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In light of its ubiquitous presence in the interstellar gas, the chemistry and reactivity of the HCO+ ion requires special attention. The availability of up-to-date collisional data between this ion and the most abundant perturbing species in the interstellar medium is a critical resource in order to derive reliable values of its molecular abundance from astronomical observations. This work intends to provide improved scattering parameters for the HCO+ and He collisional system. We have tested the accuracy of explicitly correlated coupled-cluster methods for mapping the short- and long-range multi-dimensional potential energy surface of atom-ion systems. A validation of the methodology employed for the calculation of the potential well has been obtained from the comparison with experimentally derived bound-state spectroscopic parameters. Finally, by solving the close-coupling scattering equations, we have derived the pressure broadening and shift coefficients for the first six rotational transitions of HCO+ as well as inelastic state-to-state transition rates up to j = 5 in the 5-100 K temperature interval., Comment: 8 pages, 5 figures

In light of its ubiquitous presence in the interstellar gas, the chemistry and reactivity of the HCO+ ion requires special attention. The availability of up-to-date collisional data between this ion and the most abundant perturbing species in the interstellar medium is a critical resource in order to derive reliable values of its molecular abundance from astronomical observations. This work intends to provide improved scattering parameters for the HCO+ and He collisional system. We have tested the accuracy of explicitly correlated coupled-cluster methods for mapping the short- and long-range multi-dimensional potential energy surface of atom-ion systems. A validation of the methodology employed for the calculation of the potential well has been obtained from the comparison with experimentally derived bound-state spectroscopic parameters. Finally, by solving the close-coupling scattering equations, we have derived the pressure broadening and shift coefficients for the first six rotational transitions of HCO+ as well as inelastic state-to-state transition rates up to j = 5 in the 5-100 K temperature interval., Comment: 8 pages, 5 figures

Cyanoacetylene, the simplest cyanopolyyne, is an abundant interstellar molecule commonly observed in a vast variety of astronomical sources. Despite its importance as a potential tracer of the evolution of star-forming processes, the deuterated form of cyanoacetylene is less observed and less studied in the laboratory than the main isotopologue. Here, we report the most extensive spectroscopic characterization of DC$_3$N to date, from the millimeter domain to the infrared region. Rotational and ro-vibrational spectra have been recorded using millimeter-wave frequency-modulation and Fourier-transform infrared spectrometers, respectively. All the vibrational states with energy up to 1015 cm$^{-1}$ have been analyzed in a combined fit, where the effects due to anharmonic resonances have been adequately accounted for. The analysis contains over 6500 distinct transition frequencies, from which all the vibrational energies have been determined with good precision for many fundamental, overtone, and combination states. This work provides a comprehensive line catalog for astronomical observations of DC$_3$N, Comment: 14 pages, 3 figures, 8 tables, accepted for publication in JQSRT

Deuterium fractionation processes in the interstellar medium (ISM) have been shown to be highly efficient in the family of nitrogen hydrides. To date, observations were limited to ammonia (NH$_2$D, NHD$_2$, ND$_3$) and imidogen radical (ND) isotopologues. We want to explore the high frequency windows offered by the \emph{Herschel Space Observatory} to search for deuterated forms of amidogen radical NH$_2$ and to compare the observations against the predictions of our comprehensive gas-grain chemical model. Making use of the new molecular spectroscopy data recently obtained at high frequencies for NHD and ND$_2$, both isotopologues have been searched for in the spectral survey towards the class 0 IRAS 16293-2422, a source in which NH$_3$, NH and their deuterated variants have been previously detected. We used the observations carried out with HIFI (Heterodyne Instrument for the Far Infrared) in the framework of the key program "Chemical Herschel surveys of star forming regions" (CHESS). We report the first detection of interstellar NHD and ND$_2$. Both species are observed in absorption against the continuum of the protostar. From the analysis of their hyperfine structure, accurate excitation temperature and column density values have been determined. The latter were combined with the column density of the parent species NH$_2$ to derive the deuterium fractionation in amidogen. The amidogen D/H ratio measured in the low-mass protostar IRAS 16293-2422 is comparable to the one derived for the related species imidogen and much higher than that observed for ammonia. Additional observations of these species will give more insights into the mechanism of ammonia formation and deuteration in the ISM. We finally indicate the current possibilities to further explore these species at submillimeter wavelengths., Comment: 11 pages, 5 figures, 7 tables. Accepted for publication in A&A

