Time-dependent Chemical Model Research Articles

Mapping Observations of Peptide-like Molecules around Sagittarius B2

Peptide-like molecules, which have a close connection with the origin of life, have been detected in the Universe. Mapping observations of HCONH2 and CH3CONH2, two of the simplest peptide-like molecules, are performed toward the Sagittarius B2 (Sgr B2) complex with the IRAM 30 m telescope. Seven transitions of HCONH2 and five transitions of CH3CONH2 are used in the analysis. The spatial distributions of the excitation temperature and column density of HCONH2 in the molecular envelope of Sgr B2 are obtained by rotation diagrams. Assuming the same excitation temperature of HCONH2, the column densities of CH3CONH2 are also calculated. The results show that the excitation temperature ranges from 6 to 46 K in the molecular envelope of Sgr B2. The abundance ratios between HCONH2 and CH3CONH2 are calculated to explore the relationship between them, as are those between HCONH2 and HNCO. The abundance ratio of CH3CONH2/HCONH2 varies from 10% to 20%, while that of HCONH2/HNCO ranges from 1.5% to 10%. CH3CONH2 is enhanced with respect to HCONH2 in the northwest region of Sgr B2. One transition of H13CONH2 is detected toward 12 positions of Sgr B2, from which a 12C/13C ratio of 28.7 is obtained. A time-dependent chemical model with a short-duration X-ray burst is used to explain the observed abundances of HCONH2 and CH3CONH2, with the best-fitting result at T dust = 53–56 K. More chemical reactions are required to be included in the model since the modeled abundance is lower than the observed one at the observed T dust.

Tracers of the ionization fraction in dense and translucent gas

Context.The ionization fraction in the neutral interstellar medium (ISM) plays a key role in the physics and chemistry of the ISM, from controlling the coupling of the gas to the magnetic field to allowing fast ion-neutral reactions that drive interstellar chemistry. Most estimations of the ionization fraction have relied on deuterated species such as DCO+, whose detection is limited to dense cores representing an extremely small fraction of the volume of the giant molecular clouds that they are part of. As large field-of-view hyperspectral maps become available, new tracers may be found. The growth of observational datasets is paralleled by the growth of massive modeling datasets and new methods need to be devised to exploit the wealth of information they contain.Aims.We search for the best observable tracers of the ionization fraction based on a grid of astrochemical models, with the broader aim of finding a general automated method applicable to searching for tracers of any unobservable quantity based on grids of models.Methods.We built grids of models that randomly sample a large range of physical conditions (unobservable quantities such as gas density, temperature, elemental abundances, etc.) and computed the corresponding observables (line intensities, column densities) and the ionization fraction. We estimated the predictive power of each potential tracer by training a random forest model to predict the ionization fraction from that tracer, based on these model grids.Results.In both translucent medium and cold dense medium conditions, we found several observable tracers with very good predictive power for the ionization fraction. Many tracers in cold dense medium conditions are found to be better and more widely applicable than the traditional DCO+/HCO+ratio. We also provide simpler analytical fits for estimating the ionization fraction from the best tracers, and for estimating the associated uncertainties. We discuss the limitations of the present study and select a few recommended tracers in both types of conditions.Conclusions.The method presented here is very general and can be applied to the measurement of any other quantity of interest (cosmic ray flux, elemental abundances, etc.) from any type of model (PDR models, time-dependent chemical models, etc.).

Molecular-cloud-scale Chemical Composition. III. Constraints of Average Physical Properties through Chemical Models

Abstract It is important to understand the origin of molecular line intensities and chemical composition at the molecular-cloud scale in Galactic sources because it serves as a benchmark to compare with the chemical compositions of extragalactic sources. Recent observations of 3-mm spectra averaged over a 10 pc scale show similar spectral patterns among sources for molecular lines HCN, HCO+, CCH, HNC, HNCO, c-C3H2, CS, SO, N2H+, and CN. To constrain the average physical properties emitting such spectral patterns, we model molecular spectra using a time-dependent gas-grain chemical model followed by a radiative transfer calculation. We use a grid of physical parameters such as the density n = 3 × 102–3 × 104 cm−3, temperature, T = 10–30 K, visual extinction A V = 2, 4, 10 mag, cosmic-ray ionization rate ζ = 10−17–10−16 s−1, and sulfur elemental abundance S/H = 8 ×10−8–8 × 10−7. A comparison with observations indicates that spectra are well reproduced with a relatively low density of n = (1–3) × 103 cm−3, T = 10 K, ζ = 10−17 s−1, and a short chemistry timescale of 105 yr. This short chemistry timescale may indicate that molecular clouds are constantly affected by turbulence, and exposed to low-density, low-A V regions that “refresh” the chemical clock by UV radiation. The relatively low density obtained is orders of magnitude lower than the commonly quoted critical density in the optically thin case. This range of density is consistent with results from recent observational analysis of molecular-cloud-scale mapping.

