arXiv subjects

Juan García de la Concepción

Publications and source records attributed to Juan García de la Concepción.

12 recordsLinked to original sources

arXiv2026

A detection of sulfur-bearing cyclic hydrocarbons in space

Molecules harbouring sulfur are thought to have played a key role in the biological processes of life on Earth, and thus, they are of much interest when found in space. Here we report on the astronomical detection of a six-membered sulfur-bearing cyclic hydrocarbon in the interstellar medium. Observations of the Galactic Centre molecular cloud G+0.693-0.027 reveal the presence of 2,5-cyclohexadien-1-thione, which is a structural isomer of thiophenol ($c$-C$_6$H$_6$S). For the astronomical identification, we first performed precise laboratory measurements of the thiophenol discharge products system. These measurements, conducted in the radio band using a chirped-pulse Fourier transform microwave spectrometer, enabled us to characterize this highly polar molecular species and provided unambiguous fingerprints needed to identify this organosulfur compound in space, which now ranks as the largest interstellar sulfur-bearing molecule. These results herald the discovery of a family of prebiotically relevant sulfur-bearing species, which potentially act as a bridge between the chemical inventory of the interstellar medium and the composition of the minor bodies of the Solar System.

astro-ph.GA↗

arXiv2025

Unraveling the Conglomeratic Nature of Methanol Clusters Adsorbed on Graphene Surfaces. Insights from Molecular Dynamics Simulations

The expression of chirality in adsorption phenomena constitutes an important topic, not only relevant to asymmetric transformations involving solid surfaces, but also to the emergence of homochirality in both terrestrial and extraterrestrial scenarios. Methanol (MeOH) aggregation on graphite/graphene, one of the most idealized adsorbate-adsorbent systems, lead to islands of cyclic clusters of different sizes (Nano. Lett., 2016, 16, 3142-3147). Here, we show that this aggregation occurs enantioselectively affording 2D conglomerates depending on the size of clusters, in close analogy to a Pasteurian racemate. Homochiral sequences are held together by hydrogen bonding and other non-covalent interactions, whose absolute configurations can be appropriately specified. A discussion involving the dichotomy between 2D racemates and conglomerates, is offered as well. In addition, the present simulations showcase a broad range of acyclic and cyclic structures, even if some discrete rings are the dominant species, in agreement with previous experimental data and theoretical modeling. Our results indicate that MeOH clusters show binding energies close to the experimental values, remaining intact at temperatures as high as 120 K and up to 150 K.

cond-mat.mtrl-sci↗

arXiv2024

First detection in space of the high-energy isomer of cyanomethanimine: H2CNCN

We report the first detection in the interstellar medium of $N$-cyanomethanimine (H$_2$CNCN), the stable dimer of HCN of highest energy, and the most complex organic molecule identified in space containing the prebiotically relevant NCN backbone. We have identified a plethora of $a$-type rotational transitions with 3 $\leq J_\text{up} \leq$ 11 and $K_\text{a} \leq$ 2 that belong to this species towards the Galactic Center G+0.693-0.027 molecular cloud, the only interstellar source showing the three cyanomethanimine isomers (including the $Z$- and $E$- isomers of $C$-cyanomethanimine, HNCHCN). We have derived a total column density for H$_2$CNCN of (2.9$\, \pm \,$0.1)$\times$10$^{12}$ cm$^{-2}$, which translates into a total molecular abundance with respect to H$_2$ of (2.1$\, \pm \,$0.3)$\times$10$^{-11}$. We have also revisited the previous detection of $E$- and $Z$-HNCHCN, and found a total $C/N$-cyanomethanimine abundance ratio of 31.8$\, \pm \,$1.8 and a $Z/E$-HNCHCN ratio of 4.5$\, \pm \,$0.2. While the latter can be explained on the basis of thermodynamic equilibrium, chemical kinetics are more likely responsible for the observed $C/N$-cyanomethanimine abundance ratio, where the gas-phase reaction between methanimine (CH$_2$NH) and the cyanogen radical (CN) arises as the primary formation route.

astro-ph.GA↗

arXiv2023

H2CN/H2NC abundance ratio: a new potential temperature tracer for the interstellar medium

