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Sulphur-bearing species play crucial roles in interstellar chemistry, yet their precise characterisation remains challenging. Here, we present laboratory experiments aimed at extending the high-resolution spectroscopy of protonated carbonyl sulphide (HOCS$^+$), a recently detected molecular ion in space. Using a frequency-modulated free-space absorption spectrometer, we detected rotational transitions of HOCS$^+$ in an extended negative glow discharge with a mixture of H$_2$ and OCS, extending the high-resolution rotational characterisation of the cation well into the millimetre wave region (200-370 GHz). Comparisons with prior measurements and quantum chemical calculations revealed an overall agreement in the spectroscopic parameters. With the new spectroscopic dataset in hand, we re-investigated the observations of HOCS$^+$ towards G+0.693-0.027, which were initially based solely on K$_a$ = 0 lines contaminated by HNC$^{34}$S. This re-investigation enabled the detection of weak K$_a$ = 0 transitions, free from HNC$^{34}$S contamination. Our high-resolution spectroscopic characterisation also provides valuable insights for future millimetre and submillimetre astronomical observations of these species in different interstellar environments. In particular, the new high-resolution catalogue will facilitate the search for this cation in cold dark clouds, where very narrow line widths are typically observed., Comment: 9 pages, 3 figures, and 3 tables. Accepted for publication in Astronomy & Astrophysics

Seven rotational and fine-structure transitions of the deuterated molecular ion SD+ in the X 3S- ground electronic state have been measured in the 271-863 GHz region in the laboratory. This ion has been produced by DC-glow discharge using a mixture of D2S and argon in a free space cell in a temperature range of -140 to -160C. The rotational, centrifugal distortion, spin-spin interaction, and hyperfine constants have been determined; the standard deviation of the residuals in the fitting is 109 kHz. The set of obtained spectroscopic parameters provides a list of accurate sub-millimeter rest frequencies of SD+ for astronomical detection. We have investigated lines of SD+ toward the quasar PKS 1830-211 using the ALMA archive, as the z = 0.89 molecular absorber exists in front of this quasar. A data set covering the 297 GHz region includes the N_J = 2_3-1_2 transition at 561 GHz due to redshift, providing an upper limit of the column density Ntot = 3 x 10^12 cm-2 for SD+.

The synergy between high-resolution rotational spectroscopy and quantum-chemical calculations is essential for exploring future detection of molecules, especially when spectroscopy parameters are not available yet. By using highly correlated ab initio quartic force fields (QFFs) from explicitly correlated coupled cluster theory, a complete set of rotational constants and centrifugal distortion constants for D$_2$CS and cis/trans-DCSD isomers have been produced. Comparing our new ab initio results for D$_2$CS with new rotational spectroscopy laboratory data for the same species, the accuracy of the computed B and C rotational constants is within 0.1% while the A constant is only slightly higher. Additionally, quantum chemical vibrational frequencies are also provided, and these spectral reference data and new experimental rotational lines will provide additional references for potential observation of these deuterated sulfur species with either ground-based radio telescopes or space-based infrared observatories., Comment: 15 pages, 2 figures and 1 appendix table; published in Molecular Physics (Tim Lee Memorial Issue)

We revise the rates of reactions CH + S -> CS + H and C_2 + S -> CS + C, important CS formation routes in dark and diffuse warm gas. We performed ab initio calculations to characterize the main features of all the electronic states correlating to the open shell reactants. For CH+S we have calculated the full potential energy surfaces for the lowest doublet states and the reaction rate constant with a quasi-classical method. For C_2+S, the reaction can only take place through the three lower triplet states, which all present deep insertion wells. A detailed study of the long-range interactions for these triplet states allowed to apply a statistic adiabatic method to determine the rate constants. This study of the CH + S reaction shows that its rate is nearly independent on the temperature in a range of 10-500 K with an almost constant value of 5.5 10^{-11} cm^3/s at temperatures above 100~K. This is a factor \sim 2-3 lower than the value obtained with the capture model. The rate of the reaction C_2 + S depends on the temperature taking values close to 2.0 10^{-10} cm^3/s at low temperatures and increasing to 5. 10^{-10} cm^3/s for temperatures higher than 200~K. Our modeling provides a rate higher than the one currently used by factor of \sim 2. These reactions were selected for involving open-shell species with many degenerate electronic states, and the results obtained in the present detailed calculations provide values which differ a factor of \sim 2-3 from the simpler classical capture method. We have updated the sulphur network with these new rates and compare our results in the prototypical case of TMC1 (CP). We find a reasonable agreement between model predictions and observations with a sulphur depletion factor of 20 relative to the sulphur cosmic abundance, but it is not possible to fit all sulphur-bearing molecules better than a factor of 10 at the same chemical time., Comment: 13 pages, 10 figures

