O-bearing Species Research Articles

The complexity of Orion: an ALMA view

We report the first detection and high angular resolution (1.8" $\times$ 1.1") imaging of acetic acid (CH$_3$COOH) and gGg$^{\prime}$--ethylene glycol (gGg$^{\prime}$(CH$_2$OH)$_2$) towards the Orion Kleinmann--Low nebula. The observations were carried out at $\sim$1.3mm with ALMA during the Cycle~2. A notable result is that the spatial distribution of the acetic acid and ethylene glycol emission differs from that of the other O-bearing molecules within Orion-KL. Indeed, while the typical emission of O-bearing species harbors a morphology associated with a "V-shape" linking the Hot Core region to the Compact Ridge (with an extension towards the BN object), that of acetic acid and ethylene glycol mainly peaks at about 2" southwest from the hot core region (near sources I and n). We find that the measured CH$_3$COOH:aGg$^{\prime}$(CH$_2$OH)$_2$ and CH$_3$COOH:gGg$^{\prime}$(CH$_2$OH)$_2$ ratios differ from the ones measured towards the low-mass protostar IRAS 16293--2422 by more than one order of magnitude. Our best hypothesis to explain these findings is that CH$_3$COOH, aGg$^{\prime}$(CH$_2$OH)$_2$ and gGg$^{\prime}$(CH$_2$OH)$_2$ are formed on the icy-surface of grains and then released into the gas-phase, via co-desorption with water, due to a bullet of matter ejected during the explosive event that occurred in the heart of the Nebula about 500-700 years ago.

Resolving the chemical substructure of Orion-KL(Corrigendum)

The Kleinmann-Low nebula in Orion (Orion-KL) is the nearest example of a high-mass star-forming environment. For the first time, we complemented 1.3 mm Submillimeter Array (SMA) interferometric line survey with IRAM 30 m single-dish observations of the Orion-KL region. Covering a 4 GHz bandwidth in total, this survey contains over 160 emission lines from 20 species (25 isotopologues), including 11 complex organic molecules (COMs). At a spatial resolution of 1200 AU, the continuum substructures are resolved. Extracting the spectra from individual substructures and providing the intensity-integrated distribution map for each species, we studied the small-scale chemical variations in this region. Our main results are: (1) We identify lines from the low-abundance COMs CH3COCH3 and CH3CH2OH, as well as tentatively detect CH3CHO and long carbon-chains C6H and HC7N. (2) We find that while most COMs are segregated by type, peaking either towards the hot core (e.g., N-bearing species) or the compact ridge (e.g., O-bearing species like HCOOCH3 and CH3OCH3), while the distributions of others do not follow this segregated structure (e.g., CH3CH2OH, CH3OH, CH3COCH3). (3) We find a second velocity component of HNCO, SO2, 34SO2, and SO lines, which may be associated with a strong shock event in the low-velocity outflow. (4) Temperatures and molecular abundances show large gradients between central condensations and the outflow regions, illustrating a transition between hot molecular core and shock-chemistry dominated regimes. Our observations of spatially resolved chemical variations in Orion-KL provide the nearest reference source for hot molecular core and outflow chemistry, which will be an important example for interpreting the chemistry of more distant HMSFRs.

Searching for trans ethyl methyl ether in Orion KL.

We report on the tentative detection of trans ethyl methyl ether (tEME), t-CH3CH2OCH3, through the identification of a large number of rotational lines from each one of the spin states of the molecule towards Orion KL. We also search for gauche-trans-n-propanol, Gt-n-CH3CH2CH2OH, an isomer of tEME in the same source. We have identified lines of both species in the IRAM 30 m line survey and in the ALMA Science Verification data. We have obtained ALMA maps to establish the spatial distribution of these species. Whereas tEME mainly arises from the compact ridge component of Orion, Gt-n-propanol appears at the emission peak of ethanol (south hot core). The derived column densities of these species at the location of their emission peaks are ≤(4.0 ± 0.8) × 1015 cm-2 and ≤(1.0 ± 0.2)× 1015 cm-2 for tEME and Gt-n-propanol, respectively. The rotational temperature is ~100 K for both molecules. We also provide maps of CH3OCOH, CH3CH2OCOH, CH3OCH3, CH3OH, and CH3CH2OH to compare the distribution of these organic saturated O-bearing species containing methyl and ethyl groups in this region. Abundance ratios of related species and upper limits to the abundances of non-detected ethers are provided. We derive an abundance ratio N(CH3OCH3)/N(tEME) ≥ 150 in the compact ridge of Orion.