The ${\rm H_2NC}$ radical is the high-energy metastable isomer of ${\rm H_2CN}$ radical, which has been recently detected for the first time in the interstellar medium towards a handful of cold galactic sources, besides a warm galaxy in front of the PKS 1830-211 quasar. These detections have shown that the ${\rm H_2CN}$/${\rm H_2NC}$ isomeric ratio, likewise the HCN/HNC ratio, might increase with the kinetic temperature ($T_{\rm kin}$), but the shortage of them in warm sources still prevents us to confirm this hypothesis and shed light about their chemistry. In this work, we present the first detection of ${\rm H_2CN}$ and ${\rm H_2NC}$ towards a warm galactic source, the G+0.693-0.027 molecular cloud (with $T_{\rm kin} > 70 \, {\rm K}$), using IRAM 30m observations. We have detected multiple hyperfine components of the $N_{K_\text{a}K_\text{c}} = 1_{01} - 0_{00}$ and $2_{02} - 1_{01}$ transitions. We derived molecular abundances with respect to ${\rm H_2}$ of (6.8$\pm$1.3)$\times 10^{-11}$ for ${\rm H_2CN}$ and of (3.1$\pm$0.7)$\times 10^{-11}$ for ${\rm H_2NC}$, and a ${\rm H_2CN}$/${\rm H_2NC}$ abundance ratio of 2.2$\pm$0.5. These detections confirm that the ${\rm H_2CN}$/${\rm H_2NC}$ ratio is $\gtrsim$2 for sources with $T_{\rm kin} > 70 \, {\rm K}$, larger than the $\sim$1 ratios previously found in colder cores ($T_{\rm kin}\sim10 \, {\rm K}$). This isomeric ratio dependence with temperature cannot be fully explained with the currently proposed gas-phase formation and destruction pathways. Grain surface reactions, including the ${\rm H_2NC} \rightarrow {\rm H_2CN}$ isomerization, deserve consideration to explain the higher isomeric ratios and ${\rm H_2CN}$ abundances observed in warm sources, where the molecules can be desorbed into the gas phase through thermal and/or shock-induced mechanisms.

astro-ph.GA↗

arXiv2023

A sequential acid-base (SAB) mechanism in the interstellar medium: The emergence of cis formic acid in dark molecular clouds

The abundance ratios between isomers of a COM observed in the ISM provides valuable information about the chemistry and physics of the gas and eventually, the history of molecular clouds. In this context, the origin of an abundance of c-HCOOH acid of only 6% the isomer c-HCOOH abundance in cold cores, remains unknown. Herein, we explain the presence of c-HCOOH in dark molecular clouds through the destruction and back formation of c-HCOOH and t-HCOOH in a cyclic process that involves HCOOH and highly abundant molecules such as HCO+ and NH3. We use high-level ab initio methods to compute the potential energy profiles for the cyclic destruction/formation routes of c-HCOOH and t-HCOOH. Global rate constants and branching ratios were calculated based on the transition state theory and the master equation formalism under the typical conditions of the ISM. The destruction of HCOOH by reaction with HCO+ in the gas phase leads to three isomers of the cation HC(OH)2+. The most abundant cation can react in a second step with other abundant molecules of the ISM like NH3 to form back c-HCOOH and t-HCOOH. This mechanism explains the formation of c-HCOOH in dark molecular clouds. Considering this mechanism, the fraction of c-HCOOH with respect t-HCOOH is 25.7%. To explain the 6% reported by the observations we propose that further destruction mechanisms of the cations of HCOOH should be taken into account. The sequential acid-base (SAB) mechanism proposed in this work involves fast processes with very abundant molecules in the ISM. Thus, HCOOH very likely suffers our proposed transformations in the conditions of dark molecular clouds. This is a new approach in the framework of the isomerism of organic molecules in the ISM which has the potential to try to explain the ratio between isomers of organic molecules detected in the ISM.

astro-ph.GA↗

arXiv2022

Molecular precursors of the RNA-world in space: new nitriles in the G+0.693-0.027 molecular cloud

