Interstellar cyanomethane

We have made an observational study of the newly identified cyanomethane radical CH2CN and the possibly related species CH3CN with the goals of (1) elucidating the possible role of reactions of the type CnHm(+) + N in astrochemistry, and (2) providing a possible test of Bates's models of dissociative electron recombination. We find a remarkably different abundance ratio CH2CN/CH3CN in TMC-1 and Sgr B2, which we deduce is a result of the large difference in temperature of these objects. Studies of CH2CN and CH3CN in other sources, including two new detections of CH2CN, support this conclusion and are consistent with a monotonic increase in the CH2CN/CH3CN ratio with decreasing temperature over the range 10-120 K. This behavior may be explained by the destruction of CH2CN by reaction with O. If this reaction does not proceed, then CH2CN and CH3CN are concluded to form via different chemical pathways. Thus, they do not provide a test of Bates's conjectures (they do not both form from CH3CNH+). CH2CN is then likely to form via C2H4(+) + N --> CH2CNH+, thus demonstrating the viability of this important reaction in astrochemistry. The T dependence of the CH2CN/CH3CN ratio would then reflect the increasing rate of the C2H4(+) + N reaction with decreasing temperature.     

Calculations concerning interstellar isomeric abundance ratios for C3H and C3H2

The syntheses of interstellar c-C3H2, H2CCC, c-C3H, and HCCC, where "c" stands for the cyclic isomer, are thought to proceed via dissociative recombination of the precursor ions c-C3H3+ and H2CCCH+, which are themselves produced mainly via the radiative association reaction between C3H+ and H2. We have utilized ab initio methods to study the potential energy surface (PES) for the association of the linear ion C3H+ and H2 to form the isomers c-C3H3+ and H2CCCH+. The overall rate coefficient for radiative association has been calculated as a function of temperature via the phase space method. Our ab initio calculations show that the H2CCCH+ isomer is formed directly without an activation barrier from reactants, and that isomerization between the two isomers can occur readily via a low-energy pathway consisting of two transition states (saddle points on the PES) and one intermediate (local minimum on the PES). Calculations of the equilibrium coefficient for the isomerization H2CCCH+ <-> c-C3H3+ as a function of energy shows that equal abundances of these two ions should be produced as relaxation proceeds, in agreement with experimental measurements at high pressure. Our results confirm the important point that a simple ion-molecule association reaction can produce a cyclic hydrocarbon. If dissociative recombination reactions involving c-C3H3+ and H2CCCH+ maintain the carbon skeletal structure of the ions and produce roughly similar C3H/C3H2 branching ratios, then abundance ratios of unity are produced between the cyclic and noncyclic isomers of C3H and C3H2 via this mechanism. The large abundance ratio of c-C3H2 to H2CCC observed in TMC-1 can then be explained by differential destruction rates.     

Cyanide and isocyanide abundances in the cold, dark cloud TMC-1

We have observed emission from HCN, H13CN, HC15N, HN13C, H15NC, HC3N, CH3CN, and possibly CH3NC, and determined an upper limit for NH2CN, toward the cold, dark cloud TMC-1. The abundance ratio [HNC]/[HCN] = 1.55 +/- 0.16 is at least a factor approximately 4 and approximately 100 greater than that observed toward the giant molecular clouds DR 21(OH) and Orion KL, respectively. In contrast, for the corresponding methylated isomers we obtain [CH3NC]/CH3CN] < or approximately 0.1. We also find [NH2CN]/[CH3CN] < or approximately 0.1 and [HC3N]/[CH3CN] = 30 +/- 10. We find no evidence for anomalous hyperfine ratios for H13CN, indicating that the ratios for HCN (cf. recent work of Walmsley et al.) are the result of self-absorption by cold foreground gas.     

C-type shocks in the interstellar medium: profiles of CH+ and CH absorption lines

We have computed optical absorption-line profiles of CH⁺ and CH, as predicted by a model of a C-type shock propagating in a diffuse interstellar cloud. Both these species are produced in the shock wave in the reaction sequence that is initiated by C⁺(H₂, H)CH⁺. Whilst CH⁺ flows at the ion speed, CH, which forms in the dissociative recombination reaction CH⁺₃(e⁻, H₂)CH, flows at a speed which is intermediate between those of the ions and the neutrals. The predicted velocity shift between the CH⁺ and CH line profiles is found to be no more than approximately 2 km s⁻¹, which is smaller than has previously been assumed. We also investigate OH and HCO⁺, finding that the correlation between their column densities, recently observed in the diffuse interstellar medium, can be reproduced by the model.     