The ALMA-PILS Survey: Formaldehyde deuteration in warm gas on small scales toward IRAS 16293–2422 B

Context.The enhanced degrees of deuterium fractionation observed in envelopes around protostars demonstrate the importance of chemistry at low temperatures, relevant in pre- and protostellar cores. Formaldehyde is an important species in the formation of methanol and more complex molecules.Aims.Here, we aim to present the first study of formaldehyde deuteration on small scales around the prototypical low-mass protostar IRAS 16293–2422 using high spatial and spectral resolution Atacama Large Millimeter/submillimeter Array (ALMA) observations. We determine the excitation temperature, abundances and fractionation level of several formaldehyde isotopologues, including its deuterated forms.Methods.Excitation temperature and column densities of formaldehyde in the gas close to one of the components of the binary were constrained through modeling of optically thin lines assuming local thermodynamical equilibrium. The abundance ratios were compared to results from previous single dish observations, astrochemical models and local ISM values.Results.Numerous isotopologues of formaldehyde are detected, among them H2C17O, and D213CO for the first time in the ISM. The large range of upper energy levels covered by the HDCO lines help constrain the excitation temperature to 106 ± 13 K. Using the derived column densities, formaldehyde shows a deuterium fractionation of HDCO/H2CO = 6.5 ± 1%, D2CO/HDCO = 12.8–4.1+3.3%, and D2CO/H2CO = 0.6(4) ± 0.1%. The isotopic ratios derived are16O/18O = 805–79+43,18O/17O = 3.2–0.3+0.2, and12C/13C = 56–11+8.Conclusions.The HDCO/H2CO ratio is lower than that found in previous studies, highlighting the uncertainties involved in interpreting single dish observations of the inner warm regions. The D2CO/HDCO ratio is only slightly larger than the HDCO/H2CO ratio. This is consistent with formaldehyde forming in the ice as soon as CO has frozen onto the grains, with most of the deuteration happening toward the end of the prestellar core phase. A comparison with available time-dependent chemical models indicates that the source is in the early Class 0 stage.

ALMA imaging of C2H emission in the disk of NGC 1068

We study the feedback of star formation and nuclear activity on the chemistry of molecular gas in NGC1068, a nearby (D=14Mpc) Seyfert 2 barred galaxy, by analyzing if the abundances of key molecular species like ethynyl (C2H), a classical tracer of PDR, change in the different environments of the disk of the galaxy. We have used ALMA to map the emission of the hyperfine multiplet of C2H(N=1-0) and its underlying continuum emission in the central r~35"(2.5kpc)-region of the disk of NGC1068 with a spatial resolution 1.0"x0.7"(50-70pc). We have developed a set of time-dependent chemical models to determine the origin of the C2H gas. A sizeable fraction of the total C2H line emission is detected from the r~1.3kpc starburst (SB) ring. However, the brightest C2H emission originates from a r~200pc off-centered circumnuclear disk (CND), where evidence of a molecular outflow has been previously found in other molecular tracers imaged by ALMA. We also detect significant emission that connects the CND with the outer disk. We derived the fractional abundances of C2H (X(C2H)) assuming LTE conditions. Our estimates range from X(C2H)~a few 10^-8 in the SB ring up to X(C2H)~ a few 10^-7 in the outflow region. PDR models that incorporate gas-grain chemistry are able to account for X(C2H) in the SB ring for moderately dense (n(H2)>10^4 cm^-3) and moderately UV-irradiated gas (UV-field<10xDraine field) in a steady-state regime. However, the high fractional abundances estimated for C2H in the outflow region can only be reached at very early times (T< 10^2-10^3 yr) in models of UV/X-ray irradiated dense gas (n(H2)>10^4-10^5) cm^-3). We interpret that the transient conditions required to fit the high values of X(C2H) in the outflow are likely due to UV/X-ray irradiated non-dissociative shocks associated with the highly turbulent interface between the outflow and the molecular gas in NGC1068.