HERSCHELOBSERVATIONS OF EXTRAORDINARY SOURCES: ANALYSIS OF THE HIFI 1.2 THz WIDE SPECTRAL SURVEY TOWARD ORION KL II. CHEMICAL IMPLICATIONS

We present chemical implications arising from spectral models fit to the Herschel/HIFI spectral survey toward the Orion Kleinmann-Low nebula (Orion KL). We focus our discussion on the eight complex organics detected within the HIFI survey utilizing a novel technique to identify those molecules emitting in the hottest gas. In particular, we find the complex nitrogen bearing species CH_3CN, C_2H_3CN, C_2H_5CN, and NH_2CHO systematically trace hotter gas than the oxygen bearing organics CH_3OH, C_2H_5OH, CH_3OCH_3, and CH_3OCHO, which do not contain nitrogen. If these complex species form predominantly on grain surfaces, this may indicate N-bearing organics are more difficult to remove from grain surfaces than O-bearing species. Another possibility is that hot (T_(kin) ~ 300 K) gas phase chemistry naturally produces higher complex cyanide abundances while suppressing the formation of O-bearing complex organics. We compare our derived rotation temperatures and molecular abundances to chemical models, which include gas-phase and grain surface pathways. Abundances for a majority of the detected complex organics can be reproduced over timescales ≳10^5 years, with several species being underpredicted by less than 3σ. Derived rotation temperatures for most organics, furthermore, agree reasonably well with the predicted temperatures at peak abundance. We also find that sulfur bearing molecules that also contain oxygen (i.e., SO, SO_2, and OCS) tend to probe the hottest gas toward Orion KL, indicating the formation pathways for these species are most efficient at high temperatures.

CONSTRAINING THE ABUNDANCES OF COMPLEX ORGANICS IN THE INNER REGIONS OF SOLAR-TYPE PROTOSTARS

The high abundances of Complex Organic Molecules (COMs) with respect to methanol, the most abundant COM, detected towards low-mass protostars, tend to be underpredicted by astrochemical models. This discrepancy might come from the large beam of the single-dish telescopes, encompassing several components of the studied protostar, commonly used to detect COMs. To address this issue, we have carried out multi-line observations of methanol and several COMs towards the two low-mass protostars NGC1333-IRAS2A and -IRAS4A with the Plateau de Bure interferometer at an angular resolution of 2 arcsec, resulting in the first multi-line detection of the O-bearing species glycolaldehyde and ethanol and of the N-bearing species ethyl cyanide towards low-mass protostars other than IRAS 16293. The high number of detected transitions from COMs (more than 40 methanol transitions for instance) allowed us to accurately derive the source size of their emission and the COMs column densities. The COMs abundances with respect to methanol derived towards IRAS2A and IRAS4A are slightly, but not substantitally, lower than those derived from previous single-dish observations. The COMs abundance ratios do not vary significantly with the protostellar luminosity, over five orders of magnitude, implying that low-mass hot corinos are quite chemically rich as high-mass hot cores. Astrochemical models still underpredict the abundances of key COMs, such as methyl formate or di-methyl ether, suggesting that our understanding of their formation remains incomplete.

