Interstellar Molecules Research Articles

Deuterium Isotope Fractionation of Polycyclic Aromatic Hydrocarbons in Meteorites as an Indicator of Interstellar/Protosolar Processing History.

The stable isotope composition of soluble and insoluble organic compounds in carbonaceous chondrites can be used to determine the provenance of organic molecules in space. Deuterium enrichment in meteoritic organics could be a residual signal of synthetic reactions occurring in the cold interstellar medium or an indicator of hydrothermal parent-body reactions. δD values have been measured in grains and bulk samples for a wide range of meteorites; however, these reservoirs are highly variable and may have experienced fractionation during thermal and/or aqueous alteration. Among the plethora of organic compounds in meteorites are polycyclic aromatic hydrocarbons (PAHs), which are stable and abundant in carbonaceous chondrites, and their δD ratio may preserve evidence about their formation environment as well as the influence of parent-body processes. This study tests hypotheses about the potential links between PAHs-deuteration concentrations and their formation conditions by examining the δD ratio of PAHs in three CM carbonaceous chondrites representing an aqueous alteration gradient. We use deuterium enrichments in soluble 2–5-ring PAHs as an indicator of either photon-driven deuteration due to unimolecular photodissociation in warm regions of space, gas-phase ion–molecule reactions in cold interstellar regions of space, or UV photolysis in ices. We also test hypothesized reaction pathways during parent-body processing that differ between partially and fully aromatized PAHs. New methodological approaches were developed to extract small, volatile PAHs without fractionation. Our results suggest that meteoritic PAHs could have formed through reactions in cold regions, with possible overprinting of deuterium enrichment during aqueous parent-body alteration, but the data could not rule out PAH alteration in icy mantles as well.

Infrared spectra of complex organic molecules in astronomically relevant ice mixtures

Context. The increasing sensitivity and resolution of ground-based telescopes have enabled the detection of gas-phase complex organic molecules (COMs) across a variety of environments. Many of the detected species are expected to form on the icy surface of interstellar grains and transfer later into the gas phase. Therefore, icy material is regarded as a primordial source of complex molecules in the interstellar medium. Upcoming James Webb Space Telescope (JWST) observations of interstellar ices in star-forming regions will reveal infrared (IR) features of frozen molecules with unprecedented resolution and sensitivity. To identify COM features in the JWST data, laboratory IR spectra of ices for conditions that simulate interstellar environments are needed. Aims. This work provides laboratory mid-IR spectra of methyl cyanide (CH3CN, also known as acetonitrile) ice in its pure form and mixed with known interstellar molecules at cryogenic temperatures. The spectroscopic data presented in this work will support the interpretation of JWST ice observations and are made available to the community through the Leiden Ice Database for Astrochemistry (LIDA). Methods. Fourier transform IR spectroscopy is used to record the mid-IR spectra (500–4000 cm−1/20–2.5 µm, with a resolution of 1 cm−1 ) of methyl cyanide (acetonitrile, CH3 CN) mixed with H2O, CO, CO2, CH4, NH3, H2O:CO2, and H2O:CH4:NH3, at temperatures ranging from 15 to 150 K. The refractive index (at 632.8 nm) of pure amorphous CH3CN ice at 15 K and the band strength of selected IR transitions are also measured. Results. We present a variety of reference mid-IR spectra of frozen CH3CN that can be compared to astronomical ice observations. The peak position and full width at half maximum (FWHM) of six absorption bands of frozen methyl cyanide in its pure form and mixed ices, at temperatures between 15–150 K, are characterized. These bands are the following: the CH3 symmetric stretching at 2940.9 cm−1 (3.400 µm), the CN stretching at 2252.2 cm−1 (4.440 µm), a peak resulting from a combination of different vibrational modes at 1448.3 cm−1 (6.905 µm), the CH3 antisymmetric deformation at 1410 cm−1 (7.092 µm), the CH3 symmetric deformation at 1374.5 cm−1 (7.275 um), and the CH3 rock vibration at 1041.6 cm−1 (9.600 um). Additionally, the apparent band strength of these vibrational modes in mixed ices is derived. The laboratory spectra of CH3CN are compared to observations of interstellar ices toward W33A and three low-mass Young Stellar Objects (YSO). Since an unambiguous identification of solid methyl cyanide toward these objects is not possible, upper limits for the CH3CN column density are determined as ≤2.4 × 1017 molecules cm−2 for W33A and 5.2 × 1016, 1.9 × 1017, and 3.8 × 1016 molecules cm−2 for EC92, IRAS 03235, and L1455 IRS3, respectively. With respect to solid H2O, these values correspond to relative abundances of 1.9, 3.1, 1.3, and 4.1%, for W33A, EC92, IRAS 03235, and L1455 IRS3, respectively.