Molecular transitions as probes of the physical conditions of extragalactic environments

Ab initio grids of time dependent chemical models, varying in gas density, temperature, cosmic ray ionization rate, and radiation field, are used as input to RADEX calculations. Tables of abundances, column densities, theoretical line intensities, and line ratios for some of the most used dense gas tracers are provided. The degree of correlation as well as degeneracy inherent in molecular ratios is discussed. Comparisons of the theoretical intensities with example observations are also provided. We find that, within the parameters space explored, chemical abundances can be constrained by a well defined set of gas density-gas temperature-cosmic ray ionization rate for the species we investigate here. However, line intensities, as well as, more importantly, line ratios, from different chemical models can be very similar leading to a clear degeneracy. We also find that the gas subjected to a galactic cosmic ray ionization rate will not necessarily have reached steady state by 1 Myr. The species most affected by time dependency effects are HCN and CS, both high density tracers. We use our method to fit an example set of data from two galaxies. We find that (i) molecular line ratios can be easily matched even with erroneous individual line intensities; (ii) no set of species can be matched by a one-component ISM; (iii) a species may be a good tracer of an energetic process but only under specific density and temperature conditions. We show that by taking into consideration the chemistry behind each species and the individual line intensities, many degeneracies that arise by just using molecular line ratios can be avoided. Finally we show that using a species or a ratio as a tracer of an individual energetic process (e.g. cosmic rays, UV) ought to be done with caution.

The L1157-B1 astrochemical laboratory: testing the origin of DCN

L1157-B1 is the brightest shocked region of the large-scale molecular outflow, considered the prototype of chemically rich outflows, being the ideal laboratory to study how shocks affect the molecular gas. Several deuterated molecules have been previously detected with the IRAM 30m, most of them formed on grain mantles and then released into the gas phase due to the shock. We aim to observationally investigate the role of the different chemical processes at work that lead to formation the of DCN and test the predictions of the chemical models for its formation. We performed high-angular resolution observations with NOEMA of the DCN(2-1) and H13CN(2-1) lines to compute the deuterated fraction, Dfrac(HCN). We detected emission of DCN(2-1) and H13CN(2-1) arising from L1157-B1 shock. Dfrac(HCN) is ~4x10$^{-3}$ and given the uncertainties, we did not find significant variations across the bow-shock. Contrary to HDCO, whose emission delineates the region of impact between the jet and the ambient material, DCN is more widespread and not limited to the impact region. This is consistent with the idea that gas-phase chemistry is playing a major role in the deuteration of HCN in the head of the bow-shock, where HDCO is undetected as it is a product of grain-surface chemistry. The spectra of DCN and H13CN match the spectral signature of the outflow cavity walls, suggesting that their emission result from shocked gas. The analysis of the time dependent gas-grain chemical model UCL-CHEM coupled with a C-type shock model shows that the observed Dfrac(HCN) is reached during the post-shock phase, matching the dynamical timescale of the shock. Our results indicate that the presence of DCN in L1157-B1 is a combination of gas-phase chemistry that produces the widespread DCN emission, dominating in the head of the bow-shock, and sputtering from grain mantles toward the jet impact region.

TRACING THE EVOLUTION OF HIGH-REDSHIFT GALAXIES USING STELLAR ABUNDANCES

ABSTRACT This paper presents the first results from a model for chemical evolution that can be applied to N-body cosmological simulations and quantitatively compared to measured stellar abundances from large astronomical surveys. This model convolves the chemical yield sets from a range of stellar nucleosynthesis calculations (including asymptotic giant branch stars, Type Ia and II supernovae, and stellar wind models) with a user-specified stellar initial mass function (IMF) and metallicity to calculate the time-dependent chemical evolution model for a “simple stellar population” (SSP) of uniform metallicity and formation time. These SSP models are combined with a semianalytic model for galaxy formation and evolution that uses merger trees from N-body cosmological simulations to track several α- and iron-peak elements for the stellar and multiphase interstellar medium components of several thousand galaxies in the early (z ≥ 6) universe. The simulated galaxy population is then quantitatively compared to two complementary data sets of abundances in the Milky Way stellar halo and is capable of reproducing many of the observed abundance trends. The observed abundance ratio distributions are best reproduced with a Chabrier IMF, a chemically enriched star formation efficiency of 0.2, and a redshift of reionization of 7. Many abundances are qualitatively well matched by our model, but our model consistently overpredicts the carbon-enhanced fraction of stars at low metallicities, likely owing to incomplete coverage of Population III stellar yields and supernova models and the lack of dust as a component of our model.

