arXiv subjects

Luca Bizzocchi

Publications and source records attributed to Luca Bizzocchi.

At least 19 recordsLinked to original sources

arXiv2026

High-Resolution Infrared Spectroscopy and ASAP Analysis of Cyclopentadiene: The Vibrational Modes below 860 cm$^{-1}$ and the ${\nu}_{21}$ Mode at 961 cm$^{-1}$

The spectroscopic fingerprints of vibrationally excited states of astronomical molecules are interesting for multiple reasons. They are excellent temperature probes of the corresponding astronomical regions and are thought to be the origin of many unknown lines in astronomical survey spectra. Rovibrational spectra provide accurate vibrational energies and can guide subsequent pure rotational studies. The Automated Spectral Assignment Procedure (ASAP) greatly simplifies the rovibrational analysis when the rotational spectrum of either the upper or lower vibrational state is known with a high degree of accuracy (e.g., from a rotational analysis). Here, we present a new implementation of ASAP for the analysis of cyclopentadiene, a cyclic pure hydrocarbon that has already been detected astronomically toward the cold core of the Taurus Molecular Cloud. Using the synchrotron radiation extracted by the AILES beamline of the SOLEIL facility, we recorded mid- and far-infrared high-resolution spectra of cyclopentadiene. We analyzed the rovibrational spectrum of the $\nu_{21}$ fundamental (961 cm$^{-1}$) with ASAP and used ASAP$^2$ to determine the vibrational energies of the eight vibrational modes below 860 cm$^{-1}$. ASAP$^2$ is an extension of ASAP for rovibrational bands where the rotational structures of the lower and upper states are known with high accuracy, leaving only the vibrational band center to be determined. The presented rovibrational fingerprints agree with the results from pure rotational spectroscopy, demonstrating the efficiency and reliability of our new ASAP implementation.

physics.chem-ph↗

arXiv2026

Ab Initio Characterization of C2H4N2 Isomers: Structures, electronic energies, spectroscopic parameters and formation pathways

This work presents a comprehensive theoretical investigation of key isomers of C2H4N2 using state-of-the-art quantum chemical methods. The objective is to characterize their molecular structures, spectroscopic constants, and electronic energies, and to elucidate plausible formation and destruction pathways, providing data critical for astrochemical and atmospheric detection. High-accuracy ab initio methods were employed, notably CCSD(T)-F12/cc-pVTZ-F12 for optimized geometries. Additional calculations were performed at the CCSD(T)/aug-cc-pVTZ, CCSD(T)/cc-pVTZ, MP2/aug-cc-pVTZ, and CIS levels. Intrinsic reaction coordinate (IRC) calculations were performed at the B3LYP/6-31G(d,p) level to explore reaction pathways. Zero-point energy corrections were determined for all isomers considered. Six low-energy C2H4N2 isomers were identified, all within 1 eV of the global minimum. Among them, methylcyanamide (MCA) exhibits the lowest relative energy (~0.2 eV) and a significant electric dipole moment of 5.00 D, making it a strong candidate for gas-phase detection. The rotational constants for MCA, computed at the CCSD(T)-F12/cc-pVTZ-F12 level, are Ae = 34932.44 MHz, Be = 4995.31 MHz, and Ce = 4520.30 MHz. The V3 torsional barrier was found to be 631.19 cm^{-1}. Centrifugal distortion constants were computed up to sextic order for all isomers. Formation pathways for MCA, such as CH3N + HCN -> CH3NHCN and related isomers, were characterized. The combination of large dipole moments and distinct rotational signatures supports the detectability of methylcyanamide and related C2H4N2 isomers via radioastronomy, infrared, and microwave spectroscopy. Isomerization and reaction pathways involving radical-neutral and neutral-neutral processes were found to be key to their formation in gas-phase environments. These results provide a robust foundation for future observational and modeling efforts.

physics.chem-ph↗

arXiv2025

Statistical nuclear spin ratios of deuterated ammonia in the pre-stellar core L1544