Chloromethane is the only organochloride detected in space to date. Its recent observation towards the low-mass protostar IRAS 16293-2422 with ALMA offers a prompt for new laboratory studies of CH$_3$Cl and its isotopologues. Here, we report the investigation of the rotational spectrum of monodeuterated chloromethane CH$_2$DCl in the frequency region between 90 and 300 GHz. The measurements have been carried out with a frequency-modulation millimeter-wave spectrometer, arranged to perform saturation spectroscopy. From the analysis of hyperfine-resolved spectra of the two chlorine isotopologues CH$_2$D$^{35}$Cl and CH$_2$D$^{37}$Cl, consistent sets of accurate spectroscopic parameters have been obtained. This work provides reliable spectral predictions which can be used to guide radio-astronomical searches of CH$_2$DCl in the interstellar medium and represents a solid base for future analyses of high-resolution infrared spectra of monodeuterated chloromethane., Comment: 13 pages, 2 figures, 3 tables

Aminoacetonitrile, a molecule detected in the interstellar medium only towards the star-forming region Sagittarius B2 (Sgr B2) thus far, is considered an important prebiotic species. To date, observations were limited to ground state emission lines, whereas transitions from within vibrationally excited states remained undetected. We wanted to accurately determine the energies of the low-lying vibrational states of aminoacetonitrile, which are expected to be populated in Sgr B2(N1), the main hot core of Sgr B2(N). This step is fundamental in order to properly evaluate the vibration-rotation partition function of aminoacetonitrile as well as the line strengths of the rotational transitions of its vibrationally excited states. This is necessary to derive accurate column densities and secure the identification of these transitions in astronomical spectra. The far-infrared ro-vibrational spectrum of aminoacetonitrile has been recorded in absorption against a synchrotron source of continuum emission. Three bands, corresponding to the lowest vibrational modes of aminoacetonitrile, were observed in the frequency region below 500 cm$^{-1}$. The combined analysis of ro-vibrational and pure rotational data allowed us to prepare new spectral line catalogs for all the states under investigation. We used the imaging spectral line survey ReMoCA performed with ALMA to search for vibrationally excited aminoacetonitrile toward Sgr B2(N1). On the basis of these spectroscopic predictions, we report the interstellar detection of aminoacetonitrile in its $v_{11}=1$ and $v_{18}=1$ vibrational states toward Sgr B2(N1) in addition to emission in its vibrational ground state. The intensities of the identified $v_{11}=1$ and $v_{18}=1$ lines are consistent with the detected $v=0$ lines under LTE at a temperature of 200 K for an aminoacetonitrile column density of $1.1 \times 10^{17}$ cm$^{-2}$., Comment: 14 pages, 7 figures, 5 tables, accepted for publication in A&A

We present the study of deuteration of cyanoacetylene (HC$_3$N) towards a sample of 28 high-mass star-forming cores divided into different evolutionary stages, from starless to evolved protostellar cores. We report for the first time the detection of DC$_3$N towards 15 high-mass cores. The abundance ratios of DC$_3$N with respect HC$_3$N range in the interval 0.003$-$0.022, lower than those found in low-mas protostars and dark clouds. No significant trend with the evolutionary stage, or with the kinetic temperature of the region, has been found. We compare the level of deuteration of HC$_3$N with those of other molecules towards the same sample, finding weak correlation with species formed only or predominantly in gas phase (N$_2$H$^+$ and HNC, respectively), and no correlation with species formed only or predominantly on dust grains (CH$_3$OH and NH$_3$, respectively). We also present a single-dish map of DC$_3$N towards the protocluster IRAS 05358+3543, which shows that DC$_3$N traces an extended envelope ($\sim$0.37 pc) and peaks towards two cold condensations separated from the positions of the protostars and the dust continuum. The observations presented in this work suggest that deuteration of HC$_3$N is produced in the gas of the cold outer parts of massive star-forming clumps, giving us an estimate of the deuteration factor prior to the formation of denser gas., Comment: Accepted in Monthly Notices of the Royal Astronomical Society -- 11 pages, 7 Figures, 2 Tables. Version with some typos corrected