Radical addition and H abstraction reactions in C2H2, C2H4, and C2H6: A gateway for ethyl- and vinyl-bearing molecules in the interstellar medium

Context. Recent interstellar detections include a significant number of molecules containing vinyl (C2H3) and ethyl (C2H5) groups in their structure. For several of these molecules, there is no clear experimental or theoretical evidence that supports their formation from simpler precursors. Aims. We carried out a systematic search of viable reactions starting from closed-shell hydrocarbons containing two carbon atoms (ethane, C2H6; ethylene, C2H4; and acetylene, C2H2), with the goal of determining viable chemical routes for the formation of vinyl and ethyl molecules on top of interstellar dust grains. Methods. We used density functional theory calculations in combination with semiclassical instantem theory to derive the rate coefficients for the radical-neutral surface reactions. The effect of a surface was modeled through an implicit surface approach, profiting from the weak interaction between the considered hydrocarbons and the dust surfaces. Results. Our results show that both H and OH radicals are key in converting acetylene and ethylene into more complex radicals that are liable to continue reacting and to form interstellar complex organic molecules. The relevant reactions, for example OH additions, present rate constants above 101 s−1 that are likely competitive with OH diffusion on grains. Similarly, H atom addition to acetylene and ethylene is a very fast process, with rate constants above 104 s−1 in all cases, and is greatly enhanced by quantum tunneling. Hydrogen abstraction reactions are less relevant, but may play a role in specific cases involving the OH radical. Reactions with other radicals NH2 and CH3 are likely to have much less impact on the chemistry of ethyl- and vinyl-bearing molecules. Conclusions. The effective formation at low temperatures of four radicals (C2H3, C2H5, C2H2OH, and C2H4OH) through our proposed mechanism opens the gate for the formation of complex organic molecules, and indicates a potential prevalence of OH-bearing molecules on the grain. Following our suggested reaction pathway, we explain the formation of many of the newly detected molecules, and propose new molecules for detection. Our results reinforce the recent view on the importance of the OH radical in interstellar surface chemistry.

Resolving desorption of complex organic molecules in a hot core

Context. The presence of many interstellar complex organic molecules (COMs) in the gas phase in the vicinity of protostars has long been associated with their formation on icy dust grain surfaces before the onset of protostellar activity, and their subsequent thermal co-desorption with water, the main constituent of the grains’ ice mantles, as the protostar heats its environment to ~100 K. Aims. Using the high angular resolution provided by the Atacama Large Millimetre/submillimetre Array (ALMA), we want to resolve the COM emission in the hot molecular core Sagittarius B2 (N1) and thereby shed light on the desorption process of COMs in hot cores. Methods. We used data taken as part of the 3 mm spectral line survey Re-exploring Molecular Complexity with ALMA (ReMoCA) to investigate the morphology of COM emission in Sagittarius B2 (N1). We also used ALMA continuum data at 1 mm taken from the literature. Spectra of ten COMs (including one isotopologue) were modelled under the assumption of local thermodynamic equilibrium (LTE) and population diagrams were derived for these COMs for positions at various distances to the south and west from the continuum peak. Based on this analysis, we produced resolved COM rotation temperature and column density profiles. H2 column density profiles were derived from dust continuum emission and C18O 1–0 emission and used to derive COM abundance profiles as a function of distance and temperature. These profiles are compared to astrochemical models. Results. Based on the morphology, a rough separation into O- and N-bearing COMs can be done. The temperature profiles span a range of 80–300 K with power-law indices from −0.4 to −0.8, which is in agreement with expectations of protostellar heating of an envelope with optically thick dust. Column density and abundance profiles reflect a similar trend as seen in the morphology. While abundances of N-bearing COMs peak only at the highest temperatures, those of most O-bearing COMs peak at lower temperatures and remain constant or decrease towards higher temperatures. Many abundance profiles show a steep increase at ~100 K. To a great extent, the observed results agree with results of astrochemical models that, besides the co-desorption with water, predict that O-bearing COMs are mainly formed on dust-grain surfaces at low temperatures, while at least some N-bearing COMs and CH3CHO are substantially formed in the gas phase at higher temperatures. Conclusions. Our observational results, in comparison with model predictions, suggest that COMs that are exclusively or, to a great extent, formed on dust grains desorb thermally at ~100 K from the grain surface, likely alongside water. A dependence on the COM binding energy is not evident from our observations. Non-zero abundance values below ~100 K suggest that another desorption process of COMs is at work at these low temperatures: either non-thermal desorption or partial thermal desorption related to the lower binding energies experienced by COMs in the outer, water-poor ice layers. In either case, this is the first time that the transition between two regimes of COM desorption has been resolved in a hot core.