We determined the ortho/para (o/p) ratios of NH2D and NHD2 in the archetypical pre-stellar core L1544. The core was observed in the two lowest rotational lines of ortho- and para-NH2D using the APEX and the IRAM 30 m telescopes. The ground-state lines of ortho- and para-NHD2 were observed with APEX. The distributions of chemical abundances in the core were predicted using a gas-grain chemistry model with two different scenarios concerning proton transfer reactions in the gas. One of the scenarios, the so-called full scrambling (FS), allows protons and deuterons to be completely mixed in the intermediate reaction complex before dissociation, whereas the other describes these reactions as proton or deuteron hops (PH). We also tested assumed abundance profiles independent of the chemistry models. Radiative transfer calculations were used to simulate the observed NH2D and NHD2 lines from the predicted and assumed abundance profiles. Our modelling efforts suggest that the ground-state lines of NH2D and NHD2 at the wavelength 0.9 mm that are observable with the same beam and in the same spectrometer band are the most reliable probes of the o/p ratios. Simulations using the PH reaction scheme show systematically better agreement with the observations than simulations with the FS model. Simulations using a broken power law abundance profile as a function of the gas density give spin ratios that are close to the predictions of the PH scenario: o/p-NH2D=2.85+-0.05, o/p-NHD2=2.10+-0.06 (1 sigma). The o/p ratios predicted by the PH scenario in the gas phase correspond to the nuclear spin statistical weights, that is, o/p-NH2D=3, o/p-NHD2=2. In view of the fact that H and D atom addition reactions on grain surfaces also result in these ratios, it is reasonable to assume that the spin ratios of interstellar ammonia and its deuterated forms are in general equal to their statistical values.

astro-ph.GA↗

arXiv2025

Experimental and theoretical investigation on N2 pressure-induced coefficients of the lowest rotational transitions of HCN

We present the first experimental determination of room-temperature N2 pressure broadening, speed dependent broadening, and pressure shift coefficients of the three lowest rotational lines of HCN. The experimental results served to assess the accuracy of a low-cost yet accurate computational strategy, which relies on a simplified characterization of the HCN-N2 interaction potential, and employs a novel approximate method of solving the quantum scattering problem. Building on the validation of this computational approach, the dataset was extended to higher rotational transitions, up to J(HCN)=5-4. For these transitions, we provide the temperature dependence of the pressure broadening coefficient, its speed dependence parameter, and the Dicke narrowing parameter. This new dataset can support and refine the modeling of HCN in both the terrestrial and Titan's atmospheres. This work constitutes an important step towards populating spectroscopic databases with accurate HCN line-shape parameters.

physics.chem-ph↗

arXiv2023

Nitrogen fractionation in ammonia and its insights on nitrogen chemistry

Context. Observations of $\rm ^{14}N/^{15}N$ in the interstellar medium are becoming more frequent thanks to the increased telescope capabilities. However, interpreting these data is still puzzling. In particular, measurements of $\rm ^{14}N/^{15}N$ in diazenylium revealed high levels of anti-fractionation in cold cores. Aims. Furuya & Aikawa (2018), using astrophysical simulations coupled with a gas-grain chemical code, concluded that the $^{15}$N-depletion in prestellar cores could be inherited from the initial stages, when $\rm ^{14}N^{15}N$ is selectively photodissociated and 15N atoms deplete onto the dust grain, forming ammonia ices. We aim to test this hypothesis. Methods. We targeted three sources (the prestellar core L1544, the protostellar envelope IRAS4A, and the shocked region L1157-B1) with distinct degrees of desorption or sputtering of the ammonia ices. We observed the NH3 isotopologues with the GBT, and we inferred the $\rm ^{14}N/^{15}N$ via a spectral fitting of the observed inversion transitions. Results. $^{15}$NH3(1,1) is detected in L1544 and IRAS4A, whilst only upper limits are deduced in L1157-B1. The NH3 isotopic ratio is significantly lower towards the protostar than at the centre of L1544, where it is consistent with the elemental value. We also present the first spatially resolved map of NH3 nitrogen isotopic ratio towards L1544. Conclusions. Our results are in agreement with the hypothesis that ammonia ices are enriched in $^{15}$N, leading to a decrease of the $\rm ^{14}N/^{15}N$ ratio when the ices are sublimated into the gas phase for instance due to the temperature rise in protostellar envelopes. The ammonia $\rm ^{14}N/^{15}N$ value at the centre of L1544 is a factor of 2 lower than that of N2H+, suggesting that the dominant formation pathway is hydrogenation of N atoms on dust grains, followed by non-thermal desorption.

astro-ph.GA↗

arXiv2022

Hyperfine resolved rate coefficients of HC17O+ with H2 (j = 0)