Context. Aminoacetonitrile, a molecule detected in the interstellar medium only toward the star-forming region Sagittarius B2 (Sgr B2), is considered an important prebiotic species; in particular, it is a possible precursor of the simplest amino acid glycine. To date, observations have been limited to ground state emission lines, whereas transitions from within vibrationally excited states remained undetected.Aims. We wanted to accurately determine the energies of the low-lying vibrational states of aminoacetonitrile, which are expected to be populated in Sgr B2(N1), the main hot core of Sgr B2(N). This step is fundamental in order to properly evaluate the vibration-rotation partition function of aminoacetonitrile as well as the line strengths of the rotational transitions of its vibrationally excited states. This is necessary to derive accurate column densities and secure the identification of these transitions in astronomical spectra.Methods. The far-infrared ro-vibrational spectrum of aminoacetonitrile has been recorded in absorption against a synchrotron source of continuum emission. Three bands, corresponding to the lowest vibrational modes of aminoacetonitrile, were observed in the frequency region below 500 cm(-1). The combined analysis of ro-vibrational and pure rotational data allowed us to prepare new spectral line catalogs for all the states under investigation. We used the imaging spectral line survey ReMoCA performed with ALMA to search for vibrationally excited aminoacetonitrile toward Sgr B2(N1). The astronomical spectra were analyzed under the local thermodynamic equilibrium (LTE) approximation.Results. Almost 11 000 lines have been assigned during the analysis of the laboratory spectrum of aminoacetonitrile, thanks to which the vibrational energies of the v(11)=1, v(18)=1, and v(17)=1 states have been determined. The whole dataset, which includes high J and K-a transitions, is well reproduced within the experimental accuracy. Reliable spectral predi

Context. Aminoacetonitrile, a molecule detected in the interstellar medium only toward the star-forming region Sagittarius B2 (Sgr B2), is considered an important prebiotic species; in particular, it is a possible precursor of the simplest amino acid glycine. To date, observations have been limited to ground state emission lines, whereas transitions from within vibrationally excited states remained undetected.Aims. We wanted to accurately determine the energies of the low-lying vibrational states of aminoacetonitrile, which are expected to be populated in Sgr B2(N1), the main hot core of Sgr B2(N). This step is fundamental in order to properly evaluate the vibration-rotation partition function of aminoacetonitrile as well as the line strengths of the rotational transitions of its vibrationally excited states. This is necessary to derive accurate column densities and secure the identification of these transitions in astronomical spectra.Methods. The far-infrared ro-vibrational spectrum of aminoacetonitrile has been recorded in absorption against a synchrotron source of continuum emission. Three bands, corresponding to the lowest vibrational modes of aminoacetonitrile, were observed in the frequency region below 500 cm(-1). The combined analysis of ro-vibrational and pure rotational data allowed us to prepare new spectral line catalogs for all the states under investigation. We used the imaging spectral line survey ReMoCA performed with ALMA to search for vibrationally excited aminoacetonitrile toward Sgr B2(N1). The astronomical spectra were analyzed under the local thermodynamic equilibrium (LTE) approximation.Results. Almost 11 000 lines have been assigned during the analysis of the laboratory spectrum of aminoacetonitrile, thanks to which the vibrational energies of the v(11)=1, v(18)=1, and v(17)=1 states have been determined. The whole dataset, which includes high J and K-a transitions, is well reproduced within the experimental accuracy. Reliable spectral predi