Nitriles play a key role as molecular precursors in prebiotic experiments based on the RNA-world scenario for the origin of life. These chemical compounds could have been partially delivered to the young Earth from extraterrestrial objects, stressing the importance of establishing the reservoir of nitriles in the interstellar medium. We report here the detection towards the molecular cloud G+0.693-0.027 of several nitriles, including cyanic acid (HOCN), and three C$_4$H$_3$N isomers (cyanoallene, CH$_2$CCHCN; propargyl cyanide, HCCCH$_2$CN; and cyanopropyne (CH$_3$CCCN), and the tentative detections of cyanoformaldehyde (HCOCN), and glycolonitrile (HOCH$_2$CN). We have also performed the first interstellar search of cyanoacetaldehyde (HCOCH$_2$CN), which was not detected. Based on the derived molecular abundances of the different nitriles in G+0.693-0.027 and other interstellar sources, we have discussed their formation mechanisms in the ISM. We propose that the observed HOCN abundance in G+0.693-0.027 is mainly due to surface chemistry and subsequent shock-induced desorption, while HCOCN might be mainly formed through gas-phase chemistry. In the case of HOCH$_2$CN, several grain-surface routes from abundant precursors could produce it. The derived abundances of the three C$_4$H$_3$N isomers in G+0.693-0.027 are very similar, and also similar to those previously reported in the dark cold cloud TMC-1. This suggests that the three isomers are likely formed through gas-phase chemistry from common precursors, possibly unsaturated hydrocarbons (CH$_3$CCH and CH$_2$CCH$_2$) that react with the cyanide radical (CN). The rich nitrile feedstock found towards G+0.693-0.027 confirms that interstellar chemistry is able to synthesize in space molecular species that could drive the prebiotic chemistry of the RNA-world.

astro-ph.GA↗

arXiv2022

Hydrogen abstraction reactions in formic and thioformic acid isomers by hydrogen and deuterium atoms. Insights on isomerism and deuteration

The isomerism of molecules in the interstellar medium and the mechanisms behind it are essential questions in the chemistry of organic molecules in space. In particular, for the simple formic and thioformic acids, the low temperatures found in molecular clouds indicate that cis-trans isomerization in the gas-phase must be impeded. Reactions happening on top of interstellar dust grains may explain the isomer interconversion at low temperatures. We studied the isomerization processes of formic and thioformic acid susceptible to happen on the surface of interstellar dust grains and initiated by H abstraction reactions. Similarly, deuterium enrichment of the acids can occur by the same mechanism. Our objective is to shed light on both topics to increase our understanding of key precursors of organic molecules in space.

astro-ph.GA↗

arXiv2022

Precursors of the RNA-world in space: Detection of ($Z$)-1,2-ethenediol in the interstellar medium, a key intermediate in sugar formation

We present the first detection of ($Z$)-1,2-ethenediol, (CHOH)$_2$, the enol form of glycolaldehyde, in the interstellar medium towards the G+0.693-0.027 molecular cloud located in the Galactic Center. We have derived a column density of (1.8$\pm$0.1)$\times$10$^{13}$ cm$^{-2}$, which translates into a molecular abundance with respect to molecular hydrogen of 1.3$\times$10$^{-10}$. The abundance ratio between glycolaldehyde and ($Z$)-1,2-ethenediol is $\sim$5.2. We discuss several viable formation routes through chemical reactions from precursors such as HCO, H$_2$CO, CHOH or CH$_2$CHOH. We also propose that this species might be an important precursor in the formation of glyceraldehyde (HOCH$_2$CHOHCHO) in the interstellar medium through combination with the hydroxymethylene (CHOH) radical.

astro-ph.GA↗

arXiv2022

Ionise hard: interstellar PO$^{+}$ detection

We report the first detection of the phosphorus monoxide ion (PO$^{+}$) in the interstellar medium. Our unbiased and very sensitive spectral survey towards the G+0.693$-$0.027 molecular cloud covers four different rotational transitions of this molecule, two of which ($J$=1$-$0 and $J$=2$-$1) appear free of contamination from other species. The fit performed, assuming Local Thermodynamic Equilibrium conditions, yields a column density of $N$=(6.0$\pm$0.7)$\times$10$^{11}$ cm$^{-2}$. The resulting molecular abundance with respect to molecular hydrogen is 4.5$\times$10$^{-12}$. The column density of PO$^{+}$ normalised by the cosmic abundance of P is larger than those of NO$^{+}$ and SO$^{+}$, normalised by N and S, by factors of 3.6 and 2.3, respectively. The $N$(PO$^{+}$)/$N$(PO) ratio is 0.12$\pm$0.03, more than one order of magnitude higher than those of $N$(SO$^{+}$)/$N$(SO) and $N$(NO$^{+}$)/$N$(NO). These results indicate that P is more efficiently ionised in the ISM than N and S. We have performed new chemical models that confirm that the PO$^+$ abundance is strongly enhanced in shocked regions with high values of cosmic-ray ionisation rates (10$^{-15}-$10$^{-14}$ s$^{-1}$), as occurs in the G+0.693$-$0.027 molecular cloud. The shocks sputter the interstellar icy grain mantles, releasing into the gas phase most of their P content, mainly in the form of PH$_3$, which is converted into atomic P, and then ionised efficiently by cosmic rays, forming P$^+$. Further reactions with O$_2$ and OH produce PO$^{+}$. The cosmic-ray ionisation of PO might also contribute significantly, which would explain the high $N$(PO$^{+}$)/$N$(PO) observed. The relatively high gas-phase abundance of PO$^{+}$ with respect to other P-bearing species stresses the relevance of this species in the interstellar chemistry of P.

