Exploring Molecular Complexity With ALMA Research Articles

Interstellar glycolamide: A comprehensive rotational study and an astronomical search in Sgr B2(N).

Glycolamide is a glycine isomer and also one of the simplest derivatives of acetamide (e.g., one hydrogen atom is replaced with a hydroxyl group), which is a known interstellar molecule. In this context, the aim of our work is to provide direct experimental frequencies of the ground vibrational state of glycolamide in the centimeter-, millimeter- and submillimeter-wavelength regions in order to enable its identification in the interstellar medium. We employed a battery of state-of-the-art rotational spectroscopic techniques in the frequency and time domain to measure the frequencies of glycolamide. We used the spectral line survey named Exploring Molecular Complexity with ALMA (EMoCA), which was performed toward the star forming region Sgr B2(N) with ALMA to search for glycolamide in space. We also searched for glycolamide toward Sgr B2(N) with the Effelsberg radio telescope. The astronomical spectra were analyzed under the local thermodynamic equilibrium approximation. We used the gas-grain chemical kinetics model MAGICKAL to interpret the results of the astronomical observations. About 1500 transitions have been newly assigned up to 460 GHz to the most stable conformer, and a precise set of spectroscopic constants was determined. Spectral features of glycolamide were then searched for in the prominent hot molecular core Sgr B2(N2). We report the nondetection of glycolamide toward this source with an abundance at least six and five times lower than that of acetamide and glycolaldehyde, respectively. Our astrochemical model suggests that glycolamide may be present in this source at a level just below the upper limit, which was derived from the EMoCA survey. We could also not detect the molecule in the region's extended molecular envelope, which was probed with the Effelsberg telescope. We find an upper limit to its column density that is similar to the column densities obtained earlier for acetamide and glycolaldehyde with the Green Bank Telescope.

Exploring molecular complexity with ALMA (EMoCA): complex isocyanides in Sgr B2(N)

Context.The Exploring Molecule Complexity with ALMA (EMoCA) survey is an imaging spectral line survey using the Atacama Large Millimeter/submillimeter Array (ALMA) to study the hot-core complex Sagittarius B2(N). Recently, EMoCA revealed the presence of three new hot cores in this complex (N3-N5), in addition to providing detailed spectral data on the previously known hot cores in the complex (N1 and N2). The present study focuses on N2, which is a rich and interesting source for the study of complex molecules whose narrow line widths ameliorate the line confusion problem.Aims.We investigate the column densities and excitation temperatures of cyanide and isocyanide species in Sgr B2(N2). We then use state-of-the-art chemical models to interpret these observed quantities. We also investigate the effect of varying the cosmic-ray ionization rate (ζ) on the chemistry of these molecules.Methods.We used the EMoCA survey data to search for isocyanides in Sgr B2(N2) and their corresponding cyanide analogs. We then used the coupled three-phase chemical kinetics code MAGICKAL to simulate their chemistry. Several new species, and over 100 new reactions have been added to the network. In addition, a new single-stage simultaneous collapse/warm-up model has been implemented, thus eliminating the need for the previous two-stage models. A variable, visual extinction-dependentζwas also incorporated into the model and tested.Results.We report the tentative detection of CH3NC and HCCNC in Sgr B2(N2), which represents the first detection of both species in a hot core of Sgr B2. In addition, we calculate new upper limits for C2H5NC, C2H3NC, HNC3, and HC3NH+. Our updated chemical models can reproduce most observed NC:CN ratios reasonably well depending on the physical parameters chosen. The model that performs best has an extinction-dependent cosmic-ray ionization rate that varies from ~2 × 10−15s−1at the edge of the cloud to ~1 × 10−16s−1in the center. Models with higher extinction-dependentζthan this model generally do not agree as well, nor do models with a constantζgreater than the canonical value of 1.3 × 10−17s−1throughout the source. Radiative transfer models are run using results of the best-fit chemical model. Column densities produced by the radiative transfer models are significantly lower than those determined observationally. Inaccuracy in the observationally determined density and temperature profiles is a possible explanation. Excitation temperatures are well reproduced for the true “hot core” molecules, but are more variable for other molecules such as HC3N, for which fewer lines exist in ALMA Band 3.Conclusions.The updated chemical models do a very good job of reproducing the observed abundances ratio of CH3NC:CH3CN towards Sgr B2(N2), while being consistent with upper limits for other isocyanide/cyanide pairs. HCCNC:HC3N is poorly reproduced, however. Our results highlight the need for models withAV-depdendentζ. However, there is still much to be understood about the chemistry of these species, as evidenced by the systematic overproduction of HCCNC. Further study is also needed to understand the complex effect of varyingζon the chemistry of these species. The new single-stage chemical model should be a powerful tool in analyzing hot-core sources in the future.