Cyanoacetylene, the simplest cyanopolyyne, is an abundant interstellar molecule commonly observed in a vast variety of astronomical sources. Despite its importance as a potential tracer of the evolution of star-forming processes, the deuterated form of cyanoacetylene is less observed and less studied in the laboratory than the main isotopologue. Here, we report the most extensive spectroscopic characterization of DC$_3$N to date, from the millimeter domain to the infrared region. Rotational and ro-vibrational spectra have been recorded using millimeter-wave frequency-modulation and Fourier-transform infrared spectrometers, respectively. All the vibrational states with energy up to 1015 cm$^{-1}$ have been analyzed in a combined fit, where the effects due to anharmonic resonances have been adequately accounted for. The analysis contains over 6500 distinct transition frequencies, from which all the vibrational energies have been determined with good precision for many fundamental, overtone, and combination states. This work provides a comprehensive line catalog for astronomical observations of DC$_3$N, Comment: 14 pages, 3 figures, 8 tables, accepted for publication in JQSRT

Deuterium fractionation processes in the interstellar medium (ISM) have been shown to be highly efficient in the family of nitrogen hydrides. To date, observations were limited to ammonia (NH$_2$D, NHD$_2$, ND$_3$) and imidogen radical (ND) isotopologues. We want to explore the high frequency windows offered by the \emph{Herschel Space Observatory} to search for deuterated forms of amidogen radical NH$_2$ and to compare the observations against the predictions of our comprehensive gas-grain chemical model. Making use of the new molecular spectroscopy data recently obtained at high frequencies for NHD and ND$_2$, both isotopologues have been searched for in the spectral survey towards the class 0 IRAS 16293-2422, a source in which NH$_3$, NH and their deuterated variants have been previously detected. We used the observations carried out with HIFI (Heterodyne Instrument for the Far Infrared) in the framework of the key program "Chemical Herschel surveys of star forming regions" (CHESS). We report the first detection of interstellar NHD and ND$_2$. Both species are observed in absorption against the continuum of the protostar. From the analysis of their hyperfine structure, accurate excitation temperature and column density values have been determined. The latter were combined with the column density of the parent species NH$_2$ to derive the deuterium fractionation in amidogen. The amidogen D/H ratio measured in the low-mass protostar IRAS 16293-2422 is comparable to the one derived for the related species imidogen and much higher than that observed for ammonia. Additional observations of these species will give more insights into the mechanism of ammonia formation and deuteration in the ISM. We finally indicate the current possibilities to further explore these species at submillimeter wavelengths., Comment: 11 pages, 5 figures, 7 tables. Accepted for publication in A&A

Aminoacetonitrile, a molecule detected in the interstellar medium only towards the star-forming region Sagittarius B2 (Sgr B2) thus far, is considered an important prebiotic species. To date, observations were limited to ground state emission lines, whereas transitions from within vibrationally excited states remained undetected. We wanted to accurately determine the energies of the low-lying vibrational states of aminoacetonitrile, which are expected to be populated in Sgr B2(N1), the main hot core of Sgr B2(N). This step is fundamental in order to properly evaluate the vibration-rotation partition function of aminoacetonitrile as well as the line strengths of the rotational transitions of its vibrationally excited states. This is necessary to derive accurate column densities and secure the identification of these transitions in astronomical spectra. The far-infrared ro-vibrational spectrum of aminoacetonitrile has been recorded in absorption against a synchrotron source of continuum emission. Three bands, corresponding to the lowest vibrational modes of aminoacetonitrile, were observed in the frequency region below 500 cm$^{-1}$. The combined analysis of ro-vibrational and pure rotational data allowed us to prepare new spectral line catalogs for all the states under investigation. We used the imaging spectral line survey ReMoCA performed with ALMA to search for vibrationally excited aminoacetonitrile toward Sgr B2(N1). On the basis of these spectroscopic predictions, we report the interstellar detection of aminoacetonitrile in its $v_{11}=1$ and $v_{18}=1$ vibrational states toward Sgr B2(N1) in addition to emission in its vibrational ground state. The intensities of the identified $v_{11}=1$ and $v_{18}=1$ lines are consistent with the detected $v=0$ lines under LTE at a temperature of 200 K for an aminoacetonitrile column density of $1.1 \times 10^{17}$ cm$^{-2}$., Comment: 14 pages, 7 figures, 5 tables, accepted for publication in A&A