Rotational Spectra of Unsaturated Carbon Chains Produced by Pyrolysis: The Case of Propadienone, Cyanovinylacetylene, and Allenylacetylene.

Several interstellar molecules are highly reactive unsaturated carbon chains, which are unstable under terrestrial conditions. Laboratory studies in support of their detection in space thus face the issue of how to produce these species and how to correctly model their rotational energy levels. In this work, we introduce a general approach for producing and investigating unsaturated carbon chains by means of selected test cases. We report a comprehensive theoretical/experimental spectroscopic characterization of three species, namely, propadienone, cyanovinylacetylene, and allenylacetylene, all of them being produced by means of flash vacuum pyrolysis of a suitable precursor. For each species, quantum-chemical calculations have been carried out with the aim of obtaining accurate predictions of the missing spectroscopic information required to guide spectral analysis and assignment. Rotational spectra of the title molecules have been investigated up to 400 GHz by using a frequency-modulation millimeter-/submillimeter-wave spectrometer, thus significantly extending spectral predictions over a wide range of frequency and quantum numbers. A comparison between our results and those available in the literature points out the clear need of the reported laboratory measurements at higher frequencies for setting up accurate line catalogs for astronomical searches.

Acetaldehyde binding energies: a coupled experimental and theoretical study

ABSTRACT Acetaldehyde is one of the most common and abundant gaseous interstellar complex organic molecules found in cold and hot regions of the molecular interstellar medium. Its presence in the gas-phase depends on the chemical formation and destruction routes, and its binding energy (BE) governs whether acetaldehyde remains frozen on to the interstellar dust grains or not. In this work, we report a combined study of the acetaldehyde BE obtained via laboratory temperature programmed desorption (TPD) experiments and theoretical quantum chemical computations. BEs have been measured and computed as a pure acetaldehyde ice and mixed with both polycrystalline and amorphous water ice. Both calculations and experiments found a BE distribution on amorphous solid water that covers the 4000–6000 K range when a pre-exponential factor of $1.1\times 10^{18}\, \mathrm{s}^{-1}$ is used for the interpretation of the experiments. We discuss in detail the importance of using a consistent couple of BE and pre-exponential factor values when comparing experiments and computations, as well as when introducing them in astrochemical models. Based on the comparison of the acetaldehyde BEs measured and computed in the present work with those of other species, we predict that acetaldehyde is less volatile than formaldehyde, but much more than water, methanol, ethanol, and formamide. We discuss the astrochemical implications of our findings and how recent astronomical high spatial resolution observations show a chemical differentiation involving acetaldehyde, which can easily explained due to the different BEs of the observed molecules.

Binding Energy Evaluation Platform: A Database of Quantum Chemical Binding Energy Distributions for the Astrochemical Community

The quality of astrochemical models is highly dependent on reliable binding energy (BE) values that consider the morphological and energetic variety of binding sites on the surface of ice-grain mantles. Here, we present the Binding Energy Evaluation Platform (BEEP) and database that, using quantum chemical methods, produces full BE distributions of molecules bound to an amorphous solid water (ASW) surface model. BEEP is highly automatized and allows one to sample binding sites on a set of water clusters and to compute accurate BEs. Using our protocol, we computed 21 BE distributions of interstellar molecules and radicals on an amorphized set of 15–18 water clusters of 22 molecules each. The distributions contain between 225 and 250 unique binding sites. We apply a Gaussian fit and report the mean and standard deviation for each distribution. We compare with existing experimental results and find that the low- and high-coverage experimental BEs coincide well with the high-BE tail and mean value of our distributions, respectively. Previously reported single BE theoretical values are broadly in line with ours, even though in some cases significant differences can be appreciated. We show how the use of different BE values impacts a typical problem in astrophysics, such as the computation of snow lines in protoplanetary disks. BEEP will be publicly released so that the database can be expanded to other molecules or ice models in a community effort.

