Chemistry Of Dense Clouds Research Articles

A Yebes W-band Line Survey towards an Unshocked Molecular Cloud of Supernova Remnant 3C 391: Evidence of Cosmic-Ray-Induced Chemistry

Cosmic rays (CRs) have strong influences on the chemistry of dense molecular clouds (MCs). To study the detailed chemistry induced by CRs, we conducted a Yebes W-band line survey towards an unshocked MC (which we named 3C391:NML) associated with supernova remnant 3C 391. We detected emission lines of 18 molecular species in total and estimated their column densities with local thermodynamic equilibrium (LTE) and non-LTE analysis. Using the abundance ratio N(HCO+)/N(CO) and an upper limit of N(DCO+)/N(HCO+), we estimated that the CR ionization rate of 3C391:NML is ζ ≳ 2.7 × 10−14 s−1 with an analytic method. However, we caution against adopting this value because chemical equilibrium, which is a prerequisite of using the equations, is not necessarily reached in 3C391:NML. We observed lower N(HCO+)/N(HOC+), higher N(HCS+)/N(CS), and higher X(l-C3H+) by an order of magnitude in 3C391:NML than the typical values in quiescent dense MCs. We found that an enhanced CR ionization rate (of order ∼10−15 or ∼10−14 s−1) is needed to reproduce the observation with a chemical model. This is higher than the values found in typical MCs by 2–3 orders of magnitude.

Formation of Al containing molecular complexes in the gas phase in dense molecular clouds: quantum study of the radiative association of Al++H2 and Al++D2

ABSTRACT Radiative association (RA) of Al+ with H2 is the first step in the formation of AlH in gas phase and is here investigated theoretically. We use recent potential energy and dipole moment surfaces and a quantum approach based on the driven equations formalism for performing the dynamics for both the Al+-H2 and Al+-D2 systems. The obtained RA rate coefficients are compared with previous evaluations based on transition state theory and found to be orders of magnitude larger. They are also compared to those obtained recently for the similar systems Na+-H2/D2. The possible role played by RA of Al+ with H2 in the gas phase chemistry of dense molecular clouds is discussed.

New Bistable Solutions in Molecular Cloud Chemistry: Nitrogen and Carbon Autocatalysis

Abstract We have investigated the chemistry of dense interstellar clouds and found new bistable solutions in the nitrogen and carbon chemistries. We identify the autocatalytic processes that are present in the pure, reduced, chemical networks and find, as previously found for oxygen chemistry, that He+ plays an important role. The applicability of these results to astronomical environments is briefly discussed. The bistable solutions found for carbon chemistry occur for low densities and high ionization fractions that are not compatible with those found in cold, dense clouds. Bistability in the pure nitrogen chemistry occurs for conditions that are relevant for prestellar cores in which significant CO depletion has taken place. We conclude that several autocatalyses are embedded in gas-phase interstellar chemistry and that many more are potentially present.

Astrochemical Bistability: Autocatalysis in Oxygen Chemistry

Abstract The origin of bistable solutions in the kinetic equations describing the chemistry of dense interstellar clouds is explained as being due to the autocatalysis and feedback of oxygen nuclei from the oxygen dimer (O2). We identify four autocatalytic processes that can operate in dense molecular clouds, driven respectively by reactions of H+, He+, C+, and S+ with O2. We show that these processes can produce the bistable solutions found in previous studies, as well as the dependence on various model parameters such as the helium ionization rate, the sulfur depletion and the electron recombination rate. We also show that ion–grain neutralizations are unlikely to affect the occurrence of bistability in dense clouds. It is pointed out that many chemical models of astronomical sources should have the potential to show bistable solutions.

Desorption of N2, CO, CH4, and CO2 from interstellar carbonaceous dust analogues

ABSTRACTThe interaction of volatile species with carbonaceous interstellar dust analogues is of relevance in the chemistry and physics of dense clouds in the interstellar medium. Two deposits of hydrogenated amorphous carbon (HAC), with different morphologies and aromatic versus aliphatic ratio in their structure, have been grown to model interstellar dust. The interaction of N2, CO, CH4, and CO2 with these two surfaces has been investigated using thermal programmed desorption (TPD). Desorption energy distributions were obtained by analysing TPD spectra for one monolayer coverage with the Polanyi–Wigner equation. The desorption energies found in this work for N2, CO, and CH4 are larger by 10–20 per cent than those reported in the literature for siliceous or amorphous solid water surfaces. Moreover, the experiments suggest that the interaction of the volatiles with the aromatic substructure of HAC is stronger than that with the aliphatic part. Desorption of CO2 from the HAC surfaces follows zero-order kinetics, reflecting the predominance of CO2–CO2 interactions. A model simulation of the heating of cold cloud cores shows that the volatiles considered in this work would desorb sequentially from carbonaceous dust surfaces with desorption times ranging from hundreds to tens of thousands of years, depending on the molecule and on the mass of the core.

