arXiv subjects

A. Faure

Publications and source records attributed to A. Faure.

At least 37 records · Page 2Linked to original sources

arXiv2020

Depletion and fractionation of nitrogen in collapsing cores

Measurements of the nitrogen isotopic ratio in Solar System comets show a constant value, ~140, which is three times lower than the protosolar ratio, a highly significant difference that remains unexplained. Observations of static starless cores at early stages of collapse confirm the theoretical expectation that nitrogen fractionation in interstellar conditions is marginal for most species. Yet, observed isotopic ratios in N2H+ are at variance with model predictions. These gaps in our understanding of how the isotopic reservoirs of nitrogen evolve, from interstellar clouds to comets, and, more generally, to protosolar nebulae, may have their origin in missing processes or misconceptions in the chemistry of interstellar nitrogen. So far, theoretical studies of nitrogen fractionation in starless cores have addressed the quasi-static phase of their evolution such that the effect of dynamical collapse on the isotopic ratio is not known. In this paper, we investigate the fractionation of 14N and 15N during the gravitational collapse of a pre-stellar core through gas-phase and grain adsorption and desorption reactions. The initial chemical conditions, which are obtained in steady state after typically a few Myr, show low degrees of fractionation in the gas phase, in agreement with earlier studies. However, during collapse, the differential rate of adsorption of 14N- and 15N-containing species onto grains results in enhanced 15N:14N ratios, in better agreement with the observations. Furthermore, we find differences in the behavior, with increasing density, of the isotopic ratio in different species. We find that the collapse must take place on approximately one free-fall timescale, based on the CO abundance profile in L183 [see the end in the PDF file]

astro-ph.GA↗

arXiv2020

Ammonium salts are a reservoir of nitrogen on a cometary nucleus and possibly on some asteroids

The measured nitrogen-to-carbon ratio in comets is lower than for the Sun, a discrepancy which could be alleviated if there is an unknown reservoir of nitrogen in comets. The nucleus of comet 67P/Churyumov-Gerasimenko exhibits an unidentified broad spectral reflectance feature around 3.2 micrometers, which is ubiquitous across its surface. On the basis of laboratory experiments, we attribute this absorption band to ammonium salts mixed with dust on the surface. The depth of the band indicates that semivolatile ammonium salts are a substantial reservoir of nitrogen in the comet, potentially dominating over refractory organic matter and more volatile species. Similar absorption features appear in the spectra of some asteroids, implying a compositional link between asteroids, comets, and the parent interstellar cloud.

astro-ph.EP↗

arXiv2020

The effect of CO-H2O collisions in the rotational excitation of cometary CO

We present the first accurate rate coefficients for the rotational excitation of CO by H2O in the kinetic temperature range 5-100 K. The statistical adiabatic channel method (SACM) is combined with a high-level rigid-rotor CO-H2O intermolecular potential surface. Transitions among the first 11 rotational levels of CO and the first 8 rotational levels of both para-H2O and ortho-H2O are considered. Our rate coefficients are compared to previous data from the literature and they are also incorporated in a simple non-LTE model of cometary coma including collision-induced transitions, solar radiative pumping and radiative decay. We find that the uncertainties in the collision data have significant influence on the CO population distribution for H2O densities in the range 10^3-10^8 cm^-3. We also show that the rotational distribution of H2O plays an important role in CO excitation (owing to correlated energy transfer in both CO and H2O), while the impact of the ortho-to-para ratio of H2O is found to be negligible.