Interstellar Complex Organic Molecules in SiO-traced Massive Outflows

The interstellar medium contains dust and gas, in which molecules can proliferate at high densities and in cold conditions. Interstellar complex organic molecules (iCOMs) are C-bearing species that contain at least six atoms. As they are detected in young stellar objects, iCOMs are expected to inhabit early stages of star formation evolution. In this study, we try to determine which iCOMs are present in the outflow component of massive protostars. To do this, we analyzed the morphological extension of blue- and redshifted iCOM emission in a sample of 11 massive protostars employing mapping observations at 1 mm within a ∼1 GHz bandwidth for both the IRAM-30 m and APEX telescopes. We modeled the iCOM emission of the central pointing spectra of our objects using the XCLASS local thermal equilibrium radiative transfer code. We detected the presence of several iCOMs such as CH3OH, 13CH3OH, CH3OCHO, C2H5C15N, and (c-C3H2)CH2. In G034.41+0.24, G327.29-0.58, G328.81+0.63, G333.13-0.43, G340.97-1.02, G351.45+0.66, and G351.77-0.54, the iCOM lines show a faint broad-line profile. Due to the offset peak positions of the blue- and redshifted emission, covering from ∼0.1 to 0.5 pc, these wings are possibly related to movements external to the compact core, such as large-scale low-velocity outflows. We have also established a correlation between the parent iCOM molecule CH3OH and the shock tracer SiO, reinforcing the hypothesis that shock environments provide the conditions to boost the formation of iCOMs via gas-phase reactions.

The Remarkable Roles of the Receptor for Advanced Glycation End Products (RAGE) and Its Soluble Isoforms in COVID-19: The Importance of RAGE Pathway in the Lung Injuries.

The respiratory symptoms of acute respiratory distress syndrome (ARDS) in the coronavirus disease 2019 (COVID-19) patients is associated with accumulation of pre-inflammatory molecules such as advanced glycation end-products (AGES), calprotectin, high mobility group box family-1 (HMGB1), cytokines, angiotensin converting enzyme 2 (ACE2), and other molecules in the alveolar space of lungs and plasma. The receptor for advanced glycation end products (RAGEs), which is mediated by the mitogen-activated protein kinase (MAPK), plays a critical role in the severity of chronic inflammatory diseases such as diabetes mellitus (DM) and ARDS. The RAGE gene is most expressed in the alveolar epithelial cells (AECs) of the pulmonary system. Several clinical trials are now being conducted to determine the possible association between the levels of soluble isoforms of RAGE (sRAGE and esRAGE) and the severity of the disease in patients with ARDS and acute lung injury (ALI). In the current article, we reviewed the most recent studies on the RAGE/ligands axis and sRAGE/esRAGE levels in acute respiratory illness, with a focus on COVID-19–associated ARDS (CARDS) patients. According to the research conducted so far, sRAGE/esRAGE measurements in patients with CARDS can be used as a powerful chemical indicator among other biomarkers for assessment of early pulmonary involvement. Furthermore, inhibiting RAGE/MAPK and Angiotensin II receptor type 1 (ATR1) in CARDS patients can be a powerful strategy for diminishing cytokine storm and severe respiratory symptoms.

Thermal Energy Transfer between Helium Gas and Graphene Surface According to Molecular Dynamics Simulations and the Monte Carlo Method.