Revised models of interstellar nitrogen isotopic fractionation

Nitrogen-bearing molecules in cold molecular clouds exhibit a range of isotopic fractionation ratios and these molecules may be the precursors of $^{15}$N enrichments found in comets and meteorites. Chemical model calculations indicate that atom-molecular ion and ion-molecule reactions could account for most of the fractionation patterns observed. However, recent quantum-chemical computations demonstrate that several of the key processes are unlikely to occur in dense clouds. Related model calculations of dense cloud chemistry show that the revised $^{15}$N enrichments fail to match observed values. We have investigated the effects of these reaction rate modifications on the chemical model of Wirstr\"{o}m et al. (2012) for which there are significant physical and chemical differences with respect to other models. We have included $^{15}$N fractionation of CN in neutral-neutral reactions and also updated rate coefficients for key reactions in the nitrogen chemistry. We find that the revised fractionation rates have the effect of suppressing $^{15}$N enrichment in ammonia at all times, while the depletion is even more pronounced, reaching $^{14}$N/$^{15}$N ratios of >2000. Taking the updated nitrogen chemistry into account, no significant enrichment occurs in HCN or HNC, contrary to observational evidence in dark clouds and comets, although the $^{14}$N/$^{15}$N ratio can still be below 100 in CN itself. However, such low CN abundances are predicted that the updated model falls short of explaining the bulk $^{15}$N enhancements observed in primitive materials. It is clear that alternative fractionating reactions are necessary to reproduce observations, so further laboratory and theoretical studies are urgently needed.

INTERSTELLAR SIMULATIONS USING A UNIFIED MICROSCOPIC-MACROSCOPIC MONTE CARLO MODEL WITH A FULL GAS-GRAIN NETWORK INCLUDING BULK DIFFUSION IN ICE MANTLES

We have designed an improved algorithm that enables us to simulate the chemistry of cold dense interstellar clouds with a full gas-grain reaction network. The chemistry is treated by a unified microscopic-macroscopic Monte Carlo approach that includes photon penetration and bulk diffusion. To determine the significance of these two processes, we simulate the chemistry with three different models. In Model 1, we use an exponential treatment to follow how photons penetrate and photodissociate ice species throughout the grain mantle. Moreover, the products of photodissociation are allowed to diffuse via bulk diffusion and react within the ice mantle. Model 2 is similar to Model 1 but with a slower bulk diffusion rate. A reference Model 0, which only allows photodissociation reactions to occur on the top two layers, is also simulated. Photodesorption is assumed to occur from the top two layers in all three models. We found that the abundances of major stable species in grain mantles do not differ much among these three models, and the results of our simulation for the abundances of these species agree well with observations. Likewise, the abundances of gas-phase species in the three models do not vary. However, the abundances of radicals in grain mantles can differ by up to two orders of magnitude depending upon the degree of photon penetration and the bulk diffusion of photodissociation products. We also found that complex molecules can be formed at temperatures as low as 10 K in all three models.

The chemistry of planet-forming regions is not interstellar.

Advances in infrared and submillimeter technology have allowed for detailed observations of the molecular content of the planet-forming regions of protoplanetary disks. In particular, disks around solar-type stars now have growing molecular inventories that can be directly compared with both prestellar chemistry and that inferred for the early solar nebula. The data directly address the old question of whether the chemistry of planet-forming matter is similar or different and unique relative to the chemistry of dense clouds and protostellar envelopes. The answer to this question may have profound consequences for the structure and composition of planetary systems. The practical challenge is that observations of emission lines from disks do not easily translate into chemical concentrations. Here, we present a two-dimensional radiative transfer model of RNO 90, a classical protoplanetary disk around a solar-mass star, and retrieve the concentrations of dominant molecular carriers of carbon, oxygen and nitrogen in the terrestrial region around 1 AU. We compare our results to the chemical inventory of dense clouds and protostellar envelopes, and argue that inner disk chemistry is, as expected, fundamentally different from prestellar chemistry. We find that the clearest discriminant may be the concentration of CO2, which is extremely low in disks, but one of the most abundant constituents of dense clouds and protostellar envelopes.