Antifreeze in the hot core of Orion

Comparison of their chemical compositions shows, to first order, a good agreement between the cometary and interstellar abundances. However, a complex O-bearing organic molecule, ethylene glycol (CH$_{2}$OH)$_{2}$, seems to depart from this correlation because it was not easily detected in the interstellar medium although it proved to be rather abundant with respect to other O-bearing species in comet Hale-Bopp. Ethylene glycol thus appears, together with the related molecules glycolaldehyde CH$_{2}$OHCHO and ethanol CH$_{3}$CH$_{2}$OH, as a key species in the comparison of interstellar and cometary ices as well as in any discussion on the formation of cometary matter. We focus here on the analysis of ethylene glycol in the nearest and best studied hot core-like region, Orion-KL. We use ALMA interferometric data because high spatial resolution observations allow us to reduce the line confusion problem with respect to single-dish observations since different molecules are expected to exhibit different spatial distributions. Furthermore, a large spectral bandwidth is needed because many individual transitions are required to securely detect large organic molecules. Confusion and continuum subtraction are major issues and have been handled with care. We have detected the aGg' conformer of ethylene glycol in Orion-KL. The emission is compact and peaks towards the Hot Core close to the main continuum peak, about 2" to the south-west; this distribution is notably different from other O-bearing species. Assuming optically thin lines and local thermodynamic equilibrium, we derive a rotational temperature of 145 K and a column density of 4.6 10$^{15}$ cm$^{-2}$. The limit on the column density of the gGg' conformer is five times lower.

Acetone in Orion BN/KL

As one of the prime targets of interstellar chemistry study, Orion BN/KL clearly shows different molecular distributions between large nitrogen- (e.g., C2H5CN) and oxygen-bearing (e.g., HCOOCH3) molecules. However, acetone (CH3)2CO, a special complex O-bearing molecule, has been shown to have a very different distribution from other typical O-bearing molecules in the BN/KL region. We searched for acetone within our IRAM Plateau de Bure Interferometer 3 mm and 1.3 mm data sets. Twenty-two acetone lines were searched within these data sets. The angular resolution ranged from 1.8 X 0.8 to 6.0 X 2.3 arcsec^2, and the spectral resolution ranged from 0.4 to 1.9 km s-1. Nine of the acetone lines appear free of contamination. Three main acetone peaks (Ace-1, 2, and 3) are identified in Orion BN/KL. The new acetone source Ace-3 and the extended emission in the north of the hot core region have been found for the first time. An excitation temperature of about 150 K is determined toward Ace-1 and Ace-2, and the acetone column density is estimated to be 2-4 X 10^16 cm-2 with a relative abundance of 1-6 X 10^-8 toward these two peaks. Acetone is a few times less abundant toward the hot core and Ace-3 compared with Ace-1 and Ace-2. We find that the overall distribution of acetone in BN/KL is similar to that of N-bearing molecules, e.g., NH3 and C2H5CN, and very different from those of large O-bearing molecules, e.g., HCOOCH3 and (CH3)2O. Our findings show the acetone distribution is more extended than in previous studies and does not originate only in those areas where both N-bearing and O-bearing species are present. Moreover, because the N-bearing molecules may be associated with shocked gas in Orion BN/KL, this suggests that the formation and/or destruction of acetone may involve ammonia or large N-bearing molecules in a shocked-gas environment.

PHOSPHORUS CHEMISTRY IN THE SHOCKED REGION L1157 B1

We study the evolution of phosphorous-bearing species in one-dimensional C-shock models. We find that the abundances of P-bearing species depend sensitively on the elemental abundance of P in the gas phase and on the abundance of N atoms in the pre-shock gas. The observed abundance of PN and the non-detection of PO towards L1157 B1 are reproduced in C-shock models with shock velocity v=20km s-1 and pre-shock density n(H2) =10^4 - 10^5, if the elemental abundance of P in the gas phase is 10^-9 and the N-atom abundance is n(N)/nH - 10^-5 in the pre-shock gas. We also find that P-chemistry is sensitive to O- and N-chemistry, because N atoms are destroyed mainly by OH and NO. We identify the reactions of O-bearing and N-bearing species that significantly affect P chemistry.