astro-ph.EP↗

arXiv2019

Cyanoacetylene in the outflow/hot molecular core G331.512-0.103

Using APEX-1 and APEX-2 observations, we have detected and studied the rotational lines of the HC$_3$N molecule (cyanoacetylene) in the powerful outflow/hot molecular core G331.512-0.103. We identified thirty-one rotational lines at $J$ levels between 24 and 39; seventeen of them in the ground vibrational state $v$=0 (9 lines corresponding to the main C isotopologue and 8 lines corresponding to the $^{13}$C isotopologues), and fourteen in the lowest vibrationally excited state $v_7$=1. Using LTE-based population diagrams for the beam-diluted $v$=0 transitions, we determined $T_{\rm exc}$=85$\pm$4 K and $N$(HC$_3$N)=(6.9$\pm$0.8)$\times$10$^{14}$ cm$^{-2}$, while for the beam-diluted $v_7$=1 transitions we obtained $T_{\rm exc}$=89$\pm$10 K and $N$(HC$_3$N)=2$\pm$1$\times$10$^{15}$ cm$^{-2}$. Non-LTE calculations using H$_2$ collision rates indicate that the HC$_3$N emission is in good agreement with LTE-based results. From the non-LTE method we estimated $T_{\rm kin}$ $\simeq$90~K, $n$(H$_2$)$\simeq$2$\times$10$^7$~cm$^{-3}$ for a central core of 6 arcsec in size. A vibrational temperature in the range from 130~K to 145~K was also determined, values which are very likely lower limits. Our results suggest that rotational transitions are thermalized, while IR radiative pumping processes are probably more efficient than collisions in exciting the molecule to the vibrationally excited state $v_7$=1. Abundance ratios derived under LTE conditions for the $^{13}$C isotopologues suggest that the main formation pathway of HC$_3$N is ${\rm C}_2{\rm H}_2 + {\rm CN} \rightarrow {\rm HC}_3{\rm N} + {\rm H}$.

astro-ph.GA↗

arXiv2018

Collisional excitation of NH3 by atomic and molecular hydrogen

We report extensive theoretical calculations on the rotation-inversion excitation of interstellar ammonia (NH3) due to collisions with atomic and molecular hydrogen (both para- and ortho-H2). Close-coupling calculations are performed for total energies in the range 1-2000 cm-1 and rotational cross sections are obtained for all transitions among the lowest 17 and 34 rotation-inversion levels of ortho- and para-NH3, respectively. Rate coefficients are deduced for kinetic temperatures up to 200 K. Propensity rules for the three colliding partners are discussed and we also compare the new results to previous calculations for the spherically symmetrical He and para-H2 projectiles. Significant differences are found between the different sets of calculations. Finally, we test the impact of the new rate coefficients on the calibration of the ammonia thermometer. We find that the calibration curve is only weakly sensitive to the colliding partner and we confirm that the ammonia thermometer is robust.

physics.chem-ph↗

arXiv2018

The Dense Gas Fraction in Galactic Center Clouds

We present an analysis of gas densities in the central R=300 parsecs of the Milky Way, focusing on three clouds: GCM-0.02-0.07 (the 50 km/s cloud), GCM-0.13-0.08 (the 20 km/s cloud), and GCM0.25+0.01 (the "Brick"). Densities are determined using observations of the J=(3-2), (4-3), (5-4), (10-9), (18-17), (19-18), (21-20), and (24-23) transitions of the molecule HC3N. We find evidence of at least two excitation regimes for HC3N and constrain the low-excitation component to have a density less than 10^4 cm^-3 and the high-excitation component to have a density between 10^5 and 10^6 cm^-3. This is much less than densities of 10^7 cm^-3 that are found in Sgr B2, the most actively star-forming cloud in the Galactic center. This is consistent with the requirement of a higher density threshold for star formation in the Galactic center than is typical in the Galactic disk. We are also able to constrain the column density of each component in order to determine the mass fraction of 'dense' (n>10^5 cm^-3) gas for these clouds. We find that this is ~15% for all three clouds. Applying the results of our models to ratios of the (10-9) and (3-2) line across the entire central R=300 pc, we find that the fraction of gas with n>10^4 cm^-3 increases inward of a radius of ~140 pc, consistent with the predictions of recent models for the gas dynamics in this region. Our observations show that HC3N is an excellent molecule for probing the density structure of clouds in the Galactic center.

astro-ph.GA↗

arXiv2018

The nitrogen isotopic ratio of HC3N towards the L1544 prestellar core

The origin of the heavily fractionated reservoir of nitrogen in comets remains an issue in the theory of their formation and hence of the solar system. Whether the fractionated reservoir traced by comets is inherited from the interstellar cloud or is the product of processes taking place in the protostar, or in the protoplanetary disk, remains unclear. So far, observations of nitrogen isotopic ratios in protostars or prestellar cores have not securely identified such a fractionated reservoir owing to the intrinsic difficulty of direct isotopic ratios measurements. In this article, we report the detection of 5 rotational lines of \ce{HC3N}, {including the weaker components of the hyperfine multiplets}, and two rotational lines of its $^{15}$N isotopologue, towards the L1544 prestellar core. Based on a MCMC/non-LTE multi-line analysis at the hyperfine level, we derive the column densities of \ce{HC3N} ($8.0\pm0.4\tdix{13}$\cc) and \ce{HC3^{15}N} ($2.0\pm0.4\tdix{11}$\cc) and derive an isotopic ratio of 400$\pm$20(1$σ$). This value suggests that \ce{HC3N} is slightly depleted in $^{15}$N in L1544 with respect to the elemental $^{14}$N/$^{15}$N ratio {of $\approx$330} in the present-day local interstellar medium. Our study also stresses the need for radiative calculations at the hyperfine level. Finally, the comparison of the derived ratio with those obtained in CN and HCN in the same core seems to favor CN+C$_2$H$_2$ as the dominant formation route to HC$_3$N. However, uncertainties in the isotopic ratios preclude definitive conclusions.