Isotopic fractionation is an important tool to investigate the chemical history of our Solar System (SS). In particular, the isotopic fraction of nitrogen (14N/15N) is lower in comets and other pristine SS bodies with respect to the value measured for the protosolar nebula, suggesting a local chemical enrichment of 15N during the SS formation. Therefore, interferometric studies of nitrogen fractionation in SS precursors are imperative for us to obtain clues about our astrochemical origins. In this work, we investigated the variation of the 14N/15N ratio in one of the closest analogues of the environment in which the SS was born: the protocluster OMC-2 FIR4. We present the first comparison at high angular resolution between HCN and N2H+ using interferometric data. We analysed observations of the HCN isotopologues H13CN and HC15N in the OMC-2 FIR4 protocluster, specifically the transitions H13CN (1-0) and HC15N (1-0), from NOEMA within the context of the IRAM Seeds Of Life In Space Large Program. We combined our results with analysis of archival data obtained with ALMA of N2H+ and its 15N isotopologues. Our results show a small regional variation in the ratio for HCN from ~250 to 500. The ratios in the central regions of FIR4, where the candidate protostars are located, are largely consistent (~300). They also show little variation from the part of the protocluster known to harbour a high cosmic-ray ionisation rate, to the portion with lower rate. We also found a small variation in the ratio of N2H+ across different regions from ~200 to ~400. These results suggest that local changes in the physical parameters occurring on small linear scales probed by our observations do not seem to affect the 14N/15N ratio in either HCN or N2H+ and hence that this is independent of the molecule used. Moreover, the high level of irradiation due to cosmic rays does not affect the N-fractionation either.

Context. The deuterium fraction in low-mass prestellar cores is a good diagnostic indicator of the initial phases of star formations, and it is also a fundamental quantity to infer the ionisation degree in these objects. Aims. With the analysis of multiple transitions of $\rm N_2H^+$, $\rm N_2D^+$, $\rm HC^{18}O^+$ and $\rm DCO^+$ we are able to determine the molecular column density maps and the deuterium fraction in $\rm N_2H^+$ and $\rm HCO^+$ toward the prototypical prestellar core L1544. This is the preliminary step to derive the ionisation degree in the source. Methods. We use a non-local thermodynamic equilibrium (non-LTE) radiative transfer code, combined with the molecular abundances derived from a chemical model, to infer the excitation conditions of all the observed transitions, which allows us to derive reliable maps of each molecule's column density. The ratio between the column density of a deuterated species and its non-deuterated counterpart gives the searched deuteration level. Results. The non-LTE analysis confirms that, for the analysed molecules, higher-J transitions are characterised by excitation temperatures $\approx 1-2\,$K lower than the lower-J ones. The chemical model that provides the best fit to the observational data predict the depletion of $\rm N_2H^+$ and to a lesser extent of $\rm N_2D^+$ in the innermost region. The peak values for the deuterium fraction that we find are $\mathrm{D/H_{N_2H^+}} = 0.26^{+0.15}_{-0.14}$ and $\mathrm{D/H_{HCO^+}} = 0.035^{+0.015}_{-0.012}$, in good agreement with previous estimates in the source., Comment: Accepted for publication on A&A on 18/7/19

We report the gas-phase detection and spectroscopic characterization of ethynethiol ($\mathrm{HCCSH}$), a metastable isomer of thioketene ($\mathrm{H_2C_2S}$) using a combination of Fourier-transform microwave and submillimeter-wave spectroscopies. Several $a$-type transitions of the normal species were initially detected below 40 GHz using a supersonic expansion-electrical discharge source, and subsequent measurement of higher-frequency, $b$-type lines using double resonance provided accurate predictions in the submillimeter region. With these, searches using a millimeter-wave absorption spectrometer equipped with a radio frequency discharge source were conducted in the range 280 - 660 GHz, ultimately yielding nearly 100 transitions up to $^rR_0(36)$ and $^rQ_0(68)$. From the combined data set, all three rotational constants and centrifugal distortion terms up to the sextic order were determined to high accuracy, providing a reliable set of frequency predictions to the lower end of the THz band. Isotopic substitution has enabled both a determination of the molecular structure of $\mathrm{HCCSH}$ and, by inference, its formation pathway in our nozzle discharge source via the bimolecular radical-radical recombination reaction $\mathrm{SH + C_2H}$, which is calculated to be highly exothermic (-477 kJ/mol) using the HEAT345(Q) thermochemical scheme., Comment: Accepted for publication in Molecular Physics. 29 pages, 4 tables, 6 figures. Supporting information is available