The formyl cation (HCO+) is one of the most abundant ions in molecular clouds and plays a major role in the interstellar chemistry. For this reason, accurate collisional rate coefficients for the rotational excitation of HCO+ and its isotopes due to the most abundant perturbing species in interstellar environments are crucial for non-local thermal equilibrium models and deserve special attention. In this work, we determined the first hyperfine resolved rate coefficients of HC17O+ in collision with H2 (j=0). Indeed, despite no scattering calculations on its collisional parameters have been performed so far, the HC17O+ isotope assumes a prominent role for astrophysical modelling applications. Computations are based on a new four dimensional (4D) potential energy surface, obtained at the CCSD(T)-F12a/aug-cc-pVQZ level of theory. A test on the corresponding cross section values pointed out that, to a good approximation, the influence of the coupling between rotational levels of H2 can be ignored. For this reason, the H2 collider has been treated as a spherical body and an average of the potential based on five orientations of H2 has been employed for scattering calculations. State-to-state rate coefficients resolved for the HC17O+ hyperfine structure for temperature ranging from 5 to 100 K have been computed using recoupling techniques. This study provides the first determination of HC17O+/H2 inelastic rate coefficients directly computed from full quantum close-coupling equations, thus supporting the reliability of future radiative transfer modellings of HC17O+ in interstellar environments.

astro-ph.GA↗

arXiv2022

Nitrogen fractionation towards a pre-stellar core traces isotope-selective photodissociation

Isotopologue abundance ratios are important to understand the evolution of astrophysical objects and ultimately the origins of a planetary system like our own. Being nitrogen a fundamental ingredient of pre-biotic material, understanding its chemistry and inheritance is of fundamental importance to understand the formation of the building blocks of life. We present here single-dish observations of the ground state rotational transitions of the $^{13}$C and $^{15}$N isotopologues of HCN, HNC and CN with the IRAM 30m telescope. We analyse their column densities and compute the $^{14}$N/$^{15}$N ratio map for HCN. The $^{15}$N-fractionation of CN and HNC is computed towards different offsets across L1544. The $^{15}$N-fractionation map of HCN shows a clear decrease of the $^{14}$N/$^{15}$N ratio towards the southern edge of L1544, where carbon chain molecules present a peak, strongly suggesting that isotope-selective photodissociation has a strong effect on the fractionation of nitrogen across pre-stellar cores. The $^{14}$N/$^{15}$N ratio in CN measured towards four positions across the core also shows a decrease towards the South-East of the core, while HNC shows opposite behaviour. The uneven illumination of the pre-stellar core L1544 provides clear evidence that $^{15}$N-fractionation of HCN and CN is enhanced toward the region more exposed to the interstellar radiation field. Isotope-selective photodissociation of N$_2$ is then a crucial process to understand $^{15}$N fractionation, as already found in protoplanetary disks. Therefore, the $^{15}$N-fractionation in pre-stellar material is expected to change depending on the environment within which pre-stellar cores are embedded. The $^{12}$CN/$^{13}$CN ratio also varies across the core, but its variation does not affect our conclusions on the effect of the environment on the fractionation of nitrogen.

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

An Interferometric View of H-MM1. I. Direct Observation of NH3 Depletion

Spectral lines of ammonia, NH$_3$, are useful probes of the physical conditions in dense molecular cloud cores. In addition to advantages in spectroscopy, ammonia has also been suggested to be resistant to freezing onto grain surfaces, which should make it a superior tool for studying the interior parts of cold, dense cores. Here we present high-resolution NH$_3$ observations with the Very Large Array (VLA) and Green Bank Telescope (GBT) towards a prestellar core. These observations show an outer region with a fractional NH$_3$ abundance of X(NH$_3$) = (1.975$\pm$0.005)$\times 10^{-8}$ ($\pm 10\%$ systematic), but it also reveals that after all, the X(NH$_3$) starts to decrease above a H$_2$ column density of $\approx 2.6 \times 10^{22}$ cm$^{-2}$. We derive a density model for the core and find that the break-point in the fractional abundance occurs at the density n(H$_2$) $\sim 2\times10^5$ cm$^{-3}$, and beyond this point the fractional abundance decreases with increasing density, following the power law $n^{-1.1}$. This power-law behavior is well reproduced by chemical models where adsorption onto grains dominates the removal of ammonia and related species from the gas at high densities. We suggest that the break-point density changes from core to core depending on the temperature and the grain properties, but that the depletion power law is anyway likely to be close to $n^{-1}$ owing to the dominance of accretion in the central parts of starless cores.