astro-ph.GA↗

arXiv2018

Modelling the molecular composition and nuclear-spin chemistry of collapsing prestellar sources

We study the gravitational collapse of prestellar sources and the associated evolution of their chemical composition. We use the University of Grenoble Alpes Astrochemical Network (UGAN), which includes reactions involving the different nuclear--spin states of H2, H3+, and of the hydrides of carbon, nitrogen, oxygen, and sulfur, for reactions involving up to seven protons. In addition, species-to-species rate coefficients are provided for the ortho/para interconversion of the H3+ + H2 system and isotopic variants. The composition of the medium is followed from an initial steady state through the early phase of isothermal gravitational collapse. Both the freeze--out of the molecules on to grains and the coagulation of the grains were incorporated in the model. The predicted abundances and column densities of the spin isomers of ammonia and its deuterated forms are compared with those measured recently towards the prestellar cores H-MM1, L16293E, and Barnard B1. We find that gas--phase processes alone account satisfactorily for the observations, without recourse to grain-surface reactions. In particular, our model reproduces both the isotopologue abundance ratios and the ortho:para ratios of NH2D and NHD2 within observational uncertainties. More accurate observations are necessary to distinguish between full scrambling processes---as assumed in our gas-phase network---and direct nucleus- or atom-exchange reactions.

astro-ph.GA↗

arXiv2017

NH_3(1_0-0_0) in the pre-stellar core L1544

Pre-stellar cores represent the initial conditions in the process of star and planet formation, therefore it is important to study their physical and chemical structure. Because of their volatility, nitrogen-bearing molecules are key to study the dense and cold gas present in pre-stellar cores. The NH_3 rotational transition detected with Herschel-HIFI provides a unique combination of sensitivity and spectral resolution to further investigate physical and chemical processes in pre-stellar cores. Here we present the velocity-resolved Herschel-HIFI observations of the ortho-NH_3(1_0-0_0) line at 572 GHz and study the abundance profile of ammonia across the pre-stellar core L1544 to test current theories of its physical and chemical structure. Recently calculated collisional coefficients have been included in our non-LTE radiative transfer code to reproduce Herschel observations. A gas-grain chemical model, including spin-state chemistry and applied to the (static) physical structure of L1544 is also used to infer the abundance profile of ortho-NH_3 . The hyperfine structure of ortho-NH_3(1_0-0_0) is resolved for the first time in space. All the hyperfine components are strongly self-absorbed. The profile can be reproduced if the core is contracting in quasi-equilibrium, consistent with previous work, and if the NH_3 abundance is slightly rising toward the core centre, as deduced from previous interferometric observations of para-NH_3(1,1). The chemical model overestimates the NH_3 abundance at radii between ~ 4000 and 15000 AU by about two orders of magnitude and underestimates the abundance toward the core centre by more than one order of magnitude. Our observations show that chemical models applied to static clouds have problems in reproducing NH_3 observations.

astro-ph.GA↗

arXiv2017

State-to-state chemistry and rotational excitation of CH$^+$ in photon-dominated regions

We present a detailed theoretical study of the rotational excitation of CH$^+$ due to reactive and nonreactive collisions involving C$^+(^2P)$, H$_2$, CH$^+$, H and free electrons. Specifically, the formation of CH$^+$ proceeds through the reaction between C$^+(^2P)$ and H$_2(ν_{\rm H_2}=1, 2)$, while the collisional (de)excitation and destruction of CH$^+$ is due to collisions with hydrogen atoms and free electrons. State-to-state and initial-state-specific rate coefficients are computed in the kinetic temperature range 10-3000~K for the inelastic, exchange, abstraction and dissociative recombination processes using accurate potential energy surfaces and the best scattering methods. Good agreement, within a factor of 2, is found between the experimental and theoretical thermal rate coefficients, except for the reaction of CH$^+$ with H atoms at kinetic temperatures below 50~K. The full set of collisional and chemical data are then implemented in a radiative transfer model. Our Non-LTE calculations confirm that the formation pumping due to vibrationally excited H$_2$ has a substantial effect on the excitation of CH$^+$ in photon-dominated regions. In addition, we are able to reproduce, within error bars, the far-infrared observations of CH$^+$ toward the Orion Bar and the planetary nebula NGC~7027. Our results further suggest that the population of $ν_{\rm H_2}=2$ might be significant in the photon-dominated region of NGC~7027.