OBSERVATIONAL CONSTRAINTS ON METHANOL PRODUCTION IN INTERSTELLAR AND PREPLANETARY ICES

Methanol (CH3OH) is thought to be an important link in the chain of chemical evolution that leads from simple diatomic interstellar molecules to complex organic species in protoplanetary disks that may be delivered to the surfaces of Earthlike planets. Previous research has shown that CH3OH forms in the interstellar medium predominantly on the surfaces of dust grains. To enhance our understanding of the conditions that lead to its efficient production, we assemble a homogenized catalog of published detections and limiting values in interstellar and preplanetary ices for both CH3OH and the other commonly observed C- and O-bearing species, H2O, CO, and CO2. We use this catalog to investigate the abundance of ice-phase CH3OH in environments ranging from dense molecular clouds to circumstellar envelopes around newly born stars of low and high mass. Results show that CH3OH production arises during the CO freezeout phase of ice-mantle growth in the clouds, after an ice layer rich in H2O and CO2 is already in place on the dust, in agreement with current astrochemical models. The abundance of solid-phase CH3OH in this environment is sufficient to account for observed gas-phase abundances when the ices are subsequently desorbed in the vicinity of embedded stars. CH3OH concentrations in the ices toward embedded stars show order-of-magnitude object-to-object variations, even in a sample restricted to stars of low mass associated with ices lacking evidence of thermal processing. We hypothesize that the efficiency of CH3OH production in dense cores and protostellar envelopes is mediated by the degree of prior CO depletion.

Analysis on Binding Energy and Auger Parameter for Estimating Size and Stoichiometry of ZnO Nanorods

ZnO nanorods prepared through chemical vapor deposition technique are characterized by microscopic and X-ray photoelectron spectroscopy (XPS) techniques to correlate the effects of size on the binding energy of Zn 2p3/2 photoelectrons. A positive shift in Zn 2p3/2-binding energy as compared to that in bulk ZnO is assumed to be the effect of size of ZnO tips. The shift in binding energy has been explained in terms of relaxation energy in the photoemission process. Simultaneously, Auger parameter of the nanorods is evaluated for stoichiometric composition. The extra peak in O1s spectrum of nanorods is explained as adsorbed O-bearing species or surface contaminants.

HIGH-RESOLUTION EXPANDED VERY LARGE ARRAY IMAGE OF DIMETHYL ETHER (CH 3 ) 2 O IN ORION-KL

We report the first sub-arc second (0.65$\arcsec$ $\times$ 0.51$\arcsec$) image of the dimethyl ether molecule, (CH$_{3}$)$_{2}$O, toward the Orion Kleinmann-Low nebula (Orion--KL). The observations were carried at 43.4 GHz with the Expanded Very Large Array (EVLA). The distribution of the lower energy transition 6$_{1,5} - 6_{0,6}$, EE (E$\rm_{u}$ = 21 K) mapped in this study is in excellent agreement with the published dimethyl ether emission maps imaged with a lower resolution. The main emission peaks are observed toward the Compact Ridge and Hot Core southwest components, at the northern parts of the Compact Ridge and in an intermediate position between the Compact Ridge and the Hot Core. A notable result is that the distribution of dimethyl ether is very similar to that of another important larger O-bearing species, the methyl formate (HCOOCH$_{3}$), imaged at lower resolution. Our study shows that higher spectral resolution (WIDAR correlator) and increased spectral coverage provided by the EVLA offer new possibilities for imaging complex molecular species. The sensitivity improvement and the other EVLA improvements make this instrument well suited for high sensitivity, high angular resolution, molecular line imaging.

A molecular survey of outflow gas: velocity-dependent shock chemistry and the peculiar composition of the EHV gas

(Abridged) We present a molecular survey of the outflows powered by L1448-mm and IRAS 04166+2706, two sources with prominent wing and extremely high velocity (EHV) components in their CO spectra. The molecular composition of the two outflows presents systematic changes with velocity that we analyze by dividing the outflow in three chemical regimes, two of them associated with the wing component and the other the EHV gas. The analysis of the two wing regimes shows that species like H2CO and CH3OH favor the low-velocity gas, while SiO and HCN are more abundant in the fastest gas. We also find that the EHV regime is relatively rich in O-bearing species, as is not only detected in CO and SiO (already reported elsewhere), but also in SO, CH3OH, and H2CO (newly reported here), with a tentative detection in HCO+. At the same time, the EHV regime is relatively poor in C-bearing molecules like CS and HCN. We suggest that this difference in composition arises from a lower C/O ratio in the EHV gas. The different chemical compositions of the wing and EHV regimes suggest that these two outflow components have different physical origins. The wing component is better explained by shocked ambient gas, although none of the existing shock models explains all observed features. The peculiar composition of the EHV gas may reflect its origin as a dense wind from the protostar or its surrounding disk.