astro-ph.GA↗

arXiv2021

Diastereoselective Formation of trans-HC(O)SH Through Hydrogenation of OCS on Interstellar Dust Grains

With the presence of evermore complex S-bearing molecules being detected lately, studies on their chemical formation routes need to keep up the pace to rationalize observations, suggest new candidates for detection, and provide input for chemical evolution models. In this paper, we theoretically characterize the hydrogenation channels of OCS on top of amorphous solid water as an interstellar dust grain analog in molecular clouds. Our results show that the significant reaction outcome is trans-HC(O)SH, a recently detected prebiotic molecule toward G+0.693. The reaction is diastereoselective, explaining the seemingly absence of the cis isomer in the astronomical observations. We found that the reaction proceeds through a highly localized radical intermediate (cis-OCSH), which could be essential in the formation of other sulfur-bearing complex organic molecules due to its slow isomerization dynamics on top of amorphous solid water.

astro-ph.GA↗

arXiv2021

Formation of phosphorus monoxide (PO) in the interstellar medium: insights from quantum-chemical and kinetic calculations

In recent years, phosphorus monoxide (PO) -- an important molecule for prebiotic chemistry -- has been detected in star-forming regions and in the comet 67P/Churyumov-Gerasimenko. These studies have revealed that, in the interstellar medium, PO is systematically the most abundant P-bearing species, with abundances that are $\sim$1-3 times greater than those derived for phosphorus nitride (PN), the second most abundant P-containing molecule. The reason why PO is more abundant than PN remains still unclear. Experimental studies with phosphorus in the gas phase are not available, probably because of the difficulties in dealing with its compounds. Therefore, the reactivity of atomic phosphorus needs to be investigated using reliable computational tools. To this end, state-of-the-art quantum-chemical computations have been employed to evaluate accurate reaction rates and branching ratios for the P + OH $\rightarrow$ PO + H and P + H$_2$O $\rightarrow$ PO + H$_2$ reactions in the framework of a master equation approach based on ab-initio transition state theory. The hypothesis that OH and H${_2}$O can be potential oxidizing agents of atomic phosphorus is based on the ubiquitous presence of H${_2}$O in the ISM. Its destruction then produces OH, which is another very abundant species. While the reaction of atomic phosphorus in its gound state with water is not a relevant source of PO because of emerged energy barriers, the P + OH reaction represents an important formation route of PO in the interstellar medium. Our kinetic results show that this reaction follow an Arrhenius behavior, and thus its rate coefficients alpha=2.28$\times$10$^{-10}$ cm${^3}$ molecule$^{-1}$ s$^{-1}$, beta=0.16 and gamma=0.37 K increase by increasing the temperature.

astro-ph.GA↗

arXiv2021

The origin of the E/Z isomer ratio of imines in the interstellar medium

Recent astronomical observations of both isomers E and Z of imines such as cyanomethanimine, ethanimine and 2-propyn-1-imine, have revealed that the abundances in the ISM of these isomers differ by factors of ~3-10. Several theories have been proposed to explain the observed behavior, but none of them successfully explains the [E]/[Z] ratios. In this work we present a detailed study of the kinetics of the one-step E-Z isomerization reactions of cyanomethanimine, ethanimine and 2-propyn-1-imine under interstellar conditions (in the 10-400 K temperature range). This reaction was previously thought to be non-viable in the ISM due to its associated high-energy barrier (about 13,000 K). In this Letter, we show that considering the multidimensional small curvature tunneling approximation, the tunneling effect enables the isomerization even at low temperatures. This is due to the fact that the representative tunneling energy lies in the vibrational ground state of the least stable isomer up to approximately 150 K, making the reaction constants of the isomerization from the least stable to the most stable isomer basically constant. The predicted [E]/[Z] ratios are almost the same as those reported from the astronomical observations for all imines observed. This study demonstrates that the [E]/[Z] ratio of imines in the ISM strongly depends on their relative stability.

physics.chem-ph↗