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Register a new userDeuterium fractionation of nitrogen hydrides: detections of NHD and ND$_2$
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Although ammonia is an abundant molecule commonly observed towards the dense interstellar medium, it has not yet been established whether its main formation route is from gas-phase ion-molecule reactions or grain-surface hydrogen additions on adsorbed nitrogen atoms. Deuterium fractionation can be used as a tool to constrain formation mechanisms. High abundances of deuterated molecules are routinely observed in the dense interstellar medium, with the ratio between deuterated molecules and the main isotopologue enhanced by several orders of magnitude with respect to the elemental D/H ratio. In the case of ammonia, the detection of its triply deuterated isotopologue hints at high abundances of the deuterated intermediate nitrogen radicals, ND, NHD and ND$_2$. So far however, only ND has been detected in the interstellar medium. In this paper, to constrain the formation of ammonia, we aim at determining the NHD/NH$_2$ and ND$_2$/NHD abundance ratios, and compare them with the predictions of both pure gas-phase and grain-surface chemical models. We searched for the fundamental rotational transitions of NHD and ND$_2$ towards the class 0 protostar IRAS16293-2422, towards which NH, NH$_2$ and ND had been previously detected. Both NHD and ND$_2$ are detected in absorption towards the source. The relative abundance ratios NH$_2$ : NHD : ND$_2$ are close to 8 : 4 : 1. These ratios can be reproduced by our gas-phase chemical model within a factor of two-three. Statistical ratios as expected from grain-surface chemistry are also consistent with our data. Further investigations of the ortho-to-para ratio in ND$_2$ , both theoretical and observational, could bring new constraints to better understand nitrogen hydride chemistry.
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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.
Context. The increased sensitivity and high spectral resolution of millimeter telescopes allow the detection of an increasing number of isotopically substituted molecules in the interstellar medium. The 14N/ 15N ratio is difficult to measure directly for carbon containing molecules. Aims. We want to check the underlying hypothesis that the 13C/ 12C ratio of nitriles and isonitriles is equal to the elemental value via a chemical time dependent gas phase chemical model. Methods. We have built a chemical network containing D, 13C and 15N molecular species after a careful check of the possible fractionation reactions at work in the gas phase. Results. Model results obtained for 2 different physical conditions corresponding respectively to a moderately dense cloud in an early evolutionary stage and a dense depleted pre-stellar core tend to show that ammonia and its singly deuterated form are somewhat enriched in 15N, in agreement with observations. The 14N/ 15N ratio in N2H+ is found to be close to the elemental value, in contrast to previous models which obtain a significant enrichment, as we found that the fractionation reaction between 15N and N2H+ has a barrier in the entrance channel. The large values of the N2H+/15NNH+ and N2H+/ N15NH+ ratios derived in L1544 cannot be reproduced in our model. Finally we find that nitriles and isonitriles are in fact significantly depleted in 13C, questioning previous interpretations of observed C15N, HC15N and H15NC abundances from 13C containing isotopologues.
Nitrogen is the fifth most abundant element in the Universe, yet the gas-phase chemistry of N-bearing species remains poorly understood. Nitrogen hydrides are key molecules of nitrogen chemistry. Their abundance ratios place strong constraints on the production pathways and reaction rates of nitrogen-bearing molecules. We observed the class 0 protostar IRAS16293-2422 with the heterodyne instrument HIFI, covering most of the frequency range from 0.48 to 1.78~THz at high spectral resolution. The hyperfine structure of the amidogen radical o-NH2 is resolved and seen in absorption against the continuum of the protostar. Several transitions of ammonia from 1.2 to 1.8~THz are also seen in absorption. These lines trace the low-density envelope of the protostar. Column densities and abundances are estimated for each hydride. We find that NH:NH2:NH3=5:1:300. {Dark clouds chemical models predict steady-state abundances of NH2 and NH3 in reasonable agreement with the present observations, whilst that of NH is underpredicted by more than one order of magnitude, even using updated kinetic rates. Additional modelling of the nitrogen gas-phase chemistry in dark-cloud conditions is necessary before having recourse to heterogen processes.
Using the Green Bank Telescope (GBT), we have obtained accurate measurements of the $^{14}$N/$^{15}$N isotopic ratio in ammonia in two nearby cold, dense molecular clouds, Barnard~1 and NGC 1333. The $^{14}$N/$^{15}$N ratio in Barnard~1, $334 pm 50$ (3$sigma$), is particularly well constrained and falls in between the local interstellar medium/proto-solar value of $sim 450$ and the terrestrial atmospheric value of 272. The NGC 1333 measurement is consistent with the Barnard~1 result, but has a larger uncertainty. We do not see evidence for the very high $^{15}$N enhancements seen in cometary CN. Sensitive observations of a larger, carefully selected sample of prestellar cores with varying temperatures and gas densities can significantly improve our understanding of the nitrogen fractionation in the local interstellar medium and its relation to the isotopic ratios measured in various solar system reservoirs.
The [HDO]/[H2O] ratio is a crucial parameter for probing the history of water formation. So far, it has been measured for only three solar type protostars and yielded different results, possibly pointing to a substantially different history in their formation. In the present work, we report new interferometric observations of the HDO 4 2,2 - 4 2,3 line for two solar type protostars, IRAS2A and IRAS4A, located in the NGC1333 region. In both sources, the detected HDO emission originates from a central compact unresolved region. Comparison with previously published interferometric observations of the H218$O 3 1,3 - 2 2,0 line shows that the HDO and H$_2$O lines mostly come from the same region. A non-LTE LVG analysis of the HDO and H218$O line emissions, combined with published observations, provides a [HDO]/[H2O] ratio of 0.3 - 8 % in IRAS2A and 0.5 - 3 % in IRAS4A. First, the water fractionation is lower than that of other molecules such as formaldehyde and methanol in the same sources. Second, it is similar to that measured in the solar type protostar prototype, IRAS16293-2422, and, surprisingly enough, larger than that measured in NGC1333 IRAS4B. {The comparison of the measured values towards IRAS2A and IRAS4A with the predictions of our gas-grain model GRAINOBLE gives similar conclusions to those for IRAS 16293, arguing that these protostars {share} a similar chemical history, although they are located in different clouds.
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