arXiv subjects

Nadia Balucani

Publications and source records attributed to Nadia Balucani.

At least 37 records · Page 2Linked to original sources

arXiv2021

A Computational Study of the Reaction Cyanoacetylene and Cyano Radical leading to 2-Butynedinitrile and Hydrogen Radical

The present work focuses on the characterization of the reaction between cyanoacetylene and cyano radical by electronic structure calculations of the stationary points along the minimum energy path. One channel, leading to C4N2 (2-Butynedinitrile) + H, was selected due to the importance of its products. Using different ab initio methods, a number of stationary points of the potential energy surface were characterized. The energy values of these minima were compared in order to weight the computational costs in relation to chemical accuracy. The results of this works suggests that B2PLYP (and B2PLYPD3) gave a better description of the saddle point geometry, while B3LYP works better for minima.

physics.chem-ph↗

arXiv2021

H2 formation on interstellar grains and the fate of reaction energy

Molecular hydrogen is the most abundant molecular species in the Universe. While no doubts exist that it is mainly formed on the interstellar dust grain surfaces, many details of this process remain poorly known. In this work, we focus on the fate of the energy released by the H$_2$ formation on the dust icy mantles, how it is partitioned between the substrate and the newly formed H$_2$, a process that has a profound impact on the interstellar medium. We carried out state-of-art \textit{ab-initio} molecular dynamics simulations of H$_2$ formation on periodic crystalline and amorphous ice surface models. Our calculations show that up to two thirds of the energy liberated in the reaction ($\sim$300 kJ/mol $\sim$3.1 eV) is absorbed by the ice in less than 1 ps. The remaining energy ($\sim$140 kJ/mol $\sim$1.5 eV) is kept by the newly born H$_2$. Since it is ten times larger than the H$_2$ binding energy on the ice, the new H$_2$ molecule will eventually be released into the gas-phase. The ice water molecules within $\sim$4 Å~from the reaction site acquire enough energy, between 3 and 14 kJ/mol (360--1560 K), to potentially liberate other frozen H$_2$ and, perhaps, frozen CO molecules. If confirmed, the latter process would solve the long standing conundrum of the presence of gaseous CO in molecular clouds. Finally, the vibrational state of the newly formed H$_2$ drops from highly excited states ($ν= 6$) to low ($ν\leq 2$) vibrational levels in a timescale of the order of ps.

astro-ph.GA↗

arXiv2021

FAUST II. Discovery of a Secondary Outflow in IRAS 15398-3359: Variability in Outflow Direction during the Earliest Stage of Star Formation?

We have observed the very low-mass Class 0 protostar IRAS 15398-3359 at scales ranging from 50 au to 1800 au, as part of the ALMA Large Program FAUST. We uncover a linear feature, visible in H2CO, SO, and C18O line emission, which extends from the source along a direction almost perpendicular to the known active outflow. Molecular line emission from H2CO, SO, SiO, and CH3OH further reveals an arc-like structure connected to the outer end of the linear feature and separated from the protostar, IRAS 15398-3359, by 1200 au. The arc-like structure is blue-shifted with respect to the systemic velocity. A velocity gradient of 1.2 km/s over 1200 au along the linear feature seen in the H2CO emission connects the protostar and the arc-like structure kinematically. SO, SiO, and CH3OH are known to trace shocks, and we interpret the arc-like structure as a relic shock region produced by an outflow previously launched by IRAS 15398-3359. The velocity gradient along the linear structure can be explained as relic outflow motion. The origins of the newly observed arc-like structure and extended linear feature are discussed in relation to turbulent motions within the protostellar core and episodic accretion events during the earliest stage of protostellar evolution.

