAM 30 m and NRO 45 m telescope. Multiple lines of C2H, c-C3H2 and CH3OH have been observed to characterize the chemical composition averaged over a 1000 au scale around the protostar. The derived beam-averaged column densities show significant chemical diversity among the sources, where the column density ratios of C2H/CH3OH are spread out by 2 orders of magnitude. From previous studies, the hot corino sources have abundant CH3OH but deficient C2H, their C2H/CH3OH column density ratios being relatively low. In contrast, the warm-carbon-chain chemistry (WCCC) sources are found to reveal the high C2H/CH3OH column density ratios. We find that the majority of the sources have intermediate characters between these two distinct chemistry types. A possible trend is seen between the C2H/CH3OH ratio and the distance of the source from the edge of a molecular cloud. The sources located near cloud edges or in isolated clouds tend to have a high C2H/CH3OH ratio. On the other hand, the sources having a low C2H/CH3OH ratio tend to be located in inner regions of the molecular cloud complex. This result gives an important clue to an understanding of the origin of the chemical diversity of protostellar cores in terms of environmental effects.

astro-ph.GA↗

arXiv2018

The evolution of grain mantles and silicate dust growth at high redshift

In dense molecular clouds, interstellar grains are covered by mantles of iced molecules. The formation of the grain mantles has two important consequences: it removes species from the gas phase and promotes the synthesis of new molecules on the grain surfaces. The composition of the mantle is a strong function of the environment which the cloud belongs to. Therefore, clouds in high-zeta galaxies, where conditions -like temperature, metallicity and cosmic rays flux- are different from those in the Milky Way, will have different grain mantles. In the last years, several authors have suggested that silicate grains might grow by accretion of silicon bearing species on smaller seeds. This would occur simultaneously to the formation of the iced mantles and be greatly affected by its composition as a function of time. In this work, we present a numerical study of the grain mantle formation in high-zeta galaxies and we quantitatively address the possibility of silicate growth. We find that the mantle thickness decreases with increasing redshift, from about 120 to 20 layers for z varying from 0 to 8. Furthermore, the mantle composition is also a strong function of the cloud redshift, with the relative importance of CO, CO2, ammonia, methane and methanol highly varying with z. Finally, being Si-bearing species always a very minor component of the mantle, the formation of silicates in molecular clouds is practically impossible.

astro-ph.GA↗

arXiv2018

Seeds of Life in Space (SOLIS). III. Zooming into the methanol peak of the pre-stellar core L1544

Towards the pre-stellar core L1544, the methanol (CH$_3$OH) emission forms an asymmetric ring around the core centre, where CH$_3$OH is mostly in solid form, with a clear peak 4000~au to the north-east of the dust continuum peak. As part of the NOEMA Large Project SOLIS (Seeds of Life in Space), the CH$_3$OH peak has been spatially resolved to study its kinematics and physical structure and to investigate the cause behind the local enhancement. We find that methanol emission is distributed in a ridge parallel to the main axis of the dense core. The centroid velocity increases by about 0.2~km~s$^{-1}$ and the velocity dispersion increases from subsonic to transonic towards the central zone of the core, where the velocity field also shows complex structure. This could be indication of gentle accretion of material onto the core or interaction of two filaments, producing a slow shock. We measure the rotational temperature and show that methanol is in local thermodynamic equilibrium (LTE) only close to the dust peak, where it is significantly depleted. The CH$_3$OH column density, $N_{tot}({\rm CH_3OH})$, profile has been derived with non-LTE radiative transfer modelling and compared with chemical models of a static core. The measured $N_{tot}({\rm CH_3OH})$ profile is consistent with model predictions, but the total column densities are one order of magnitude lower than those predicted by models, suggesting that the efficiency of reactive desorption or atomic hydrogen tunnelling adopted in the model may be overestimated; or that an evolutionary model is needed to better reproduce methanol abundance.

astro-ph.GA↗