Chemical features in the circumnuclear disk of the Galactic center

The circumnuclear disk (CND) of the Galactic Center is exposed to many energetic phenomena coming from the supermassive black hole Sgr A* and stellar activities. These energetic activities can affect the chemical composition in the CND by the interaction with UV-photons, cosmic-rays, X-rays, and shock waves. We aim to constrain the physical conditions present in the CND by chemical modeling of observed molecular species detected towards it. We analyzed a selected set of molecular line data taken toward a position in the southwest lobe of the CND with the IRAM 30m and APEX 12-meter telescopes and derived the column density of each molecule using a large velocity gradient (LVG) analysis. The determined chemical composition is compared with a time-dependent gas-grain chemical model based on the UCL\_CHEM code that includes the effects of shock waves with varying physical parameters. Molecules such as CO, HCN, HCO$^+$, HNC, CS, SO, SiO, NO, CN, H$_2$CO, HC$_3$N, N$_2$H$^+$ and H$_3$O$^+$ are detected and their column densities are obtained. Total hydrogen densities obtained from LVG analysis range between $2 \times 10^4$ and $1 \times 10^6\,$cm$^{-3}$ and most species indicate values around several $\times 10^5\,$cm$^{-3}$, which are lower than values corresponding to the Roche limit, which shows that the CND is tidally unstable. The chemical models show good agreement with the observations in cases where the density is $\sim10^4\,$cm$^{-3}$, the cosmic-ray ionization rate is high, $>10^{-15} \,$s$^{-1}$, or shocks with velocities $> 40\,$km s$^{-1}$ have occurred. Comparison of models and observations favors a scenario where the cosmic-ray ionization rate in the CND is high, but precise effects of other factors such as shocks, density structures, UV-photons and X-rays from the Sgr A* must be examined with higher spatial resolution data.

Cosmic Rays and the Origin of Volatiles in Protoplanetary Disks

AbstractThe origin of water and other volatiles in protoplanetary disks can be either interstellar or due to chemical processing during the protoplanetary disk phase. Depending on the strength of the ionization field present during this stage, an active chemical evolution in the protoplanetary disk midplane can lead to formation of complex volatiles on timescales shorter than the disk dissipation timescale. For this reason, we investigate the effects of cosmic rays and the usually neglected cosmic ray induced UV ionization field in time dependent chemical models of protoplanetary disks. These results are benchmarked against our current knowledge of the chemical composition of cometary ices. We conclude that water and other, more complex volatiles can be preserved in the ice mantles of dust grains. This ice mantle growth can also have a significant impact on the dust opacity and hence on the temperature profile of the disk midplane. This effect will be observable in the near future with ALMA.

Time evolution of chemistry with fixed physical parameters in TMC-1

AbstractWe present a set of time dependent chemical evolution models (based on the UMIST† astrochemistry 2012 code, Woodall et al. (2007); McElroy et al. (2013) for a range of initial physical cloud parameters: 10 K &lt; T &lt; 20 K; 103 cm−3 &lt; n(H2) &lt; 5 · 104 cm−3; 1 &lt; AV &lt; 10 and with estimated values of scaled interstellar ultraviolet radiation field. Our computation model included the full UMIST gas-phase reaction network for 467 species Garrod et al. (2008), Graedel et al. (1982). We compare our chemical model results with the relative abundances of: CO, CH, OH, HCO+, HCN, HNC, NH3, N2H+ and H2CO molecules. We find significant time dependent variations of the chemical ratios of: X(NH3/H2); X(HCO+/H2) and X(HCO+/NH3). We derive an ammonia age spread for the parts of TMC-1 (Taurus Molecular Cloud-1) that looks more complex than previous estimated showed. Age estimates based on X(NH3/H2); X(HCO+/H2) and X(HCO+/NH3) were compared in 3 selected positions, and were found to be very similar (with ±9% differences).

Time dependent chemistry in Planck clouds?