astro-ph.SR↗

arXiv2020

Gas-phase formation of acetaldehyde: review and new theoretical computations

Among all the interstellar complex organic molecules (iCOMs), acetaldehyde is one of the most widely detected species. The question of its formation route(s) is, therefore, of a major interest regarding astrochemical models. In this paper, we provide an extensive review of the gas-phase formation paths that were, or are, reported in the literature and the major astrochemical databases. Four different gas-phase formation routes stand out : (1) CH$_3$OCH$_3$ + H$^+$ / CH$_3$CHOH$^+$ + e$^-$, (2) C$_2$H$_5$ + O($^3$P), (3) CH$_3$OH + CH and (4) CH$_3$CH$_2$OH + OH / CH$_3$CHOH + O($^3$P). Paths (2) and (3) were not studied neither via laboratory or theoretical works in the low temperature and density regime valid for the ISM. Thus, we carried out new accurate quantum chemistry computations. A theoretical kinetics study at low temperatures (7-300 K), adopting the RRKM scheme, was also performed. We confirm that reaction (2) is efficient in forming acetaldehyde in the 7-300 temperature range (alpha = 1.21 x 10$^{-10}$ cm$^3$ s$^{-1}$ and beta = 0.16). On the contrary, our new computations disprove the formation of acetaldehyde through reaction (3) (alpha = 1.84, 0.67 x 10$^{-13}$ cm$^3$ s$^{-1}$ and beta = -0.07, -0.95). Path (1) was showed to be inefficient too by recent computations, while path (4) was formerly considered for glycolaldehyde formation, having acetaldehyde as a by-product. In conclusions, of the four above paths only two, the (2) and (4), are potentially efficient gas-phase reaction routes for the formation of acetaldehyde and we encourage astrochemical modellers to only consider them. Comparison with astronomical observations suggest that path (4) may actually play the major role.

astro-ph.GA↗

arXiv2020

Chemical desorption versus energy dissipation: insights from ab-initio molecular dynamics of HCO formation

Molecular clouds are the cold regions of the Milky Way where stars form. They are enriched by rather complex molecules. Many of these molecules are believed to be synthesized on the icy surfaces of the interstellar submicron-sized dust grains that permeate the Galaxy. At 10 K thermal desorption is ineffcient and, therefore, why these molecules are found in the cold gas has tantalized astronomers for years. The assumption of the current models, called chemical desorption, is that the molecule formation energy released by the chemical reaction at the grain surface is partially absorbed by the grain and the remaining one causes the ejection of the newly formed molecule into the gas. Here we report an accurate ab-initio molecular dynamics simulations aimed to study the fate of the energy released by the first reaction of the H addition chain on CO, CO + H $\rightarrow$ HCO, occurring on a crystalline ice surface model. We show that about 90% of the HCO formation energy is injected towards the ice in the first picosecond, leaving HCO with an energy content (10-15 kJ mol$^{-1}$) more than a factor two lower than its adsorption energy (30 kJ mol$^{-1}$). As a result, in agreement with laboratory experiments, we conclude that chemical desorption is ineffcient for this specific system, namely H + CO on crystalline ice. We suspect this behavior to be quite general when dealing with hydrogen bonds, which are responsible of both the cohesive energy of the ice mantle and the interaction with adsorbates, as the HCO radical, even though ad hoc simulations are needed to draw specific conclusions on other systems.

astro-ph.GA↗

arXiv2019

The HH 212 interstellar laboratory: astrochemistry as a tool to reveal protostellar disks on Solar System scales around a rising Sun

The investigation of star forming regions have enormously benefited from the recent advent of the ALMA interferometer. More specifically, the unprecedented combination of high-sensitivity and high-angular resolution provided by ALMA allows one to shed light on the jet/disk systems associated with a Sun-like mass protostar. Also astrochemistry enjoyed the possibility to analyze complex spectra obtained using large bandwidths: several interstellar Complex Organic Molecules (iCOMs; C-bearing species with at least 6 atoms) have been imaged around protostars. This in turn boosted the study of the astrochemistry at work during the earliest phases of star formation paving the way to the chemical complexity in planetary systems where Life could emerge. There is mounting evidence that the observations of iCOMs can be used as unique tool to shed light, on Solar System scales (< 50 au), on the molecular content of protostellar disk. The increase of iCOMs abundances occur only under very selective physical conditions, such as those associated low-velocity shocks found where the infalling envelope is impacting the rotating accretion disk. The imaging of these regions with simpler molecules such as CO or CS is indeed paradoxically hampered by their high abundances and consequently high line opacities which do not allow the observers to disentangle all the emitting components at these small scales. In this respect, we review the state-of-the art of the ALMA analysis about the standard Sun-like star forming region in Orion named HH 212. We show (i) how all the physical components involved in the formation of a Sun-like star can be revealed only by observing different molecular tracers, and (ii) how the observation of iCOMs emission, observed to infer the chemical composition of star forming regions, can be used also as unique tracer to image protostellar disks on Solar System scales.

astro-ph.SR↗

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

Investigating the Efficiency of Explosion Chemistry as a Source of Complex Organic Molecules in TMC-1

Many species of complex organic molecules (COMs) have been observed in several astrophysical environments but it is not clear how they are produced, particularly in cold, quiescent regions. One process that has been proposed as a means to enhance the chemical complexity of the gas phase in such regions is the explosion of the ice mantles of dust grains. In this process, a build up of chemical energy in the ice is released, sublimating the ices and producing a short lived phase of high density, high temperature gas. The gas-grain chemical code UCLCHEM has been modified to treat these explosions in order to model the observed abundances of COMs towards the TMC-1 region. It is found that, based on our current understanding of the explosion mechanism and chemical pathways, the inclusion of explosions in chemical models is not warranted at this time. Explosions are not shown to improve the model's match to the observed abundances of simple species in TMC-1. Further, neither the inclusion of surface diffusion chemistry, nor explosions, results in the production of COMs with observationally inferred abundances.