Fundamental vibrational transitions of hydrogen chloride detected in CRL 2136

We would like to understand the chemistry of dense clouds and their hot cores more quantitatively by obtaining more complete knowledge of the chemical species present in them. We have obtained high-resolution infrared absorption spectroscopy at 3-4 um toward the bright infrared source CRL 2136. The fundamental vibration-rotation band of HCl has been detected within a dense cloud for the first time. The HCl is probably located in the warm compact circumstellar envelope or disk of CRL 2136. The fractional abundance of HCl is (4.9-8.7)e-8, indicating that approximately 20 % of the elemental chlorine is in gaseous HCl. The kinetic temperature of the absorbing gas is 250 K, half the value determined from infrared spectroscopy of 13CO and water. The percentage of chlorine in HCl is approximately that expected for gas at this temperature. The reason for the difference in temperatures between the various molecular species is unknown.

Using deuterated H 3 + and other molecular species to understand the formation of stars and planets

The ion plays a key role in the chemistry of dense interstellar gas clouds where stars and planets are forming. The low temperatures and high extinctions of such clouds make direct observations of impossible, but lead to large abundances of H 2 D + and D 2 H + that are very useful probes of the early stages of star and planet formation. Maps of H 2 D + and D 2 H + pure rotational line emission towards star-forming regions show that the strong deuteration of is the result of near-complete molecular depletion of CNO-bearing molecules onto grain surfaces, which quickly disappears as cores warm up after stars have formed. In the warmer parts of interstellar gas clouds, transfers its proton to other neutrals such as CO and N 2 , leading to a rich ionic chemistry. The abundances of such species are useful tracers of physical conditions such as the radiation field and the electron fraction. Recent observations of HF line emission towards the Orion Bar imply a high electron fraction, and we suggest that observations of OH + and H 2 O + emission may be used to probe the electron density in the nuclei of external galaxies.

Upper limit for the D2H+ortho-to-para ratio in the prestellar core 16293E (CHESS)

The H3+ ion plays a key role in the chemistry of dense interstellar gas clouds where stars and planets are forming. The low temperatures and high extinctions of such clouds make direct observations of H3+ impossible, but lead to large abundances of H2D+ and D2H+, which are very useful probes of the early stages of star and planet formation. The ground-state rotational ortho-D2H+ 111-000 transition at 1476.6 GHz in the prestellar core 16293E has been searched for with the Herschel/HIFI instrument, within the CHESS (Chemical HErschel Surveys of Star forming regions) Key Program. The line has not been detected at the 21 mK km/s level (3 sigma integrated line intensity). We used the ortho-H2D+ 110-111 transition and para-D2H+ 110-101 transition detected in this source to determine an upper limit on the ortho-to-para D2H+ ratio as well as the para-D2H+/ortho-H2D+ ratio from a non-LTE analysis. The comparison between our chemical modeling and the observations suggests that the CO depletion must be high (larger than 100), with a density between 5e5 and 1e6 cm-3. Also the upper limit on the ortho-D2H+ line is consistent with a low gas temperature (~ 11 K) with a ortho-to-para ratio of 6 to 9, i.e. 2 to 3 times higher than the value estimated from the chemical modeling, making it impossible to detect this high frequency transition with the present state of the art receivers.

Does the H+5 hydrogen cluster exist in dense interstellar clouds?

AbstractThe clustering of hydrogen molecules around a cation in dense interstellar clouds is examined taking into account recent accurate information about the structure and thermochemistry of these clusters. In general, these clustering processes are not important due to the small probability of occurrence of radiative association at low densities. However, the long lived metastable complex (H)* makes the concentration of the H clusters to be of the same order of the concentration of H in these media. This result may have considerable implications for the chemistry of dense interstellar clouds. © 2012 Wiley Periodicals, Inc.

A KINETIC DATABASE FOR ASTROCHEMISTRY (KIDA)

We present a novel chemical database for gas-phase astrochemistry. Named the KInetic Database for Astrochemistry (KIDA), this database consists of gas-phase reactions with rate coefficients and uncertainties that will be vetted to the greatest extent possible. Submissions of measured and calculated rate coefficients are welcome, and will be studied by experts before inclusion into the database. Besides providing kinetic information for the interstellar medium, KIDA is planned to contain such data for planetary atmospheres and for circumstellar envelopes. Each year, a subset of the reactions in the database (kida.uva) will be provided as a network for the simulation of the chemistry of dense interstellar clouds with temperatures between 10 K and 300 K. We also provide a code, named Nahoon, to study the time-dependent gas-phase chemistry of 0D and 1D interstellar sources.