The scattering of gases on solid surfaces plays a vital role in many advanced technologies. In this study, the scattering behavior of helium on graphene surfaces was investigated, including the thermal accommodation coefficient (TAC), outgoing zenith angle of helium, bounce number, and interaction time. First, we performed molecular dynamics simulations to describe the incident angle-resolved behaviors, and showed that the scattering is highly dependent on the zenith angle of incident helium but insensitive to the azimuthal angle. The contribution of the normal velocity component of the incident helium dominated the energy transfer. The nonlinear relationship of the parameters to the zenith angle of the incident helium could be suppressed by increasing the graphene temperature or decreasing the speed of the incident helium. Subsequently, the scattering performance considering all gas molecules in the hemispherical space was evaluated using the Monte Carlo method with angle-resolved results. The result showed that the TAC, its nominal components, and the zenith angle of the scattered helium increased with higher speeds of incident helium and lower temperatures of graphene. This study should provide a fundamental understanding of energy transfer between gas and two-dimensional materials and guidelines to tune the scattering behavior between them.

Searching for biosignatures by their rotational spectrum: global fit and methyl group internal rotation features of dimethylsulphoxide up to 116 GHz

AbstractThe identification and quantification of molecules in interstellar space and atmospheres of planets in the solar systems and in exoplanets rely on spectroscopic methods and laboratory work is essential to provide the community with the spectral features needed to analyse cosmological observations. Rotational spectroscopy in particular, with its intrinsic high resolution, allows the unambiguous identification of biomolecular building blocks and biosignature gases which can be correlated with the origin of life or the identification of habitable planets. We report the extension of the measured rotational transition frequencies of dimethylsulphoxide and its 34S and 13C isotopologues in the millimetre wave range (59.6–78.4 GHz) by use of an absorption spectrometer based on the supersonic expansion technique. Hyperfine patterns related to the methyl group internal rotation were analysed in the microwave range region (6–18 GHz) with a Pulsed Jet Fourier Transform spectrometer at extremely high resolution (2 kHz) and reliable predictions up to 116 GHz are provided. The focus on sulphur-bearing molecules is motivated by the fact that sulphur is largely involved in the intra- and inter-molecular hydrogen bonds in proteins and although it is the 10th most abundant element in the known Universe, understanding its chemistry is still a matter of debate. Moreover, sulphur-bearing molecules, in particular dimethylsulphoxide, have been indicated as possible biosignature gases to be monitored in the search of habitable exoplanets.

Desorption of organic molecules from interstellar ices, combining experiments and computer simulations: Acetaldehyde as a case study

Context. Explaining the presence of complex organic molecules (COMs) in interstellar environments requires a thorough understanding of the physics and chemistry occurring in the interplay between the gas phase and interstellar surfaces. Experiments and computer simulations are pivotal in building a comprehensive catalogue of processes of relevance for the build up of organic molecules in those environments. Aims. We combine experiments with tailored computer simulations to study the desorption dynamics of acetaldehyde CH3CHO – an important organic precursor in cold interstellar environments - on amorphous solid water for the first time. Our goals with this paper are twofold. Firstly, we want to contextualise the role of this molecule in the evolution of organic molecules in space. Secondly, we want to suggest a joint scheme to produce quantitative information on desorption magnitudes based on the combination of computations and experiments. This scheme can be adopted to refine measurements of other molecules. Methods. We determined desorption energies and pre-exponential factors of desorption theoretically using molecular dynamics simulations that combine semi-empirical and density functional calculations. We also performed temperature-programmed desorption experiments with acetaldehyde on top of non-porous amorphous solid water. The combination of theoretical and experimental results allows us to derive reliable quantities, which are required for understanding the desorption dynamics of interstellar COMs (iCOMs) atop interstellar ices. Results. The average theoretical and experimental desorption energies found for CH3CHO desorbing from non-porous amorphous solid water (np-ASW) surfaces are 3624 K and 3774 K, respectively. The pre-exponential factor determined theoretically is vtheo = 2.4 × 1012 s−1 while from the experiments it was possible to constrain this magnitude to 1012±1 s−1. Conclusions. The comparison of the desorption energies of CH3CHO with other COMs, such as CH3NH2 or CH3NO, shows that CH3CHO is more volatile. Therefore, we suggest that, in consideration of the average binding energy, CH3CHO should undergo preferential desorption during the ice-sublimation phase in hot cores enriching the gas-phase in this particular component. In addition, the overall low binding energy suggests a possible early return to the gas phase of pre-stellar cores due to non-thermal effects (i.e. reactive desorption or cosmic-ray-induced desorption). This could explain the prevalence of CH3CHO in the gas phase of pre-stellar cores. Dedicated laboratory and theoretical efforts are required to confirm this last point.