Degradation of C 2–C 15 volatile organic compounds in a landfill cover soil

The composition of non-methane volatile organic compounds (hereafter VOCs) in i) the cover soil, at depths of 30, 50 and 70 cm, and ii) gas recovery wells from Case Passerini landfill site, (Florence, Italy) was determined by GC-MS. The study, based on the analysis of interstitial gases sampled along vertical profiles within the cover soil, was aimed to investigate the VOC behaviour as biogas transits from a reducing to a relatively more oxidizing environment. A total of 48 and 63 different VOCs were identified in the soil and well gases, respectively. Aromatics represent the dominant group (71.5% of total VOC) in soil gases, followed by alkanes (6.8%), ketones (5.7%), organic acids (5.2%), aldehydes (3.0%), esters (2.6%), halogenated compounds (2.1%) and terpenes (1.3%). Cyclics, heterocyclics, S-bearing compounds and phenols are ≤ 1%. In the wells the VOC composition is characterized by higher concentrations of cyclic (7.6%) and S-bearing compounds (2%) and lower concentrations of O-bearing compounds. The vertical distribution of VOCs in the cover soil shows significant variations: alkanes, aromatics and cyclics decrease at decreasing depth, whereas an inverse trend is displayed by the O-bearing species. Total VOC and CH 4 concentrations at a depth of 30 cm in the soil are comparable, inferring that microbial activity is likely affecting VOCs at a very minor extent with respect to CH 4. According to these considerations, to assess the biogas emission impact, usually carried out on the sole basis of CO 2 and CH 4 emission rates, the physical–chemical behaviour of VOCs in the cover soil, regulating the discharge of these highly contaminant compounds in ambient air, has to be taken into account. The soil vertical distribution of these species can be used to better evaluate the efficiency of oxidative capability of intermediate and final covers.

Reactive conversion of polycrystalline SnO2 into single-crystal nanofiber arrays at low oxygen partial pressure

Single-crystal SnO2 nanofibers have been formed from SnO2 polycrystals via reaction at low oxygen partial pressures. Polycrystalline SnO2 disks coated with Au nanoparticles were exposed to humid H2/N2 at 700 to 800 °C. Single-crystal SnO2 nanofibers formed beneath Au nanoparticles, with the nanofiber length oriented parallel to the [100] crystallographic direction of SnO2. Because this simple process does not require either a separate source of a Sn–O-bearing vapor species located upstream of the substrate or a temperature gradient, single-crystal nanofibers may be formed on large area SnO2-bearing substrates.

Oxygen Chemistry in the Circumstellar Envelope of the Carbon‐Rich Star IRC +10216

In this paper we study the oxygen chemistry in the C-rich circumstellar shells of IRC +10216. The recent discoveries of oxygen-bearing species (water, hydroxyl radical, and formaldehyde) toward this source challenge our current understanding of the chemistry in C-rich circumstellar envelopes. The presence of icy comets surrounding the star or catalysis on iron grain surfaces have been invoked to explain the presence of such unexpected species. This detailed study aims at evaluating the chances of producing O-bearing species in the C-rich circumstellar envelope only by gas-phase chemical reactions. For the hot inner envelope we show that although most of the oxygen is locked in CO near the photosphere (as expected for a C/O ratio greater than 1), for radial distances larger than ~15 stellar radii, species such as H2O and CO2 have a large abundance under the assumption of thermochemical equilibrium. It is also shown how non-LTE chemistry makes the CO → H2O, CO2 transformation predicted in LTE very difficult. Concerning the chemistry in the colder, outer envelope, we show that formaldehyde can be formed through gas-phase reactions. However, in order to form water vapor, it is necessary to include a radiative association between atomic oxygen and molecular hydrogen with quite a high rate constant. The chemical models explain the presence of HCO+ and predict the existence of SO and H2CS (which has been detected in a 3 mm line survey to be published). We have modeled the line profiles of H2CO, H2O, HCO+, SO, and H2CS using a nonlocal radiative transfer model and the abundance profiles predicted by our chemical model. The results have been compared to the observations and discussed.