The complex chemistry of hot cores in Sgr B2(N): influence of cosmic-ray ionization and thermal history

Context. As the number of complex organic molecules (COMs) detected in the interstellar medium increases, it becomes even more important to place meaningful constraints on the origins and formation pathways of such chemical species. The molecular cloud Sagittarius B2(N) is host to several hot molecular cores in the early stage of star formation, where a great variety of COMs are detected in the gas phase. Given its exposure to the extreme conditions of the Galactic center (GC) region, Sgr B2(N) is one of the best targets to study the impact of environmental conditions on the production of COMs. Aims. Our main goal is to characterize the physico-chemical evolution of Sgr B2(N)’s sources in order to explain their chemical differences and constrain their environmental conditions. Methods. The chemical composition of Sgr B2(N)’s hot cores, N2, N3, N4, and N5 is derived by modeling their 3 mm emission spectra extracted from the Exploring Molecular Complexity with ALMA (EMoCA) imaging spectral line survey performed with the Atacama Large Millimeter/submillimeter Array (ALMA). We derived the density distribution in the envelope of the sources based on the masses computed from the ALMA dust continuum emission maps. We used the radiative transfer code RADMC-3D to compute temperature profiles and inferred the current luminosity of the sources based on the COM rotational temperatures derived from population diagrams. We used published results of 3D radiation-magnetohydrodynamical (RMHD) simulations of high-mass star formation to estimate the time evolution of the source properties. We employed the astrochemical code MAGICKAL to compute time-dependent chemical abundances in the sources and to investigate how physical properties and environmental conditions influence the production of COMs. Results. The analysis of the abundances of 11 COMs detected toward Sgr B2(N2-N5) reveals that N3 and N5 share a similar chemical composition while N2 differs significantly from the other sources. We estimate the current luminosities of N2, N3, N4, and N5 to be 2.6 × 105 L⊙, 4.5 × 104 L⊙, 3.9 × 105 L⊙, and 2.8 × 105 L⊙, respectively. We find that astrochemical models with a cosmic-ray ionization rate of 7 × 10−16 s−1 best reproduce the abundances with respect to methanol of ten COMs observed toward Sgr B2(N2-N5). We also show that COMs still form efficiently on dust grains with minimum dust temperatures in the prestellar phase as high as 15 K, but that minimum temperatures higher than 25 K are excluded. Conclusions. The chemical evolution of Sgr B2(N2-N5) strongly depends on their physical history. A more realistic description of the hot cores’ physical evolution requires a more rigorous treatment with RMHD simulations tailored to each hot core.

Rotational rest frequencies of the low lying vibrational states of n-propyl cyanide from extensive laboratory measurements up to 506 GHz

Context. The spectra of four low-lying vibrational states of both anti and gauche conformers of normal-propyl cyanide were previously measured and analyzed in two spectral windows between 36 and 127 GHz. All states were then identified in a spectral line survey called Exploring Molecular Complexity with ALMA (EMoCA) toward Sagittarius B2(N) between 84.1 and 114.4 GHz with the Atacama Large Millimeter/submillimeter Array (ALMA) in its Cycles 0 and 1. Aims. We wanted to extend the measurements and analysis up to 506 GHz to provide accurate predictions over a much wider range of frequencies, quantum numbers and energies. Methods. We carried out measurements in two additional frequency windows up to 506 GHz. Results. For the gauche conformer, a large number of both a- and b-type transitions were identified. For the anti conformer, transitions were predominantly, but not exclusively, a-type. We hence improved molecular parameters for the ground states of both anti- and gauche-n-propyl cyanide and for excited vibrational states of the gauche conformer (v30 = 1, v29 = 1, v30 = 2, v28 = 1) and anti conformer (v30 = 1, v18 = 1, v30 = 2, v29 = 1) with high order coupling parameters determined between v18 = 1 and v30 = 2. Parameters are published for the first time for v18 = v30 = 1 of the anti conformer and for v29 = v30 = 1 of the gauche conformer. Conclusions. In total 15385 lines have been incorporated in the fits and should allow good predictions for unperturbed lines over the whole operating range of radio-telescopes. Evidence is found for vibrational coupling for some levels above 380 GHz. The coupling between v18 = 1 and v30 = 2 of the anti conformer has been well characterized. An additional list of 740 lines showing potential but as yet unidentified coupling has been provided for astrophysical identification.