Chloromethane is the only organochloride detected in space to date. Its recent observation towards the low-mass protostar IRAS 16293-2422 with ALMA offers a prompt for new laboratory studies of CH$_3$Cl and its isotopologues. Here, we report the investigation of the rotational spectrum of monodeuterated chloromethane CH$_2$DCl in the frequency region between 90 and 300 GHz. The measurements have been carried out with a frequency-modulation millimeter-wave spectrometer, arranged to perform saturation spectroscopy. From the analysis of hyperfine-resolved spectra of the two chlorine isotopologues CH$_2$D$^{35}$Cl and CH$_2$D$^{37}$Cl, consistent sets of accurate spectroscopic parameters have been obtained. This work provides reliable spectral predictions which can be used to guide radio-astronomical searches of CH$_2$DCl in the interstellar medium and represents a solid base for future analyses of high-resolution infrared spectra of monodeuterated chloromethane., Comment: 13 pages, 2 figures, 3 tables

We present the study of deuteration of cyanoacetylene (HC$_3$N) towards a sample of 28 high-mass star-forming cores divided into different evolutionary stages, from starless to evolved protostellar cores. We report for the first time the detection of DC$_3$N towards 15 high-mass cores. The abundance ratios of DC$_3$N with respect HC$_3$N range in the interval 0.003$-$0.022, lower than those found in low-mas protostars and dark clouds. No significant trend with the evolutionary stage, or with the kinetic temperature of the region, has been found. We compare the level of deuteration of HC$_3$N with those of other molecules towards the same sample, finding weak correlation with species formed only or predominantly in gas phase (N$_2$H$^+$ and HNC, respectively), and no correlation with species formed only or predominantly on dust grains (CH$_3$OH and NH$_3$, respectively). We also present a single-dish map of DC$_3$N towards the protocluster IRAS 05358+3543, which shows that DC$_3$N traces an extended envelope ($\sim$0.37 pc) and peaks towards two cold condensations separated from the positions of the protostars and the dust continuum. The observations presented in this work suggest that deuteration of HC$_3$N is produced in the gas of the cold outer parts of massive star-forming clumps, giving us an estimate of the deuteration factor prior to the formation of denser gas., Comment: Accepted in Monthly Notices of the Royal Astronomical Society -- 11 pages, 7 Figures, 2 Tables. Version with some typos corrected

We have mapped the dense dark core L1544 in H13CO+(1-0), DCO+(2-1), DCO+(3-2), N2H+(1-0), NTH+(3-2), N2D+(2-1), N2D+(3-2), C18O(1-0), and C17O(1-0) using the IRAM 30-m telescope. We have obtained supplementary observations of HC18O+(1-0), HC17O+(1-0), and D13CO+(2-1). Many of the observed maps show a general correlation with the distribution of dust continuum emission in contrast to C18O(1-0) and C17O(1-0) which give clear evidence for depletion of CO at positions close to the continuum peak. In particular N2D+(2-1) and (3-2) and to a lesser extent N2H+(1-0) appear to be excellent tracers of the dust continuum. We find that the tracers of high density gas (in particular N2D+) show a velocity gradient along the minor axis of the L1544 core and that there is evidence for larger linewidths close to the dust emission peak. We interpret this using the model of the L1544 proposed by Ciolek & Basu (2000) and by comparing the observed velocities with those expected on the basis of their model. The results show reasonable agreement between observations and model in that the velocity gradient along the minor axis and the line broadening toward the center of L1544 are predicted by the model. This is evidence in favour of the idea that amipolar diffusion across field lines is one of the basic processes leading to gravitational collapse. However, line widths are significantly narrower than observed and are better reproduced by the Myers & Zweibel (2001) model which considers the quasistatic vertical contraction of a layer due to dissipation of its Alfvenic turbulence, indicating the importance of this process for cores in the verge of forming a star., Comment: 24 pages, 9 figures, to be published in ApJ