Protonated molecular species have been proven to be abundant in the interstellar gas. This class of molecules is also pivotal for the determination of important physical parameters for the ISM evolution (e.g. gas ionisation fraction) or as tracers of non-polar, hence not directly observable, species. The identification of these molecular species through radioastronomical observations is directly linked to a precise laboratory spectral characterisation. The goal of the present work is to extend the laboratory measurements of the pure rotational spectrum of the ground electronic state of protonated carbonyl sulfide (HSCO$^+$) and its deuterium substituted isotopomer (DSCO$^+$). At the same time, we show how implementing different laboratory techniques allows the determination of different spectroscopical properties of asymmetric-top protonated species. Three different high-resolution experiments were involved to detected for the first time the $b-$type rotational spectrum of HSCO$^+$, and to extend, well into the sub-millimeter region, the $a-$type spectrum of the same molecular species and DSCO$^+$. The electronic ground-state of both ions have been investigated in the 273-405 GHz frequency range, allowing the detection of 60 and 50 new rotational transitions for HSCO$^+$ and DSCO$^+$, respectively. The combination of our new measurements with the three rotational transitions previously observed in the microwave region permits the rest frequencies of the astronomically most relevant transitions to be predicted to better than 100 kHz for both HSCO$^+$ and DSCO$^+$ up to 500 GHz, equivalent to better than 60 m/s in terms of equivalent radial velocity. The present work illustrates the importance of using different laboratory techniques to spectroscopically characterise a protonated species at high frequency, and how a similar approach can be adopted when dealing with reactive species., Comment: 7 pages, 4 figures. Accepted for publication in Astronomy and Astrophysics

HOCO$^+$ is a polar molecule that represents a useful proxy for its parent molecule CO$_2$, which is not directly observable in the cold interstellar medium. This cation has been detected towards several lines of sight, including massive star forming regions, protostars, and cold cores. Despite the obvious astrochemical relevance, protonated CO$_2$ and its deuterated variant, DOCO$^+$, still lack an accurate spectroscopic characterisation. The aim of this work is to extend the study of the ground-state pure rotational spectra of HOCO$^+$ and DOCO$^+$ well into the sub-millimetre region. Ground-state transitions have been recorded in the laboratory using a frequency-modulation absorption spectrometer equipped with a free-space glow-discharge cell. The ions were produced in a low-density, magnetically-confined plasma generated in a suitable gas mixture. The ground-state spectra of HOCO$^+$ and DOCO$^+$ have been investigated in the 213-967 GHz frequency range, with the detection of 94 new rotational transitions. Additionally, 46 line positions taken from the literature have been accurately remeasured. The newly-measured lines have significantly enlarged the available data sets for HOCO$^+$ and DOCO$^+$, thus enabling the determination of highly accurate rotational and centrifugal distortion parameters. Our analysis showed that all HOCO$^+$ lines with Ka $\geq$ 3 are perturbed by a ro-vibrational interaction that couples the ground state with the v$_ 5$ = 1 vibrationally-excited state. This resonance has been explicitly treated in the analysis in order to obtain molecular constants with clear physical meaning. The improved sets of spectroscopic parameters provide enhanced lists of very accurate, sub-millimetre rest-frequencies of HOCO$^+$ and DOCO$^+$ for astrophysical applications. These new data challenges a recent tentative identification of DOCO$^+$ toward a pre-stellar core., Comment: 7 pages, 1 figure, accepted for publication in A&A

The rotational spectra of thioisocyanic acid (HNCS), and its three energetic isomers (HSCN, HCNS, and HSNC) have been observed at high spectral resolution by a combination of chirped-pulse and Fabry-P\'{e}rot Fourier-transform microwave spectroscopy between 6 and 40~GHz in a pulsed-jet discharge expansion. Two isomers, thiofulminic acid (HCNS) and isothiofulminic acid (HSNC), calculated here to be 35-37~kcal/mol less stable than the ground state isomer HNCS, have been detected for the first time. Precise rotational, centrifugal distortion, and nitrogen hyperfine coupling constants have been determined for the normal and rare isotopic species of both molecules; all are in good agreement with theoretical predictions obtained at the coupled cluster level of theory. On the basis of isotopic spectroscopy, precise molecular structures have been derived for all four isomers by correcting experimental rotational constants for the effects of rotation-vibration calculated theoretically. Formation and isomerization pathways have also been investigated; the high abundance of HSCN relative to ground state HNCS, and the detection of strong lines of SH using CH$_3$CN and H$_2$S, suggest that HSCN is preferentially produced by the radical-radical reaction HS + CN. A radio astronomical search for HSCN and its isomers has been undertaken toward the high-mass star-forming region Sgr B2(N) in the Galactic Center with the 100 m Green Bank Telescope. While we find clear evidence for HSCN, only a tentative detection of HNCS is proposed, and there is no indication of HCNS or HSNC at the same rms noise level. HSCN, and tentatively HNCS, displays clear deviations from a single-excitation temperature model, suggesting weak masing may be occurring in some transitions in this source., Comment: Accepted in Physical Chemistry Chemical Physics