astro-ph.GA↗

arXiv2016

History of the solar-type protostar IRAS16293-2422 as told by the cyanopolyynes

Cyanopolyynes are chains of carbon atoms with an atom of hydrogen and a CN group on either side. They are detected almost everywhere in the ISM, as well as in comets. In the past, they have been used to constrain the age of some molecular clouds, since their abundance is predicted to be a strong function of time. We present an extensive study of the cyanopolyynes distribution in the solar-type protostar IRAS16293-2422 based on TIMASSS IRAM-30m observations. The goals are (i) to obtain a census of the cyanopolyynes in this source and of their isotopologues; (ii) to derive how their abundance varies across the protostar envelope; and (iii) to obtain constraints on the history of IRAS16293-2422. We detect several lines from HC3N and HC5N, and report the first detection of DC3N, in a solar-type protostar. We found that the HC3N abundance is roughly constant (~1.3x10^(-11)) in the outer cold envelope of IRAS16293-2422, and it increases by about a factor 100 in the inner region where Tdust>80K. The HC5N has an abundance similar to HC3N in the outer envelope and about a factor of ten lower in the inner region. The HC3N abundance derived in the inner region, and where the increase occurs, also provide strong constraints on the time taken for the dust to warm up to 80K, which has to be shorter than ~10^3-10^4yr. Finally, the cyanoacetylene deuteration is about 50\% in the outer envelope and <5$\% in the warm inner region. The relatively low deuteration in the warm region suggests that we are witnessing a fossil of the HC3N abundantly formed in the tenuous phase of the pre-collapse and then frozen into the grain mantles at a later phase. The accurate analysis of the cyanopolyynes in IRAS16293-2422 unveils an important part of its past story. It tells us that IRAS16293-2422 underwent a relatively fast (<10^5yr) collapse and a very fast (<10^3-10^4yr) warming up of the cold material to 80K.

astro-ph.GA↗

arXiv2016

Collisional excitation of HC3N by para- and ortho-H2

New calculations for rotational excitation of cyanoacetylene by collisions with hydrogen molecules are performed to include the lowest 38 rotational levels of HC3N and kinetic temperatures to 300 K. Calculations are based on the interaction potential of Wernli et al. A&A, 464, 1147 (2007) whose accuracy is checked against spectroscopic measurements of the HC3N-H2 complex. The quantum coupled-channel approach is employed and complemented by quasi-classical trajectory calculations. Rate coefficients for ortho-H2 are provided for the first time. Hyperfine resolved rate coefficients are also deduced. Collisional propensity rules are discussed and comparisons between quantum and classical rate coefficients are presented. This collisional data should prove useful in interpreting HC3N observations in the cold and warm ISM, as well as in protoplanetary disks.

astro-ph.GA↗

arXiv2016

N$_2$H$^+$ and N$^{15}$NH$^+$ towards the prestellar core 16293E in L1689N

Understanding the processes that could lead to enrichment of molecules in $^{15}$N atoms is of particular interest in order to shed light on the relatively large variations observed in the $^{14}$N/$^{15}$N ratio in various solar system environments. Currently, the sample of molecular clouds where $^{14}$N/$^{15}$N ratios have been measured is small and has to be enlarged in order to allow statistically significant studies. In particular, the N$_2$H$^+$ molecule currently shows the largest spread of $^{14}$N/$^{15}$N ratios in high-mass star forming regions. However, the $^{14}$N/$^{15}$N ratio in N$_2$H$^+$ was obtained in only two low-mass star forming regions (L1544 and B1b). The current work extends this sample to a third dark cloud. We targeted the 16293E prestellar core, where the N$^{15}$NH$^+$ $J$=1-0 line was detected. Using a model previously developed for the physical structure of the source, we solved the molecular excitation with a non-local radiative transfer code. For that purpose, we computed specific collisional rate coefficients for the N$^{15}$NH$^+$-H$_2$ collisional system. As a first step of the analysis, the N$_2$H$^+$ abundance profile was constrained by reproducing the N$_2$H$^+$ $J$=1-0 and 3-2 maps. A scaling factor was then applied to this profile to match the N$^{15}$NH$^+$ $J$=1-0 spectrum. We derive a column density ratio N$_2$H$^+$ / N$^{15}$NH$^+$ = $330^{+170}_{-100}$. The current estimate $\sim$330 agrees with the value typical of the elemental isotopic ratio in the local ISM. It is however lower than in some other cores, where values as high as 1300 have been reported.