The maps presented in Paper I are here used to infer the variation of the column densities of HCO+, DCO+, N2H+, and N2D+ as a function of distance from the dust peak. These results are interpreted with the aid of a crude chemical model which predicts the abundances of these species as a function of radius in a spherically symmetric model with radial density distribution inferred from the observations of dust emission at millimeter wavelengths and dust absorption in the infrared. Our main observational finding is that the N(N2D+)/N(N2H+) column density ratio is of order 0.2 towards the L1544 dust peak as compared to N(DCO+)/N(HCO+) = 0.04. We conclude that this result as well as the general finding that N2H+ and N2D+ correlate well with the dust is caused by CO being depleted to a much higher degree than molecular nitrogen in the high density core of L1544. Depletion also favors deuterium enhancement and thus N2D+, which traces the dense and highly CO-depleted core nucleus, is much more enhanced than DCO+. Our models do not uniquely define the chemistry in the high density depleted nucleus of L1544 but they do suggest that the ionization degree is a few times 10^{-9} and that the ambipolar diffusion time scale is locally similar to the free fall time. It seems likely that the lower limit which one obtains to ionization degree by summing all observable molecular ions is not a great underestimate of the true ionization degree. We predict that atomic oxygen is abundant in the dense core and, if so, H3O+ may be the main ion in the central highly depleted region of the core., Comment: 31 pages, 8 figures, to be published in ApJ

We have mapped the dense dark core L1544 in H13CO+(1-0), DCO+(2-1), DCO+(3-2), N2H+(1-0), NTH+(3-2), N2D+(2-1), N2D+(3-2), C18O(1-0), and C17O(1-0) using the IRAM 30-m telescope. We have obtained supplementary observations of HC18O+(1-0), HC17O+(1-0), and D13CO+(2-1). Many of the observed maps show a general correlation with the distribution of dust continuum emission in contrast to C18O(1-0) and C17O(1-0) which give clear evidence for depletion of CO at positions close to the continuum peak. In particular N2D+(2-1) and (3-2) and to a lesser extent N2H+(1-0) appear to be excellent tracers of the dust continuum. We find that the tracers of high density gas (in particular N2D+) show a velocity gradient along the minor axis of the L1544 core and that there is evidence for larger linewidths close to the dust emission peak. We interpret this using the model of the L1544 proposed by Ciolek & Basu (2000) and by comparing the observed velocities with those expected on the basis of their model. The results show reasonable agreement between observations and model in that the velocity gradient along the minor axis and the line broadening toward the center of L1544 are predicted by the model. This is evidence in favour of the idea that amipolar diffusion across field lines is one of the basic processes leading to gravitational collapse. However, line widths are significantly narrower than observed and are better reproduced by the Myers & Zweibel (2001) model which considers the quasistatic vertical contraction of a layer due to dissipation of its Alfvenic turbulence, indicating the importance of this process for cores in the verge of forming a star., Comment: 24 pages, 9 figures, to be published in ApJ

The maps presented in Paper I are here used to infer the variation of the column densities of HCO+, DCO+, N2H+, and N2D+ as a function of distance from the dust peak. These results are interpreted with the aid of a crude chemical model which predicts the abundances of these species as a function of radius in a spherically symmetric model with radial density distribution inferred from the observations of dust emission at millimeter wavelengths and dust absorption in the infrared. Our main observational finding is that the N(N2D+)/N(N2H+) column density ratio is of order 0.2 towards the L1544 dust peak as compared to N(DCO+)/N(HCO+) = 0.04. We conclude that this result as well as the general finding that N2H+ and N2D+ correlate well with the dust is caused by CO being depleted to a much higher degree than molecular nitrogen in the high density core of L1544. Depletion also favors deuterium enhancement and thus N2D+, which traces the dense and highly CO-depleted core nucleus, is much more enhanced than DCO+. Our models do not uniquely define the chemistry in the high density depleted nucleus of L1544 but they do suggest that the ionization degree is a few times 10^{-9} and that the ambipolar diffusion time scale is locally similar to the free fall time. It seems likely that the lower limit which one obtains to ionization degree by summing all observable molecular ions is not a great underestimate of the true ionization degree. We predict that atomic oxygen is abundant in the dense core and, if so, H3O+ may be the main ion in the central highly depleted region of the core., Comment: 31 pages, 8 figures, to be published in ApJ