Rotational spectrum of 3-aminopropionitrile and searches for it in Sagittarius B2(N)

Aminoacetonitrile (NH2CH2CN) was detected in the interstellar medium (ISM) one decade ago in the course of a spectral survey of the hot molecular core Sagittarius (Sgr) B2(N) with the IRAM 30 m telescope. With the advent of sensitive telescopes such as the Atacama Large Millimeter/submillimeter Array (ALMA), the degree of chemical complexity in the ISM can be further explored. In the family of aminoacetonitrile, the next stage in complexity with one additional CH2 group is aminopropionitrile. This molecule has two structural isomers, a chain-like (3-aminopropionitrile, NH2CH2CH2CN) and a branched, chiral one (2-aminopropionitrile, CH3CH(NH2) CN). The latter was studied in the laboratory a few years ago and was not detected in the IRAM 30 m survey. We present the search for both isomers in the EMoCA (Exploring Molecular Complexity with ALMA) survey, a sensitive spectral survey of Sgr B2(N) performed with ALMA. The rotational spectrum of 3-aminopropionitrile has been recorded in laboratory with a submillimeter spectrometer using solid-state sources. Helped by ab initio calculations performed for the different possible conformations, we present here the analysis based on a Watson Hamiltonian for an asymmetric one-top rotor in A-reduction performed in the frequency range 150–500 GHz for two conformers. More than 6200 lines of the ground-state and lowest excited vibrational states, corresponding to more than 8200 transitions, were assigned in the experimental spectrum. Partition functions, including the vibrational contribution of these states, and predictions in the JPL-CDMS catalog format were determined in order to search for both conformers of 3-aminopropionitrile in Sgr B2(N). Neither 3-aminopropionitrile, nor 2-aminopropionitrile are detected. The derived upper limits imply that they are at least 12 and 5 times less abundant than aminoacetonitrile, respectively. A comparison to ethyl cyanide and n-propyl cyanide detected in this source suggests that an improvement by a factor three in sensitivity may be sufficient to detect 3-aminopropionitrile, which should be within the range of our on-going follow-up project with ALMA.

Exploring molecular complexity with ALMA (EMoCA): Detection of three new hot cores in Sagittarius B2(N)

The SgrB2 molecular cloud contains several sites forming high-mass stars. SgrB2(N) is one of its main centers of activity. It hosts several compact and UCHII regions, as well as two known hot molecular cores (SgrB2(N1) and SgrB2(N2)), where complex organic molecules are detected. Our goal is to use the high sensitivity of ALMA to characterize the hot core population in SgrB2(N) and shed a new light on the star formation process. We use a complete 3 mm spectral line survey conducted with ALMA to search for faint hot cores in SgrB2(N). We report the discovery of three new hot cores that we call SgrB2(N3), SgrB2(N4), and SgrB2(N5). The three sources are associated with class II methanol masers, well known tracers of high-mass star formation, and SgrB2(N5) also with a UCHII region. The chemical composition of the sources and the column densities are derived by modelling the whole spectra under the assumption of LTE. The H2 column densities are computed from ALMA and SMA continuum emission maps. The H2 column densities of these new hot cores are found to be 16 up to 36 times lower than the one of the main hot core Sgr B2(N1). Their spectra have spectral line densities of 11 up to 31 emission lines per GHz, assigned to 22-25 molecules. We derive rotational temperatures around 140-180 K for the three new hot cores and mean source sizes of 0.4 for SgrB2(N3) and 1.0 for SgrB2(N4) and SgrB2(N5). SgrB2(N3) and SgrB2(N5) show high velocity wing emission in typical outflow tracers, with a bipolar morphology in their integrated intensity maps suggesting the presence of an outflow, like in SgrB2(N1). The associations of the hot cores with class II methanol masers, outflows, and/or UCHII regions tentatively suggest the following age sequence: SgrB2(N4), SgrB2(N3), SgrB2(N5), SgrB2(N1). The status of SgrB2(N2) is unclear. It may contain two distinct sources, a UCHII region and a very young hot core.

Exploring molecular complexity with ALMA (EMoCA): Simulations of branched carbon-chain chemistry in Sgr B2(N)