astro-ph.GA↗

arXiv2016

Detection of protonated formaldehyde in the prestellar core L1689B

Complex organic molecules (COMs) are detected in many regions of the interstellar medium, including prestellar cores. However, their formation mechanisms in cold (~10 K) cores remain to this date poorly understood. The formyl radical HCO is an important candidate precursor for several O-bearing terrestrial COMs in cores, as an abundant building block of many of these molecules. Several chemical routes have been proposed to account for its formation, both on grain surfaces, as an incompletely hydrogenated product of H addition to frozen-out CO molecules, or in the gas phase, either the product of the reaction between H2CO and a radical, or as a product of dissociative recombination of protonated formaldehyde H2COH+. The detection and abundance determination of H2COH+, if present, could provide clues as to whether this latter scenario might apply. We searched for protonated formaldehyde H2COH+ in the prestellar core L1689B using the IRAM 30m telescope. The H2COH+ ion is unambiguously detected, for the first time in a cold (~10 K) source. The derived abundance agrees with a scenario in which the formation of H2COH+ results from the protonation of formaldehyde. We use this abundance value to constrain the branching ratio of the dissociative recombination of H2COH+ towards the HCO channel to ~10-30%. This value could however be smaller if HCO can be efficiently formed from gas-phase neutral-neutral reactions, and we stress the need for laboratory measurements of the rate constants of these reactions at 10 K. Given the experimental difficulties in measuring branching ratios experimentally, observations can bring valuable constraints on these values, and provide a useful input for chemical networks.

astro-ph.GA↗

arXiv2016

Collisional excitation of doubly and triply deuterated ammonia ND$_2$H and ND$_3$ by H$_2$

The availability of collisional rate coefficients is a prerequisite for an accurate interpretation of astrophysical observations, since the observed media often harbour densities where molecules are populated under non--LTE conditions. In the current study, we present calculations of rate coefficients suitable to describe the various spin isomers of multiply deuterated ammonia, namely the ND$_2$H and ND$_3$ isotopologues. These calculations are based on the most accurate NH$_3$--H$_2$ potential energy surface available, which has been modified to describe the geometrical changes induced by the nuclear substitutions. The dynamical calculations are performed within the close--coupling formalism and are carried out in order to provide rate coefficients up to a temperature of $T$ = 50K. For the various isotopologues/symmetries, we provide rate coefficients for the energy levels below $\sim$ 100 cm$^{-1}$. Subsequently, these new rate coefficients are used in astrophysical models aimed at reproducing the NH$_2$D, ND$_2$H and ND$_3$ observations previously reported towards the prestellar cores B1b and 16293E. We thus update the estimates of the corresponding column densities and find a reasonable agreement with the previous models. In particular, the ortho--to--para ratios of NH$_2$D and NHD$_2$ are found to be consistent with the statistical ratios.

astro-ph.GA↗

arXiv2016

The NH$_2$D hyperfine structure revealed by astrophysical observations

The 1$_{11}$-1$_{01}$ lines of ortho and para--NH$_2$D (o/p-NH$_2$D), respectively at 86 and 110 GHz, are commonly observed to provide constraints on the deuterium fractionation in the interstellar medium. In cold regions, the hyperfine structure due to the nitrogen ($^{14}$N) nucleus is resolved. To date, this splitting is the only one which is taken into account in the NH$_2$D column density estimates. We investigate how the inclusion of the hyperfine splitting caused by the deuterium (D) nucleus affects the analysis of the rotational lines of NH$_2$D. We present 30m IRAM observations of the above mentioned lines, as well as APEX o/p-NH$_2$D observations of the 1$_{01}$-0$_{00}$ lines at 333 GHz. The hyperfine spectra are first analyzed with a line list that only includes the hyperfine splitting due to the $^{14}$N nucleus. We find inconsistencies between the line widths of the 1$_{01}$-0$_{00}$ and 1$_{11}$-1$_{01}$ lines, the latter being larger by a factor of $\sim$1.6$\pm0.3$. Such a large difference is unexpected given the two sets of lines are likely to originate from the same region. We next employ a newly computed line list for the o/p-NH$_2$D transitions, where the hyperfine structure induced by both nitrogen and deuterium nuclei is included. With this new line list, the analysis of the previous spectra leads to linewidths which are compatible. Neglecting the hyperfine structure owing to D leads to overestimate the linewidths of the o/p-NH$_2$D lines at 3 mm. The error for a cold molecular core is about 50\%. This error propagates directly to the column density estimate. It is therefore recommended to take into account the hyperfine splittings caused by both the $^{14}$N and D nuclei in any analysis relying on these lines.