Many sulphur-bearing species have been detected in different astronomical environments and have allowed to derive important information about the chemical and physical composition of interstellar regions. In particular, these species have also been showed to trace and probe hot-core environment time evolution. Among the most prominent sulphur-bearing molecules, SO, sulphur monoxide radical, is one of the more ubiquitous and abundant, observed also in its isotopic substituted species such as $^{34}$SO and S$^{18}$O. Due to the importance of this simple diatomic system and to face the challenge of modern radioastronomical facilities, an extension to THz range of the rare isotopologues of sulphur monoxide has been performed. High-resolution rotational molecular spectroscopy has been employed to extend the available dataset of four isotopic species, SO, $^{34}$SO, S$^{17}$O, and S$^{18}$O up to the 1.5 THz region. The frequency coverage and the spectral resolution of our measurements allowed a better constraint of the molecular constants of the four species considered, focusing especially for the two oxygen substituted isotopologues. Our measurements were also employed in an isotopically invariant fit including all available pure rotational and ro-vibrational transitions for all SO isotopologues, thus enabling accurate predictions for rotational transitions at higher frequencies. Comparison with recent works performed on the same system are also provided, showing the quality of our experiment and the improvement of the datasets for all the species here considered. Transition frequencies for this system can now be used with confidence by the astronomical community well into the THz spectral region., Comment: 18 pages, 3 figures, to be published in ApJ

We have performed reaction product screening measurements using broadband rotational spectroscopy to identify rotational transition matches between laboratory spectra and the Green Bank Telescope PRIMOS radio astronomy survey spectra in Sagittarius B2 North (Sgr B2(N)). The broadband rotational spectrum of molecules created in an electrical discharge of CH3CN and H2S contained several frequency matches to unidentified features in the PRIMOS survey that did not have molecular assignments based on standard radio astronomy spectral catalogs. Several of these transitions are assigned to the E- and Z-isomers of ethanimine. Global fits of the rotational spectra of these isomers in the range of 8 to 130 GHz have been performed for both isomers using previously published mm-wave spectroscopy measurements and the microwave measurements of the current study. Possible interstellar chemistry formation routes for E-ethanimine and Z-ethanimine are discussed. The detection of ethanimine is significant because of its possible role in the formation of alanine - one of the twenty amino acids in the genetic code., Comment: Accepted in The Astrophysical Journal Letters, 21 pages, 4 figures, 1 table

The rotational spectrum of the higher-energy trans conformational isomer of methyl formate has been assigned for the first time using several pulsed-jet Fourier transform microwave spectrometers in the 6-60 GHz frequency range. This species has also been sought toward the Sagittarius B2(N) molecular cloud using the publicly available PRIMOS survey from the Green Bank Telescope. We detect seven absorption features in the survey that coincide with laboratory transitions of trans-methyl formate, from which we derive a column density of 3.1 (+2.6, -1.2) \times 10^13 cm-2 and a rotational temperature of 7.6 \pm 1.5 K. This excitation temperature is significantly lower than that of the more stable cis conformer in the same source but is consistent with that of other complex molecular species recently detected in Sgr B2(N). The difference in the rotational temperatures of the two conformers suggests that they have different spatial distributions in this source. As the abundance of trans-methyl formate is far higher than would be expected if the cis and trans conformers are in thermodynamic equilibrium, processes that could preferentially form trans-methyl formate in this region are discussed. We also discuss measurements that could be performed to make this detection more certain. This manuscript demonstrates how publicly available broadband radio astronomical surveys of chemically rich molecular clouds can be used in conjunction with laboratory rotational spectroscopy to search for new molecules in the interstellar medium., Comment: 40 pages, 7 figures, 4 tables; accepted for publication in ApJ

We have measured new submillimeter-wave data around 600 GHz and around 1.1 THz for the 13C isotopologue of formic acid and for the two deuterium isotopomers; in each case for both the trans and cis rotamer. For cis-DCOOH and cis-HCOOD in particular only data up to 50 GHz was previously available. For all species the quality and quantity of molecular parameters has been increased providing new measured frequencies and more precise and reliable frequencies in the range of existing and near-future submillimeter and far-infrared astronomical spectroscopy instruments such as Herschel, SOFIA and ALMA.