Using mm-wavelength data from ALMA, the EMoCA spectral line survey revealed the presence of both the straight-chain and branched forms of propyl cyanide (C$_3$H$_7$CN) toward the Galactic Center star-forming source Sgr B2(N2). This was the first interstellar detection of a branched aliphatic molecule. Through computational methods, we seek to explain the observed $i$:$n$ ratio for propyl cyanide, and to predict the abundances of the four different forms of the homologous nitrile, butyl cyanide (C$_4$H$_9$CN). We also investigate whether other molecules will show a similar degree of branching, by modeling alkanes up to pentane (C$_5$H$_{12}$). We use a coupled three-phase chemical kinetics model to simulate the chemistry of Sgr B2(N2), using an updated chemical network that includes grain-surface/ice-mantle formation routes for branched nitriles and alkanes. We use the EMoCA survey data to search for the straight-chain form of butyl cyanide toward Sgr B2(N2). The observed $i$:$n$ ratio for propyl cyanide is reproduced by the models. Butyl cyanide is predicted to show similar abundances to propyl cyanide, and to exhibit strong branching, with the $sec$ form clearly dominant over all others. The addition of CN to acetylene and ethene is found to be important to the production of vinyl, ethyl, propyl, and butyl cyanide. We report a non-detection of $n$-C$_4$H$_9$CN toward Sgr B2(N2), with an abundance at least 1.7 times lower than that of $n$-C$_3$H$_7$CN. This value is within the range predicted by the chemical models. The models indicate that the degree of branching rises with increasing molecular size. The efficiency of CN addition to unsaturated hydrocarbons boosts the abundances of nitriles in the model, and enhances the ratio of straight-to-branched molecule production. The predicted abundance of $s$-C$_4$H$_9$CN makes it a good candidate for future detection toward Sgr B2(N2).

Laboratory spectroscopic study and astronomical detection of vibrationally excitedn-propyl cyanide

We performed a spectral line survey called Exploring Molecular Complexity with ALMA (EMoCA) toward Sagittarius~B2(N) between 84.1 and 114.4 GHz with the Atacama Large Millimeter/submillimeter Array (ALMA) in its Cycles 0 and 1. We determined line intensities of n-propyl cyanide in the ground vibrational states of its gauche and anti conformers toward the hot molecular core Sagittarius B2(N2) which suggest that we should also be able to detect transitions pertaining to excited vibrational states. We wanted to determine spectroscopic parameters of low-lying vibrational states of both conformers of n-propyl cyanide to search for them in our ALMA data. We recorded laboratory rotational spectra of n-propyl cyanide in two spectral windows between 36 and 127 GHz. We searched for emission lines produced by these states in the ALMA spectrum of Sagittarius B2(N2). We modeled their emission and the emission of the ground vibrational states assuming local thermodynamic equilibrium (LTE). We have made extensive assignments of a- and b-type transitions of the four lowest vibrational states of the gauche conformer which reach J and Ka quantum numbers of 65 and 20, respectively. We assigned mostly a-type transitions for the anti conformer with J and Ka quantum numbers up to 48 and 24, respectively. Rotational and Fermi perturbations between two anti states allowed us to determine their energy difference. The resulting spectroscopic parameters enabled us to identify transitions of all four vibrational states of each conformer in our ALMA data. The emission features of all states, including the ground vibrational state, are well-reproduced with the same LTE modeling parameters, which gives us confidence in the reliability of the identifications, even for the states with only one clearly detected line.

Exploring molecular complexity with ALMA (EMoCA): Deuterated complex organic molecules in Sagittarius B2(N2)

Deuteration is a powerful tracer of the history of the cold prestellar phase in star forming regions. Apart from methanol, little is known about deuterium fractionation of complex organic molecules in the interstellar medium, especially in high mass star forming regions. We use a spectral line survey performed with ALMA to search for deuterated complex organic molecules toward the hot molecular core Sgr B2(N2). Population diagrams and integrated intensity maps are constructed to fit rotational temperatures and emission sizes for each molecule. Column densities are derived by modelling the full spectrum under the LTE assumption. The results are compared to predictions of two astrochemical models that treat the deuteration process. We report the detection of CH2DCN toward Sgr B2(N2) with a deuteration level of 0.4%, and tentative detections of CH2DOH, CH2DCH2CN, the chiral molecule CH3CHDCN, and DC3N with levels in the range 0.05%-0.12%. A stringent deuteration upper limit is obtained for CH3OD (<0.07%). Upper limits in the range 0.5-1.8% are derived for the three deuterated isotopologues of vinyl cyanide, the four deuterated species of ethanol, and CH2DOCHO. Ethyl cyanide is less deuterated than methyl cyanide by at least a factor five. Except for methyl cyanide, the measured deuteration levels lie at least a factor four below the predictions of current astrochemical models. The deuteration levels in Sgr B2(N2) are also lower than in Orion KL by a factor of a few up to a factor ten. The discrepancy between the deuteration levels of Sgr B2(N2) and the predictions of chemical models, and the difference between Sgr B2(N2) and Orion KL may both be due to the higher kinetic temperatures that characterize the Galactic Center region compared to nearby clouds. Alternatively, they may result from a lower overall abundance of deuterium itself in the Galactic Center region by up to a factor ten.