Detection of a hot core in the intermediate-mass Class 0 protostar NGC 7129–FIRS 2

We report high angular resolution (HPBW ∼ 0.6 �� × 0.5 �� at 1.3 mm) observations of the Class 0 intermediate-mass (IM) protostar NGC 7129- FIRS 2 using the Plateau de Bure Interferometer. Our observations show the existence of an intense unresolved source in the continuum at 1.3 mm and 3 mm at the position of the Class 0 object. In addition, compact CH3CN emission is detected at this position. The high rotational temperature derived from the CH3CN lines (Trot ≈ 50 K), as well as the enhanced CH3CN fractional abundance (X(CH3CN) ∼ 7.0×10 −9 ), shows the existence of a hot core in this IM young stellar object. This is to our knowledge the first IM hot core detected so far. Interferometric maps of the region in the CH3OH 5kk� →4kkand D2CO 404→303 lines are also presented in this paper. The methanol emission presents two condensations, one associated with the hot core, which was very intense in the high upper state energy lines (Eu > 100 K), and the other associated with the bipolar outflow which dominates the emission in the low excitation lines. Enhanced CH3OH abundances (X(CH3OH) ∼ 3 × 10 −8 -af ew 10 −7 ) were measured in both components. While intense D2CO 404 → 303 emission was detected towards the hot core, the N2D + 3 → 2 line was not detected in our interferometric observations. The different behaviors of D2CO and N2D + emissions suggest different formation mechanisms for the two species and different deuteration processes for H2CO and N2H + (surface and gas-phase chemistry, respectively). Finally, the spectrum of the large bandwidth correlator shows a forest of lines at the hot core position, revealing that this object is extraordinarily rich in complex molecules. For deeper insight into the chemistry of complex molecules, we compared the fractional abundances of the complex O- and N- bearing species in FIRS 2 with those in hot corinos and massive hot cores. Within the large uncertainty involved in fractional abundance estimates towards hot cores, we did not detect any variation in the relative abundances of O- and N-bearing molecules ((CH3CN)/(CH3OH)) with the hot core luminosity. However, the O-bearing species H2CO and HCOOH seemed to be more abundant in low and intermediate mass stars than in massive star-forming regions. We propose that this could be the consequence of a different grain mantle composition in low and massive star-forming regions.

Univariant Three- and Four-Phase Vaporization Equilibria in the Ternary Mn−Te−O System: A High-Temperature Mass Spectrometric Study of Binary xMnO + (1 − x)TeO2 with x ≥ 0.5

High-temperature mass spectrometric studies on xMnO + (1 − x)TeO2 samples with x = 0.50, 0.54, 0.57, 0.67, 0.75, and 0.79 were conducted to investigate the vaporization behavior of the MnO−TeO2 binary system. Along with MnTeO3, a phase of equimolar composition, another ternary phase Mn3TeO6 lying on the oxygen-rich side of the MnO−TeO2 binary line was generated during preparations as well as during isothermal dynamic effusion experiments. Experiments were also conducted by adding a known excess of MnO or Mn to aliquots from different samples to examine whether the resulting condensed phase−vapor phase equilibrium would preclude or at least retard the buildup of Mn3TeO6. On the contrary, these experiments, many being characterized by high Te2(g) evolution in the initial stages, yielded residues of MnTeO3 + Mn3TeO6 or Mn3O4 + Mn3TeO6, the latter when the MnO addition was such that the resulting overall x(MnO) was as high as 0.80. The vapor phase in all cases consisted only of Te- and O-bearing species: TeO2, TeO, Te2, and O2. These observations led to the inference that the MnO-rich region of the MnO + TeO2 system is not inclined to remain binary during vaporization. Anomalous vaporization behavior was observed for Te2(g) in some isothermal experiments. While for all other gaseous species monotonic decrease in partial pressures ended with values stabilizing around the respective minimum, that in the p(Te2) ended with a turn-around in its value; there was a rapid increase to eventually stabilize at a value that was not only about four times higher than the minimum but also even higher than that measured before the onset of monotonic decrease. These features and other aspects associated with different univariant vaporization equilibria in the Mn−Te−O ternary system are discussed.