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

The Central 1000 au of a Pre-stellar Core Revealed with ALMA. II. Almost Complete Freeze-out

Pre-stellar cores represent the initial conditions in the process of star and planet formation. Their low temperatures ($<$10 K) allow the formation of thick icy dust mantles, which will be partially preserved in the future protoplanetary disks, ultimately affecting the chemical composition of planetary systems. Previous observations have shown that carbon- and oxygen-bearing species, in particular CO, are heavily depleted in pre-stellar cores due to the efficient molecular freeze-out onto the surface of cold dust grains. However, N-bearing species such as NH$_3$ and, in particular, its deuterated isotopologues, appear to maintain high abundances where CO molecules are mainly in solid phase. Thanks to ALMA, we present here the first clear observational evidence of NH$_2$D freeze-out toward the L1544 pre-stellar core, suggestive of the presence of a"complete-depletion zone" within a $\simeq$1800 au radius, in agreement with astrochemical pre-stellar core model predictions. Our state-of-the-art chemical model coupled with a non-LTE radiative transfer code demonstrates that NH$_2$D becomes mainly incorporated in icy mantles in the central 2000 au and starts freezing-out already at $\simeq$7000 au. Radiative transfer effects within the pre-stellar core cause the NH$_2$D(1$_{11}$-1$_{01}$) emission to appear centrally concentrated, with a flattened distribution within the central $\simeq$3000 au, unlike the 1.3 mm dust continuum emission which shows a clear peak within the central $\simeq$1800 au. This prevented NH$_2$D freeze-out to be detected in previous observations, where the central 1000 au cannot be spatially resolved.

astro-ph.SR↗

arXiv2020

Propargylimine in the laboratory and in space: millimetre-wave spectroscopy and first detection in the ISM

Small imines containing up to three carbon atoms are present in the interstellar medium. As alkynyl compounds are abundant in this medium, propargylimine thus represents a promising candidate for a new interstellar detection. The goal of the present work is to perform a comprehensive laboratory investigation of the rotational spectrum of propargylimine in its ground vibrational state in order to obtain a highly precise set of rest-frequencies and to search it in space. The rotational spectra of $E$ and $Z$ geometrical isomers of propargylimine have been recorded in laboratory in the 83-500 GHz frequency interval. The measurements have been performed using a source-modulation millimetre-wave spectrometer equipped with a pyrolysis system for the production of unstable species. High-level ab initio calculations were performed to assist the analysis and to obtain reliable estimates for an extended set of spectroscopic quantities. The improved spectral data allow us to perform a successful search for this new imine in the quiescent G+0.693-0.027 molecular cloud. Eighteen lines of $Z$-propargylimine have been detected at level $>2.5 \sigma$, resulting in a column density estimate of $N = (0.24\pm 0.02)\times 10^{14}$ cm$^{-2}$. An upper limit was retrieved for the higher-energy $E$ isomer, which was not detected in the data. The fractional abundance (w.r.t. H$_2$) derived for $Z$-propargylimine is $1.8\times 10^{-10}$. We discuss the possible formation routes by comparing the derived abundance with those measured in the source for possible chemical precursors.

astro-ph.GA↗

arXiv2020

Submillimetre and far-infrared spectroscopy of monodeuterated amidogen radical (NHD): improved rest-frequencies for astrophysical observations

Observations of ammonia in interstellar environments have revealed high levels of deuteration, and all its D-containing variants, including ND$_3$, have been detected in cold prestellar cores and around young protostars. The observation of these deuterated isotopologues is very useful to elucidate the chemical and physical processes taking place during the very early stages of star formation, as the abundance of deuterated molecules is highly enhanced in dense and cold gas. Nitrogen hydride radicals are key species lying at the very beginning of the reaction pathway leading to the formation of NH$_3$ and organic molecules of pre-biotic interest, but relatively little information is known about their D-bearing isotopologues. To date, only ND has been detected in the interstellar gas. To aid the identification of further deuterated nitrogen radicals, we have thoroughly re-investigated the rotational spectrum of NHD employing two different instruments: a frequency-modulation submillimetre spectrometer operating in the THz region and a synchrotron-based Fourier Transform infrared spectrometer operating in the 50-240 cm$^{-1}$ wavelength range. NHD was produced in a plasma of NH$_3$ and D$_2$. A wide range of rotational energy levels has been probed thanks to the observation of high $N$ (up to 15) and high $K_a$ (up to 9) transitions. A global analysis including our new data and those already available in the literature has provided a comprehensive set of very accurate spectroscopic parameters. A highly reliable line catalogue has been generated to assist archival data searches and future astronomical observations of NHD at submillimetre and THz regimes.