The emergence of interstellar molecular complexity explained by interacting networks

Recent years have witnessed the detection of an increasing number of complex organic molecules in interstellar space, some of them being of prebiotic interest. Disentangling the origin of interstellar prebiotic chemistry and its connection to biochemistry and ultimately, to biology is an enormously challenging scientific goal where the application of complexity theory and network science has not been fully exploited. Encouraged by this idea, we present a theoretical and computational framework to model the evolution of simple networked structures toward complexity. In our environment, complex networks represent simplified chemical compounds and interact optimizing the dynamical importance of their nodes. We describe the emergence of a transition from simple networks toward complexity when the parameter representing the environment reaches a critical value. Notably, although our system does not attempt to model the rules of real chemistry nor is dependent on external input data, the results describe the emergence of complexity in the evolution of chemical diversity in the interstellar medium. Furthermore, they reveal an as yet unknown relationship between the abundances of molecules in dark clouds and the potential number of chemical reactions that yield them as products, supporting the ability of the conceptual framework presented here to shed light on real scenarios. Our work reinforces the notion that some of the properties that condition the extremely complex journey from the chemistry in space to prebiotic chemistry and finally, to life could show relatively simple and universal patterns.

Strategies for Controlling the Spatial Orientation of Single Molecules Tethered on DNA Origami Templates Physisorbed on Glass Substrates: Intercalation and Stretching.

Nanoarchitectural control of matter is crucial for next-generation technologies. DNA origami templates are harnessed to accurately position single molecules; however, direct single molecule evidence is lacking regarding how well DNA origami can control the orientation of such molecules in three-dimensional space, as well as the factors affecting control. Here, we present two strategies for controlling the polar (θ) and in-plane azimuthal (ϕ) angular orientations of cyanine Cy5 single molecules tethered on rationally-designed DNA origami templates that are physically adsorbed (physisorbed) on glass substrates. By using dipolar imaging to evaluate Cy5′s orientation and super-resolution microscopy, the absolute spatial orientation of Cy5 is calculated relative to the DNA template. The sequence-dependent partial intercalation of Cy5 is discovered and supported theoretically using density functional theory and molecular dynamics simulations, and it is harnessed as our first strategy to achieve θ control for a full revolution with dispersion as small as ±4.5°. In our second strategy, ϕ control is achieved by mechanically stretching the Cy5 from its two tethers, being the dispersion ±10.3° for full stretching. These results can in principle be applied to any single molecule, expanding in this way the capabilities of DNA as a functional templating material for single-molecule orientation control. The experimental and modeling insights provided herein will help engineer similar self-assembling molecular systems based on polymers, such as RNA and proteins.

JmjC Family of Histone Demethylases Form Nuclear Condensates.

The Jumonji-C (JmjC) family of lysine demethylases (KDMs) (JMJC-KDMs) plays an essential role in controlling gene expression and chromatin structure. In most cases, their function has been attributed to the demethylase activity. However, accumulating evidence demonstrates that these proteins play roles distinct from histone demethylation. This raises the possibility that they might share domains that contribute to their functional outcome. Here, we show that the JMJC-KDMs contain low-complexity domains and intrinsically disordered regions (IDR), which in some cases reached 70% of the protein. Our data revealed that plant homeodomain finger protein (PHF2), KDM2A, and KDM4B cluster by phase separation. Moreover, our molecular analysis implies that PHF2 IDR contributes to transcription regulation. These data suggest that clustering via phase separation is a common feature that JMJC-KDMs utilize to facilitate their functional responses. Our study uncovers a novel potential function for the JMJC-KDM family that sheds light on the mechanisms to achieve the competent concentration of molecules in time and space within the cell nucleus.