Chemical Evolution of the Circumstellar Envelopes of Carbon‐rich Post–Asymptotic Giant Branch Objects

We have observed, with the 30 m IRAM telescope, the Caltech Submillimeter Observatory telescope, and the Infrared Space Observatory (ISO) satellite, 3 the rotational lines of CO at millimeter, submillimeter, and far-IR wavelengths in the direction of carbon-rich stellar objects at different stages of evolution: CRL 2688 (a very young proto–planetary nebula), CRL 618 (a proto–planetary nebula), and NGC 7027 (a young planetary nebula). Several changes in the longwave emission of CO and other molecules are discussed here in relation with the degree of evolution of the objects. In the early stages, represented by CRL 2688, the longwave emission is dominated by CO lines. In the intermediate stage, e.g., CRL 618, very fast outflows are present which, together with the strong UV field from the central star, dissociate CO. The released atomic oxygen is seen via its atomic lines and allows the formation of new O-bearing species, such as H2O and OH. The abundance of HNC is enhanced with respect to HCN as a result of the chemical processes occurring in the photodissociation region. At this stage, CO lines and [O i] lines are the dominant coolants, while the cooling effect of [C ii] is rising. At the planetary nebula stage, e.g., NGC 7027, large parts of the old CO AGB material have been reprocessed. The spectrum is then dominated by atomic and ionic lines. New species, such as CH + , appear. Water has probably been reprocessed in OH. Subject headings: infrared: stars — line: identification — planetary nebulae: individual (CRL 618, CRL 2688, NGC 7027) — stars: abundances — stars: carbon — stars: evolution

Vibrational spectroscopy of ion-irradiated ices

In the last 20 years we have studied some effects induced by fast ions (E∼keV-MeV) impinging on solid materials (mainly ices) with a view to their astrophysical relevance. The main techniques used have been infrared and Raman spectroscopy. Here we review some of the results obtained so far concerning, in particular, the formation of new species not present in the original sample. When hydrocarbons are an important constituent of the target ion irradiation gives rise also to a refractory residue which is left over after warming up. In addition we present some preliminary results of a new study, still in progress, on the infrared properties of the organic residue formed after irradiation of an icy mixture with H-, C-, N- and O-bearing species. Furthermore we present the micro-Raman spectra of some fragments of Orgueil, a carbonaceous chondrite meteorite. Some astrophysical applications of these laboratory results are also discussed.

O-bearing Molecules in Carbon-rich Proto-Planetary Objects.

We present Infrared Space Observatory long-wavelength spectrometer observations of the proto-planetary nebula CRL 618, a star evolving very fast toward the planetary nebula stage. In addition to the lines of 12CO, 13CO, HCN, and HNC, we report on the detection of H2O and OH emission together with the fine-structure lines of [O i] at 63 and 145 µm. The abundance of the latter three species relative to 12CO are 4x10-2, 8x10-4, and 4.5 (approximate value) in the regions where they are produced. We suggest that O-bearing species other than CO are produced in the innermost region of the circumstellar envelope. The UV photons from the central star photodissociate most of the molecular species produced in the asymptotic giant branch (AGB) phase and allow a chemistry dominated by standard ion-neutral reactions. They not only allow these reactions for the formation of O-bearing species but also modify the abundances of C-rich molecules like HCN and HNC for which we found an abundance ratio of approximately 1, which is much lower than in AGB stars. The molecular abundances in the different regions of the circumstellar envelope have been derived from radiative transfer models and from our knowledge of its physical structure.