astro-ph.GA↗

arXiv2020

Efficient methanol production on the dark side of a prestellar core

We present ALMA maps of the starless molecular cloud core Ophiuchus/H-MM1 in the lines of deuterated ammonia (ortho-NH2D), methanol (CH3OH), and sulphur monoxide (SO). The dense core is seen in NH2D emission, whereas the CH3OH and SO distributions form a halo surrounding the core. Because methanol is formed on grain surfaces, its emission highlights regions where desorption from grains is particularly efficient. Methanol and sulphur monoxide are most abundant in a narrow zone that follows the eastern side of the core. This side is sheltered from the stronger external radiation field coming from the west. We show that photodissociation on the illuminated side can give rise to an asymmetric methanol distribution, but that the stark contrast observed in H-MM1 is hard to explain without assuming enhanced desorption on the shaded side. The region of the brightest emission has a wavy structure that rolls up at one end. This is the signature of Kelvin-Helmholtz instability occurring in sheared flows. We suggest that in this zone, methanol and sulphur are released as a result of grain-grain collisions induced by shear vorticity.

astro-ph.GA↗

arXiv2019

The first steps of Interstellar Phosphorus Chemistry

Phosphorus-bearing species are an essential key to form life on Earth, however they have barely been detected in the interstellar medium. Since only PN and PO have been identified so far towards star-forming regions, the chemical formation pathways of P-bearing molecules are not easy to constrain and are thus highly debatable. An important factor still missing in the chemical models is the initial elemental abundance of phosphorus, i.e. the depletion level of P. In order to overcome this problem, we study P-bearing species in diffuse/translucent clouds. In these objects phosphorus is mainly in the gas phase and therefore the elemental initial abundance needed in our chemical simulations corresponds to the cosmic one and is thus well constrained. An advanced chemical model with an updated P-chemistry network has been used. Single-pointing observations were performed with the IRAM 30m telescope towards the line of sight to the blazar B0355+508 aiming for the (2-1) transitions of PN, PO, HCP and CP. This line of sight incorporates five diffuse/translucent clouds. The (2-1) transitions of the PN, PO, HCP and CP were not detected. We report detections of the (1-0) lines of $\mathrm{^{13}CO}$, HNC and CN along with a first detection of $\mathrm{C^{34}S}$. We have reproduced the observations of HNC, CN, CS and CO in every cloud by applying typical conditions for diffuse/translucent clouds. According to our best-fit model, the most abundant P-bearing species are HCP and CP ($\sim10^{-10}$), followed by PN, PO and $\mathrm{PH_3}$ ($\sim10^{-11}$). We show that the production of P-bearing species is favoured towards translucent rather than diffuse clouds, where the environment provides a stronger shielding from the interstellar radiation. Based on our improved model, the (1-0) transitions of HCP, CP, PN and PO are expected to be detectable with estimated intensities up to $\sim200$ mK.

astro-ph.GA↗

arXiv2019

High sensitivity maps of molecular ions in L1544: I. Deuteration of N2H+ and HCO+ and first evidence of N2D+ depletion

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.

astro-ph.SR↗

arXiv2018

The rotational spectrum of $^{15}$ND. Isotopic-independent Dunham-type analysis of the imidogen radical

The rotational spectrum of $^{15}$ND in its ground electronic $X^{3}Σ^{-}$ state has been observed for the first time. Forty-three hyperfine-structure components belonging to the ground and v = 1 vibrational states have been recorded with a frequency-modulation millimeter-/submillimeter-wave spectrometer. These new measurements, together with the ones available for the other isotopologues NH, ND, and $^{15}$NH, have been simultaneously analysed using the Dunham model to represent the ro-vibrational, fine, and hyperfine energy contributions. The least-squares fit of more than 1500 transitions yielded an extensive set of isotopically independent $U_{lm}$ parameters plus 13 Born--Oppenheimer Breakdown coefficients $Δ_{lm}$. As an alternative approach, we performed a Dunham analysis in terms of the most abundant isotopologue coefficients $Y_{lm}$ and some isotopically dependent Born--Oppenheimer Breakdown constants $δ_{lm}$ [R. J. Le Roy, J. Mol. Spectrosc. 194, 189 (1999)]. The two fits provide results of equivalent quality. The Born--Oppenheimer equilibrium bond distance for the imidogen radical has been calculated [$r_e^{BO}$ =103.606721(13) pm] and zero point energies have been derived for all the isotopologues.

astro-ph.GA↗

arXiv2018

HSCO$^+$ and DSCO$^+$: a multi-technique approach in the laboratory for the spectroscopy of interstellar ions

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.

astro-ph.GA↗