Theoretical Study on Formamide (NH2CHO) and Methylidene (CH2) Reactions for the Formation of Interstellar N-Methylformamide

N-methylformamide (NMF), E & Z containing an amide bond, a vital component of peptides, is one of the simplest derivatives of formamides. It is detected towards the hot molecular core of the Sgr B2(N2) molecular cloud with the Atacama Large Millimeter/submillimeter Array (ALMA). It is proposed that the radical-molecule mechanism can be used as a strong contrivance to investigate the formation of NMF in the interstellar medium (ISM) via some interstellar molecules like methylidene CH2(1Σ1 & 3Σ1) and formamide (NH2CHO). The density functional theory (DFT) at B3LYP/6-311G (d,p) has been applied to study the mechanisms. All the possible cases of E- & Z-NMF formation with singlet and triplet CH2 have been investigated. It is found that the formation of E-NMF with CH2(1Σ1) and Z-NMF with CH2(3Σ1) is more feasible and favorable in comparison to E-NMF formation from CH2(3Σ1) and Z-NMF with CH2(1Σ1).

Ultrafast Excited State Dynamics of Spatially Confined Organic Molecules.

This Feature Article highlights the role of spatial confinement in controlling the fundamental behavior of molecules. Select examples illustrate the value of using space as a tool to control and understand excited-state dynamics through a combination of ultrafast spectroscopy and conventional steady-state methods. Molecules of interest were confined within a closed molecular capsule, derived from a cavitand known as octa acid (OA), whose internal void space is sufficient to accommodate molecules as long as tetracene and as wide as pyrene. The free space, i.e., the space that is left following the occupation of the guest within the host, is shown to play a significant role in altering the behavior of guest molecules in the excited state. The results reported here suggest that in addition to weak interactions that are commonly emphasized in supramolecular chemistry, the extent of empty space (i.e., the remaining void space within the capsule) is important in controlling the excited-state behavior of confined molecules on ultrafast time scales. For example, the role of free space in controlling the excited-state dynamics of guest molecules is highlighted by probing the cis-trans isomerization of stilbenes and azobenzenes within the OA capsule. Isomerization of both types of molecule are slowed when they are confined within a small space, with encapsulated azobenzenes taking a different reaction pathway compared to that in solution upon excitation to S2. In addition to steric constraints, confinement of reactive molecules in a small space helps to override the need for diffusion to bring the reactants together, thus enabling the measurement of processes that occur faster than the time scale for diffusion. The advantages of reducing free space and confining reactive molecules are illustrated by recording unprecedented excimer emission from anthracene and by measuring ultrafast electron transfer rates across the organic molecular wall. By monitoring the translational motion of anthracene pairs in a restricted space, it has been possible to document the pathway undertaken by excited anthracene from inception to the formation of the excimer on the excited-state surface. Similarly, ultrafast electron transfer experiments pursued here have established that the process is not hindered by a molecular wall. Apparently, the electron can cross the OA capsule wall provided the donor and acceptor are in close proximity. Measurements on the ultrafast time scale provide crucial insights for each of the examples presented here, emphasizing the value of both "space" and "time" in controlling and understanding the dynamics of excited molecules.

Hydrogen abstraction reactions in formic and thioformic acid isomers by hydrogen and deuterium atoms

Context.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 the particular case of 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 taking place on top of interstellar dust grains may explain the isomer interconversion at low temperatures.Aims.We studied the isomerization processes of formic and thioformic acid that are likely to take place on the surface of interstellar dust grains after being 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 expand our understanding of the key precursors of organic molecules in space.Methods.We determined the rate constants for the H abstraction reactions as well as the binding energies for the acids on water ice using ab initio calculations and the instanton method for calculating the rate constants, including quantum tunneling. In addition, we tested the viability of the deuteration of formic acid with tailored experiments and looked for it on the L1544 source.Results.For formic acid, there is a clear dependence of the H abstraction reactions on the isomer of the reactant, with rate constants at ~50 K that differ by five orders of magnitude. Correspondingly, we did not observe the trans-cis reaction in our experiments. In the case of thioformic acid, a very similar cis-trans reactivity is found for abstraction reactions at the thiol (-SH) group in contrast to a preferential reactivity that is found when abstractions take place at the -CH moiety. We found comparable binding energies for both isomers with average binding energies of around −6200 and −3100 K for formic and thioformic acid, respectively. Our binding energy calculations show that the reactions are precluded for specific orientations, affecting the overall isomerization rate. For H abstractions initiated by deuterium atoms, we found very similar trends, with kinetic isotope effects varying in most cases between 13 and 20.Conclusions.Our results support the cis-trans interconversion of cis-formic acid on dust grains, suggesting that such an acid should not withstand the conditions found on these objects. On the other hand, the trans isomer is very resilient. Both isomers of thioformic acid are much more reactive. A non-trivial chemistry is behind the apparent excess of its trans isomer that is found in cold molecular clouds and star-forming regions due to a subtle combination of preferential reactivity and binding with the surface. In light of our results, all the deuterated counterparts of thioformic acid are viable molecules to be present on the ISM. In contrast, only the trans isomer of deuterated formic acid is expected, for which we provide upper bounds of detection. Given the mechanisms presented in this paper, other mechanisms must be at play to explain the tiny fraction of cis-formic acid observed in interstellar cold environments, as well as the current trans-DCOOH and trans-HCOOD abundances in hot-corinos.