astro-ph.GA↗

arXiv2015

Ortho-to-para ratio of NH2. Herschel-HIFI observations of ortho- and para-NH2 rotational transitions towards W31C, W49N, W51 and G34.3+0.1

We have used the Herschel-HIFI instrument to observe both nuclear spin symmetries of amidogen (NH2) towards the high-mass star-forming regions W31C (G10.6-0.4), W49N (G43.2-0.1), W51 (G49.5-0.4) and G34.3+0.1. The aim is to investigate the ratio of nuclear spin types, the ortho-to-para ratio (OPR), of NH2. The excited NH2 transitions are used to construct radiative transfer models of the hot cores and surrounding envelopes in order to investigate the excitation and possible emission of the ground state rotational transitions of ortho-NH2 N_(K_a,K_c} J=1_(1,1) 3/2 - 0_(0,0) 1/2 and para-NH2 2_(1,2) 5/2 - 1_(0,1) 3/2$ used in the OPR calculations. Our best estimate of the average OPR in the envelopes lie above the high temperature limit of three for W49N, specifically 3.5 with formal errors of \pm0.1, but for W31C, W51, and G34.3+0.1 we find lower values of 2.5\pm0.1, 2.7\pm0.1, and 2.3\pm0.1, respectively. Such low values are strictly forbidden in thermodynamical equilibrium since the OPR is expected to increase above three at low temperatures. In the translucent interstellar gas towards W31C, where the excitation effects are low, we find similar values between 2.2\pm0.2 and 2.9\pm0.2. In contrast, we find an OPR of 3.4\pm0.1 in the dense and cold filament connected to W51, and also two lower limits of >4.2 and >5.0 in two other translucent gas components towards W31C and W49N. At low temperatures (T \lesssim 50 K) the OPR of H2 is <10^-1, far lower than the terrestrial laboratory normal value of three. In such a "para-enriched H2" gas, our astrochemical models can reproduce the variations of the observed OPR, both below and above the thermodynamical equilibrium value, by considering nuclear-spin gas-phase chemistry. The models suggest that values below three arise in regions with temperatures >20-25 K, depending on time, and values above three at lower temperatures.

astro-ph.GA↗

arXiv2015

Hydrogen isotope exchanges between water and methanol in interstellar ices

The deuterium fractionation of gas-phase molecules in hot cores is believed to reflect the composition of interstellar ices. The deuteration of methanol is a major puzzle, however, because the isotopologue ratio [CH2DOH]/[CH3OD], which is predicted to be equal to 3 by standard grain chemistry models, is much larger (~20) in low-mass hot corinos and significantly lower (~1) in high-mass hot cores. This dichotomy in methanol deuteration between low-mass and massive protostars is currently not understood. In this study, we report a simplified rate equation model of the deuterium chemistry occurring in the icy mantles of interstellar grains. We apply this model to the chemistry of hot corinos and hot cores, with IRAS 16293-2422 and the Orion~KL Compact Ridge as prototypes, respectively. The chemistry is based on a statistical initial deuteration at low temperature followed by a warm-up phase during which thermal hydrogen/deuterium (H/D) exchanges occur between water and methanol. The exchange kinetics is incorporated using laboratory data. The [CH2DOH]/[CH3OD] ratio is found to scale inversely with the D/H ratio of water, owing to the H/D exchange equilibrium between the hydroxyl (-OH) functional groups of methanol and water. Our model is able to reproduce the observed [CH2DOH]/[CH3OD] ratios provided that the primitive fractionation of water ice [HDO]/[H2O] is ~ 2% in IRAS 16293-2422 and ~0.6% in Orion~KL. We conclude that the molecular D/H ratios measured in hot cores may not be representative of the original mantles because molecules with exchangeable deuterium atoms can equilibrate with water ice during the warm-up phase.

astro-ph.SR↗