AbstractWe present a set of time dependent chemical evolution models (based on the UMIST† astrochemistry 2012 code, McElroy et al. (2013) for a range of initial physical cloud parameters: 10 K &lt; T &lt; 20 K; 103 cm−3 &lt; n(H2) &lt; 5 ⋅ 104 cm−3; 1 &lt; AV &lt; 10 and with estimated values of scaled interstellar ultraviolet radiation field. We compare our chemical model results with the relative abundances of: CO, CH, OH, HCO+, HCN, HNC, NH3, N2H+ and H2CO molecules. We find significant time dependent variations of the chemical ratios of: X(NH3/H2); X(HCO+/H2) and X(HCO+/NH3). The input physical conditions were taken from Fehér O. et al. (2015) at 16 positions along the TMC-1 dark cloud. The NH3 and HCO+ relative densities based on the observations of Fehér O. et al. (2015) help to find the “chemical age” of the given position in the evolution curves.

Mapping CS in starburst galaxies: Disentangling and characterising dense gas

Aims. We observe the dense gas tracer CS in two nearby starburst galaxies to determine how the conditions of the dense gas varies across the circumnuclear regions in starburst galaxies. Methods. Using the IRAM-30m telescope, we mapped the distribution of the CS(2-1) and CS(3-2) lines in the circumnuclear regions of the nearby starburst galaxies NGC 3079 and NGC 6946. We also detected the formaldehyde (H2CO) and methanol (CH3OH) in both galaxies. We marginally detect the isotopologue C34S. Results. We calculate column densities under LTE conditions for CS and CH3OH. Using the detections accumulated here to guide our inputs, we link a time and depth dependent chemical model with a molecular line radiative transfer model; we reproduce the observations, showing how conditions where CS is present are likely to vary away from the galactic centres. Conclusions. Using the rotational diagram method for CH3OH, we obtain a lower limit temperature of 14 K. In addition to this, by comparing the chemical and radiative transfer models to observations, we determine the properties of the dense gas as traced by CS (and CH3OH). We also estimate the quantity of the dense gas. We find that, provided that there are a between 10^5 and 10^6 dense cores in our beam, for both target galaxies, emission of CS from warm (T = 100 - 400 K), dense (n(H2) = 10^5-6 cm-3) cores, possibly with a high cosmic ray ionisation rate (zeta = 100 zeta0) best describes conditions for our central pointing. In NGC 6946, conditions are generally cooler and/or less dense further from the centre, whereas in NGC 3079, conditions are more uniform. The inclusion of shocks allows for more efficient CS formation, leading to an order of magnitude less dense gas being required to replicate observations in some cases.

Isotopic fractionation of carbon, deuterium, and nitrogen: a full chemical study

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.

Upper limits to interstellar NH+and para-NH2−abundances

The understanding of interstellar nitrogen chemistry has improved significantly with recent results from the Herschel Space Observatory. To set even better constraints, we report here on deep searches for the NH+ ground state rotational transition J = 1.5−0.5 of the 2Π1/2 lower spin ladder, with fine-structure transitions at 1013 and 1019 GHz, and the para-NH2− 11,1−00,0 rotational transition at 934 GHz towards Sgr B2 (M) and G10.6−0.4 (W31C) using the Herschel Heterodyne Instrument for the Far-Infrared (HIFI). No clear detections of NH+ are made and the derived upper limits relative to the total number of hydrogen nuclei are ≲2 × 10-12 and ≲7 × 10-13 in the Sgr B2 (M) molecular envelope and in the G10.6−0.4 molecular cloud, respectively. The searches are, however, complicated by the fact that the 1 013 GHz transition lies only −2.5 km s-1 from a CH2NH line, which is seen in absorption in Sgr B2 (M), and that the hyperfine structure components in the 1019 GHz transition are spread over 134 km s-1. Searches for the so far undetected NH2− anion turned out to be unfruitful towards G10.6−0.4, while the para-NH2− 11,1−00,0 transition was tentatively detected towards Sgr B2 (M) at a velocity of 19 km s-1. Assuming that the absorption occurs at the nominal source velocity of +64 km s-1, the rest frequency would be 933.996 GHz, offset by 141 MHz from our estimated value. Using this feature as an upper limit, we found N(p-NH2−) ≲4 × 1011 cm-2, which implies an abundance of ≲8 × 10-13 in the Sgr B2 (M) molecular envelope. The upper limits for both species in the diffuse line-of-sight gas are less than 0.1 to 2% of the values found for NH, NH2, and NH3 towards both sources, and the abundance limits are ≲2−4 × 10-11. An updated pseudo time-dependent chemical model with constant physical conditions, including both gas-phase and surface chemistry, predicts an NH+ abundance a few times lower than our present upper limits in diffuse gas and under typical Sgr B2 (M) envelope conditions. The NH2− abundance is predicted to be several orders of magnitudes lower than our observed limits, hence not supporting our tentative detection. Thus, while NH2− may be very difficult to detect in interstellar space, it could, on the other hand, be possible to detect NH+ in regions where theionisation rates of H2 and N are greatly enhanced.