Chemical and Physical Characterization of the Isolated Protostellar Source CB68: FAUST IV

The chemical diversity of low-mass protostellar sources has so far been recognized, and environmental effects are invoked as its origin. In this context, observations of isolated protostellar sources without the influence of nearby objects are of particular importance. Here, we report the chemical and physical structures of the low-mass Class 0 protostellar source IRAS 16544−1604 in the Bok globule CB 68, based on 1.3 mm Atacama Large Millimeter/submillimeter Array observations at a spatial resolution of ∼70 au that were conducted as part of the large program FAUST. Three interstellar saturated complex organic molecules (iCOMs), CH3OH, HCOOCH3, and CH3OCH3, are detected toward the protostar. The rotation temperature and the emitting region size for CH3OH are derived to be 131 ± 11 K and ∼10 au, respectively. The detection of iCOMs in close proximity to the protostar indicates that CB 68 harbors a hot corino. The kinematic structure of the C18O, CH3OH, and OCS lines is explained by an infalling–rotating envelope model, and the protostellar mass and the radius of the centrifugal barrier are estimated to be 0.08–0.30 M ⊙ and <30 au, respectively. The small radius of the centrifugal barrier seems to be related to the small emitting region of iCOMs. In addition, we detect emission lines of c-C3H2 and CCH associated with the protostar, revealing a warm carbon-chain chemistry on a 1000 au scale. We therefore find that the chemical structure of CB 68 is described by a hybrid chemistry. The molecular abundances are discussed in comparison with those in other hot corino sources and reported chemical models.

FAUST VI. VLA1623−2417 B: a new laboratory for astrochemistry around protostars on 50 au scale

ABSTRACT The ALMA (Atacama Large Millimeter Array) interferometer, with its unprecedented combination of high sensitivity and high angular resolution, allows for (sub-)mm wavelength mapping of protostellar systems at Solar system scales. Astrochemistry has benefitted from imaging interstellar complex organic molecules in these jet–disc systems. Here, we report the first detection of methanol (CH3OH) and methyl formate (HCOOCH3) emission towards the triple protostellar system VLA1623−2417 A1+A2+B, obtained in the context of the ALMA Large Programme FAUST (Fifty AU STudy of the chemistry in the disc/envelope system of solar-like protostars). Compact methanol emission is detected in lines from Eu = 45 K up to 61 K and 537 K towards components A1 and B, respectively. Large velocity gradient analysis of the CH3OH lines towards VLA1623−2417 B indicates a size of 0.11–0.34 arcsec (14–45 au), a column density $N_{\rm CH_3OH}$ = 1016–1017 cm−2, kinetic temperature ≥ 170 K, and volume density ≥ 108 cm−3. A local thermodynamic equilibrium approach is used for VLA1623−2417 A1, given the limited Eu range, and yields Trot ≤ 135 K. The methanol emission around both VLA1623−2417 A1 and B shows velocity gradients along the main axis of each disc. Although the axial geometry of the two discs is similar, the observed velocity gradients are reversed. The CH3OH spectra from B show two broad (4–5 km s−1) peaks, which are red- and blueshifted by ∼ 6–7 km s−1 from the systemic velocity. Assuming a chemically enriched ring within the accretion disc, close to the centrifugal barrier, its radius is calculated to be 33 au. The methanol spectra towards A1 are somewhat narrower (∼ 4 km s−1), implying a radius of 12–24 au.