ON THE FORMATION OF INTERSTELLAR WATER ICE: CONSTRAINTS FROM A SEARCH FOR HYDROGEN PEROXIDE ICE IN MOLECULAR CLOUDS

Recent surface chemistry experiments have shown that the hydrogenation of molecular oxygen on interstellar dust grains is a plausible formation mechanism, via hydrogen peroxide (H2O2), for the production of water (H2O) ice mantles in the dense interstellar medium. Theoretical chemistry models also predict the formation of a significant abundance of H2O2 ice in grain mantles by this route. At their upper limits, the predicted and experimental abundances are sufficiently high that H2O2 should be detectable in molecular cloud ice spectra. To investigate this further, laboratory spectra have been obtained for H2O2/H2O ice films between 2.5 and 200 micron, from 10 to 180 K, containing 3%, 30%, and 97% H2O2 ice. Integrated absorbances for all the absorption features in low-temperature H2O2 ice have been derived from these spectra. For identifying H2O2 ice, the key results are the presence of unique features near 3.5, 7.0, and 11.3 micron. Comparing the laboratory spectra with the spectra of a group of 24 protostars and field stars, all of which have strong H2O ice absorption bands, no absorption features are found that can definitely be identified with H2O2 ice. In the absence of definite H2O2 features, the H2O2 abundance is constrained by its possible contribution to the weak absorption feature near 3.47 micron found on the long-wavelength wing of the 3 micron H2O ice band. This gives an average upper limit for H2O2, as a percentage of H2O, of 9% +/- 4%. This is a strong constraint on parameters for surface chemistry experiments and dense cloud chemistry models.

First hyperfine resolved far-infrared OH spectrum from a star-forming region

OH is an important molecule in the H2O chemistry and the cooling budget of star-forming regions. The goal of the Herschel key program `Water in Star-forming regions with Herschel' (WISH) is to study H2O and related species during protostellar evolution. Our aim in this letter is to assess the origin of the OH emission from star-forming regions and constrain the properties of the emitting gas. High-resolution observations of the OH 2Pi1/2 J = 3/2-1/2 triplet at 1837.8 GHz (163.1 micron) towards the high-mass star-forming region W3 IRS 5 with the Heterodyne Instrument for the Far-Infrared (HIFI) on Herschel reveal the first hyperfine velocity-resolved OH far-infrared spectrum of a star-forming region. The line profile of the OH emission shows two components: a narrow component (FWHM approx. 4-5 km/s) with partially resolved hyperfine structure resides on top of a broad (FWHM approx. 30 km/s) component. The narrow emission agrees well with results from radiative transfer calculations of a spherical envelope model for W3 IRS 5 with a constant OH abundance of approx. 8e-9. Comparison with H2O yields OH/H2O abundance ratios of around 1e-3 for T > 100 K and around unity for T < 100K, consistent with the current picture of the dense cloud chemistry with freeze-out and photodesorption. The broad component is attributed to outflow emission. An abundance ratio of OH/H2O > 0.028 in the outflow is derived from comparison with results of water line modeling. This ratio can be explained by a fast J-type shock or a slower UV-irradiated C-type shock.

Polycyclic Aromatic Hydrocarbons in Dense Cloud Chemistry

Virtually all detailed gas-phase models of the chemistry of dense interstellar clouds exclude polycyclic aromatic hydrocarbons (PAHs). This omission is unfortunate because from the few studies that have been done on the subject, it is known that the inclusion of PAHs can affect the gas-phase chemistry strongly. We have added PAHs to our network to determine the role they play in the chemistry of cold dense cores. Initially, only the chemistry of neutral and negatively charged PAH species was considered, since it was assumed that positively charged PAHs are of little importance. Subsequently, this assumption was checked and confirmed. In the models presented here, we include radiative attachment to form PAH−, mutual neutralization between PAH anions and small positively charged ions, and photodetachment. We also test the sensitivity of our results to changes in the size and abundance of the PAHs. Our results confirm that the inclusion of PAHs changes many of the calculated abundances of smaller species considerably. In TMC-1, the general agreement with observations is significantly improved, unlike in L134N. This may indicate a difference in PAH properties between the two regions. With the inclusion of PAHs in dense cloud chemistry, high-metal elemental abundances give a satisfactory agreement with observations. As a result, we do not need to decrease the observed elemental abundances of all metals, and we do not need to vary the elemental C/O ratio in order to produce large abundances of carbon species in TMC-1 (CP).