CHEMODYNAMICAL DEUTERIUM FRACTIONATION IN THE EARLY SOLAR NEBULA: THE ORIGIN OF WATER ON EARTH AND IN ASTEROIDS AND COMETS

Formation and evolution of water in the solar system and the origin of water on Earth constitute one of the most interesting questions in astronomy. The prevailing hypothesis for the origin of water on Earth is by delivery through water-rich small solar system bodies. In this paper, the isotopic and chemical evolution of water during the early history of the solar nebula, before the onset of planetesimal formation, is studied. A gas–grain chemical model that includes multiply deuterated species and nuclear spin-states is combined with a steady-state solar nebula model. To calculate initial abundances, we simulated 1 Myr of evolution of a cold and dark TMC-1-like prestellar core. Two time-dependent chemical models of the solar nebula are calculated over 1 Myr: (1) a laminar model and (2) a model with two-dimensional (2D) turbulent mixing. We find that the radial outward increase of the H2O D/H ratio is shallower in the chemodynamical nebular model than in the laminar model. This is related to more efficient defractionation of HDO via rapid gas-phase processes because the 2D mixing model allows the water ice to be transported either inward and thermally evaporated or upward and photodesorbed. The laminar model shows the Earth water D/H ratio at r ≲ 2.5 AU, whereas for the 2D chemodynamical model this zone is larger, r ≲ 9 AU. Similarly, the water D/H ratios representative of the Oort-family comets, ∼2.5–10 × 10−4, are achieved within ∼2–6 AU and ∼2–20 AU in the laminar and the 2D model, respectively. We find that with regards to the water isotopic composition and the origin of the comets, the mixing model seems to be favored over the laminar model.

Gas-phase CO depletion and N2H+abundances in starless cores

Seven isolated, nearby low-mass starless molecular cloud cores have been observed as part of the Herschel key program Earliest Phases of Star formation (EPoS). By applying a ray-tracing technique to the obtained continuum emission and complementary (sub)mm emission maps, we derive the physical structure (density, dust temperature) of these cloud cores. We present observations of the 12CO, 13CO, and C18O (2-1) and N2H+ (1-0) transitions towards the same cores. Based on the density and temperature profiles, we apply time-dependent chemical and line-radiative transfer modeling and compare the modeled to the observed molecular emission profiles. CO is frozen onto the grains in the center of all cores in our sample. The level of CO depletion increases with hydrogen density and ranges from 46% up to more than 95% in the core centers in the core centers in the three cores with the highest hydrogen density. The average hydrogen density at which 50% of CO is frozen onto the grains is 1.1+-0.4 10^5 cm^-3. At about this density, the cores typically have the highest relative abundance of N2H+. The cores with higher central densities show depletion of N2H+ at levels of 13% to 55%. The chemical ages for the individual species are on average 2+-1 10^5 yr for 13CO, 6+-3 10^4 yr for C18O, and 9+-2 10^4 yr for N2H+. Chemical modeling indirectly suggests that the gas and dust temperatures decouple in the envelopes and that the dust grains are not yet significantly coagulated. We observationally confirm chemical models of CO-freezeout and nitrogen chemistry. We find clear correlations between the hydrogen density and CO depletion and the emergence of N2H+. The chemical ages indicate a core lifetime of less than 1 Myr.