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

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↗

arXiv2017

The genealogical tree of ethanol: gas-phase formation of glycolaldehyde, acetic acid and formic acid

Despite the harsh conditions of the interstellar medium, chemistry thrives in it, especially in star forming regions where several interstellar complex organic molecules (iCOMs) have been detected. Yet, how these species are synthesised is a mystery. The majority of current models claim that this happens on interstellar grain surfaces. Nevertheless, evidence is mounting that neutral gas-phase chemistry plays an important role. In this article, we propose a new scheme for the gas-phase synthesis of glycolaldehyde, a species with a prebiotic potential and for which no gas-phase formation route was previously known. In the proposed scheme, the ancestor is ethanol and the glycolaldehyde sister species are acetic acid (another iCOM with unknown gas-phase formation routes) and formic acid. For the reactions of the new scheme with no available data, we have performed electronic structure and kinetics calculations deriving rate coefficients and branching ratios. Furthermore, after a careful review of the chemistry literature, we revised the available chemical networks, adding and correcting several reactions related to glycolaldehyde, acetic acid and formic acid. The new chemical network has been used in an astrochemical model to predict the abundance of glycolaldehyde, acetic acid and formic acid. The predicted abundance of glycolaldehyde depends on the ethanol abundance in the gas phase and is in excellent agreement with the measured one in hot corinos and shock sites. Our new model overpredicts the abundance of acetic acid and formic acid by about a factor of ten, which might imply a yet incomplete reaction network.

astro-ph.SR↗

arXiv2016

The (impossible?) formation of acetaldehyde on the grain surfaces: insights from quantum chemical calculations

Complex Organic Molecules (COMs) have been detected in the interstellar medium (ISM). However, it is not clear whether their synthesis occurs on the icy surfaces of interstellar grains or via a series of gas-phase reactions. As a test case of the COMs synthesis in the ISM, we present new quantum chemical calculations on the formation of acetaldehyde (CH3CHO) from the coupling of the HCO and CH3 radicals, both in gas phase and on water ice surfaces. The binding energies of HCO and CH3 on the amorphous water ice were also computed (2333 and 734 K, respectively). Results indicate that, in gas phase, the products could be either CH3CHO, CH4 + CO, or CH3OCH, depending on the relative orientation of the two radicals. However, on the amorphous water ice, only the CH4 + CO product is possible due to the geometrical constraints imposed by the water ice surface. Therefore, acetaldehyde cannot be synthesized by the CH3 + HCO coupling on the icy grains. We discuss the implications of these results and other cases, such as ethylene glycol and dimethyl ether, in which similar situations can occur, suggesting that formation of these molecules on the grain surfaces might be unlikely.

astro-ph.EP↗

arXiv2015

Formation of complex organic molecules in cold objects: the role of gas phase reactions

While astrochemical models are successful in reproducing many of the observed interstellar species, they have been struggling to explain the observed abundances of complex organic molecules. Current models tend to privilege grain surface over gas phase chemistry in their formation. One key assumption of those models is that radicals trapped in the grain mantles gain mobility and react on lukewarm (>30 K) dust grains. Thus, the recent detections of methyl formate (MF) and dimethyl ether (DME) in cold objects represent a challenge and may clarify the respective role of grain surface and gas phase chemistry. We propose here a new model to form DME and MF with gas phase reactions in cold environments, where DME is the precursor of MF via an efficient reaction overlooked by previous models. Furthermore, methoxy, a precursor of DME, is also synthetized in the gas phase from methanol, which is desorbed by a non-thermal process from the ices. Our new model reproduces fairy well the observations towards L1544. It also explains, in a natural way, the observed correlation between DME and MF. We conclude that gas phase reactions are major actors in the formation of MF, DME and methoxy in cold gas. This challenges the exclusive role of grain-surface chemistry and favours a combined grain-gas chemistry.

astro-ph.SR↗