Chemical sensitivity to the ratio of the cosmic-ray ionization rates of He and H2in dense clouds

Aim: To determine whether or not gas-phase chemical models with homogeneous and time-independent physical conditions explain the many observed molecular abundances in astrophysical sources, it is crucial to estimate the uncertainties in the calculated abundances and compare them with the observed abundances and their uncertainties. Non linear amplification of the error and bifurcation may limit the applicability of chemical models. Here we study such effects on dense cloud chemistry. Method: Using a previously studied approach to uncertainties based on the representation of rate coefficient errors as log normal distributions, we attempted to apply our approach using as input a variety of different elemental abundances from those studied previously. In this approach, all rate coefficients are varied randomly within their log normal (Gaussian) distribution, and the time-dependent chemistry calculated anew many times so as to obtain good statistics for the uncertainties in the calculated abundances. Results: Starting with so-called ``high-metal'' elemental abundances, we found bimodal rather than Gaussian like distributions for the abundances of many species and traced these strange distributions to an extreme sensitivity of the system to changes in the ratio of the cosmic ray ionization rate zeta\_He for He and that for molecular hydrogen zeta\_H2. The sensitivity can be so extreme as to cause a region of bistability, which was subsequently found to be more extensive for another choice of elemental abundances. To the best of our knowledge, the bistable solutions found in this way are the same as found previously by other authors, but it is best to think of the ratio zeta\_He/zeta\_H2 as a control parameter perpendicular to the ''standard'' control parameter zeta/n\_H.

Temperature variable ion trap studies of C3Hn+ with H2 and HD

Hydrogenation and deuteration of C3+, C3H+, C3H2+ in collisions with H2 and HD has been studied from room temperature down to 10 K using a 22-pole ion trap. Although exothermic, hydrogenation of C3+ is rather slow at room temperature but becomes faster with decreasing temperature. In addition to the increasing lifetime of the collision complex this behavior may be caused by the floppy structure of C3+ and the freezing of soft bending modes below 50 K. For C3(+) + HD it has been shown that production of C3D+ is slightly favored over C3H+ formation. The controversy over which products are really formed in C3H(+) + H2 collisions and deuterated variants has a long history. Previous and new ion trap results prove that formation of C3H2(+) + H is not endothermic but rather fast, in contradiction to erroneous conclusions from flow tube experiments and ab initio calculations. In addition the reaction shows a complicated isotope dependence, most probably caused by the influence of zero point energies in entrance and exit transition states. For example hydrogen abstraction with HD is faster than with H2 while radiative association is slower. The most surprising result has been obtained for C3H(+) + HD. Here C3HD+ formation is over one hundred times faster than C3H2+. In addition to the details of the potential energy surface it may be that in this case an H-HD exchange reaction takes place via an open-chain propargyl cation intermediate (H2CCCH+). Reactions of C3H2+ and C3H3+ with H2 are very slow but, due to the unique sensitivity of the trapping technique, significant rate coefficients have been determined. The presented results are of fundamental importance for understanding the energetics, structures and reaction dynamics of the deuterated variant of the C3Hn+ collision system. They indicate that the previous quantum chemical calculations are not accurate enough for understanding the low energy behavior of the Cn,Hm+ reaction systems. The laboratory experiments are of essential relevance for the carbon chemistry of dense interstellar clouds, both for formation of small hydrocarbons and deuterium fractionation.

Probing the Nature of Grain Surface- and Photo-Chemistry by Laboratory Simulation

AbstractThe experimental results that have been obtained in simulation experiments of grain surface- and photochemistry are reviewed, and ways to include these in models of dense cloud chemistry are indicated.

Thermal desorption of water ice in the interstellar medium

Water (H2O) ice is an important solid constituent of many astrophysical environments. To comprehend the role of such ices in the chemistry and evolution of dense molecular clouds and comets, it is necessary to understand the freeze-out, potential surface reactivity, and desorption mechanisms of such molecular systems. Consequently, there is a real need from within the astronomical modelling community for accurate empirical molecular data pertaining to these processes. Here we give the first results of a laboratory programme to provide such data. Measurements of the thermal desorption of H2O ice, under interstellar conditions, are presented. For ice deposited under conditions that realistically mimic those in a dense molecular cloud, the thermal desorption of thin films (~50 molecular layers) is found to occur with zero order kinetics characterised by a surface binding energy, E_{des}, of 5773 +/- 60 K, and a pre-exponential factor, A, of 10^(30 +/- 2) molecules cm^-2 s^-1. These results imply that, in the dense interstellar medium, thermal desorption of H2O ice will occur at significantly higher temperatures than has previously been assumed.