Combined IRAM andHerschel/HIFI study of cyano(di)acetylene in Orion KL: tentative detection of DC3N

We present a study of cyanoacetylene (HC3N) and cyanodiacetylene (HC5N) in Orion KL, through observations from two line surveys performed with the IRAM 30m telescope and the HIFI instrument on board the Herschel telescope. The frequency ranges covered are 80-280 GHz and 480-1906 GHz. We model the observed lines of HC3N, HC5N, their isotopologues (including DC3N), and vibrational modes, using a non-LTE radiative transfer code. To investigate the chemical origin of HC3N and DC3N in Orion KL, we use a time-dependent chemical model. We detect 40 lines of the ground state of HC3N and 68 lines of its 13C isotopologues. We also detect 297 lines of six vibrational modes of this molecule (nu_7, 2nu_7, 3nu_7, nu_6, nu_5, and nu_6+nu_7) and 35 rotational lines of the ground state of HC5N. We report the first tentative detection of DC3N in a giant molecular cloud with a DC3N/HC3N abundance ratio of 0.015. We provide column densities and isotopic and molecular abundances. We also perform a 2x2" map around Orion IRc2 and we present maps of HC3N lines and maps of lines of the HC3N vibrational modes nu_6 and nu_7. In addition, a comparison of our results for HC3N with those in other clouds allows us to derive correlations between the column density, the FWHM, the mass, and the luminosity of the clouds. The high column densities of HC3N obtained in the hot core, make this molecule an excellent tracer of hot and dense gas. In addition, the large frequency range covered reveals the need to consider a temperature and density gradient in the hot core in order to obtain better line fits. The high D/H ratio (comparable to that obtained in cold clouds) that we derive suggests a deuterium enrichment. Our chemical models indicate that the possible deuterated HC3N present in Orion KL is formed during the gas-phase. This fact provides new hints concerning the processes leading to deuteration.

74 MHz Nonthermal Emission from Molecular Clouds: Evidence for a Cosmic Ray Dominated Region at the Galactic Center

We present 74 MHz radio continuum observations of the Galactic center region. These measurements show nonthermal radio emission arising from molecular clouds that is unaffected by free–free absorption along the line of sight. We focus on one cloud, G0.13-0.13, representative of the population of molecular clouds that are spatially correlated with steep spectrum (α(327MHz)(74MHz) = 1.3 ± 0.3) nonthermal emission from the Galactic center region. This cloud lies adjacent to the nonthermal radio filaments of the Arc near l 0.2° and is a strong source of 74 MHz continuum, SiO (2-1), and Fe I Kα 6.4 keV line emission. This three-way correlation provides the most compelling evidence yet that relativistic electrons, here traced by 74 MHz emission, are physically associated with the G0.13-0.13 molecular cloud and that low-energy cosmic ray electrons are responsible for the Fe I Kα line emission. The high cosmic ray ionization rate 10(–1)3 s(–1) H(–1) is responsible for heating the molecular gas to high temperatures and allows the disturbed gas to maintain a high-velocity dispersion. Large velocity gradient (LVG) modeling of multitransition SiO observations of this cloud implies H2 densities 10(4–5) cm(–3) and high temperatures. The lower limit to the temperature of G0.13-0.13 is 100 K, whereas the upper limit is as high as 1000 K. Lastly, we used a time-dependent chemical model in which cosmic rays drive the chemistry of the gas to investigate for molecular line diagnostics of cosmic ray heating. When the cloud reaches chemical equilibrium, the abundance ratios of HCN/HNC and N2H+/HCO+ are consistent with measured values. In addition, significant abundance of SiO is predicted in the cosmic ray dominated region of the Galactic center. We discuss different possibilities to account for the origin of widespread SiO emission detected from Galactic center molecular clouds.

WIDESPREAD METHANOL EMISSION FROM THE GALACTIC CENTER: THE ROLE OF COSMIC RAYS

We report the discovery of a widespread population of collisionally excited methanol J = 4_{-1} to 3$_0 E sources at 36.2 GHz from the inner 66'x18' (160x43 pc) of the Galactic center. This spectral feature was imaged with a spectral resolution of ~16.6 km/s taken from 41 channels of a VLA continuum survey of the Galactic center region. The revelation of 356 methanol sources, most of which are maser candidates, suggests a large abundance of methanol in the gas phase in the Galactic center region. There is also spatial and kinematic correlation between SiO (2--1) and CH3OH emission from four Galactic center clouds: the +50 and +20 km/s clouds and G0.13-0.13 and G0.25+0.01. The enhanced abundance of methanol is accounted for in terms of induced photodesorption by cosmic rays as they travel through a molecular core, collide, dissociate, ionize, and excite Lyman Werner transitions of H2. A time-dependent chemical model in which cosmic rays drive the chemistry of the gas predicts CH3OH abundance of 10^{-8} to 10^{-7} on a chemical time scale of 5x10^4 to 5x10^5 years. The average methanol abundance produced by the release of methanol from grain surfaces is consistent with the available data.