Extraterrestrial amino acids identified in metal‐rich CH and CB carbonaceous chondrites from Antarctica

Carbonaceous chondrites contain numerous indigenous organic compounds and could have been an important source of prebiotic compounds required for the origin of life on Earth or elsewhere. Extraterrestrial amino acids have been reported in five of the eight groups of carbonaceous chondrites and are most abundant in CI, CM, and CR chondrites but are also present in the more thermally altered CV and CO chondrites. We report the abundance, distribution, and enantiomeric and isotopic compositions of simple primary amino acids in six metal‐rich CH and CB carbonaceous chondrites that have not previously been investigated for amino acids: Allan Hills (ALH) 85085 (CH3), Pecora Escarpment (PCA) 91467 (CH3), Patuxent Range (PAT) 91546 (CH3), MacAlpine Hills (MAC) 02675 (CBb), Miller Range (MIL) 05082 (CB), and Miller Range (MIL) 07411 (CB). Amino acid abundances and carbon isotopic values were obtained by using both liquid chromatography time‐of‐flight mass spectrometry and fluorescence, and gas chromatography isotope ratio mass spectrometry. The δ¹³C/¹²C ratios of multiple amino acids fall outside of the terrestrial range and support their extraterrestrial origin. Extracts of CH chondrites were found to be particularly rich in amino acids (13–16 parts per million, ppm) while CB chondrite extracts had much lower abundances (0.2–2 ppm). The amino acid distributions of the CH and CB chondrites were distinct from the distributions observed in type 2 and 3 CM and CR chondrites and contained elevated levels of β‐, γ‐, and δ‐amino acids compared to the corresponding α‐amino acids, providing evidence that multiple amino acid formation mechanisms were important in CH and CB chondrites.     

Ferrous silicate spherules with euhedral iron‐nickel metal grains from CH carbonaceous chondrites: Evidence for supercooling and condensation under oxidizing conditions

Abstract— The CH carbonaceous chondrites contain a population of ferrous (Fe/(Fe + Mg) ? 0.1‐0.4) silicate spherules (chondrules), about 15–30 μm in apparent diameter, composed of cryptocrystalline olivinepyroxene normative material, ±SiO₂‐rich glass, and rounded‐to‐euhedral Fe, Ni metal grains. The silicate portions of the spherules are highly depleted in refractory lithophile elements (CaO, Al₂O₃, and TiO₂ <0.04 wt%) and enriched in FeO, MnO, Cr₂O₃, and Na₂O relative to the dominant, volatile‐poor, magnesian chondrules from CH chondrites. The Fe/(Fe + Mg) ratio in the silicate portions of the spherules is positively correlated with Fe concentration in metal grains, which suggests that this correlation is not due to oxidation, reduction, or both of iron (FeO_sil ? Fe_met) during melting of metal‐silicate solid precursors. Rather, we suggest that this is a condensation signature of the precursors formed under oxidizing conditions. Each metal grain is compositionally uniform, but there are significant intergrain compositional variations: about 8–18 wt% Ni, <0.09 wt% Cr, and a sub‐solar Co/Ni ratio. The precursor materials of these spherules were thus characterized by extreme elemental fractionations, which have not been observed in chondritic materials before. Particularly striking is the fractionation of Ni and Co in the rounded‐to‐euhedral metal grains, which has resulted in a Co/Ni ratio significantly below solar. The liquidus temperatures of the euhedral Fe, Ni metal grains are lower than those of the coexisting ferrous silicates, and we infer that the former crystallized in supercooled silicate melts. The metal grains are compositionally metastable; they are not decomposed into taenite and kamacite, which suggests fast postcrystallization cooling at temperatures below 970 K and lack of subsequent prolonged thermal metamorphism at temperatures above 400–500 K.     

Abundances of ethylene oxide and acetaldehyde in hot molecular cloud cores.

We have searched for millimetre-wave line emission from ethylene oxide (c-C2H4O) and its structural isomer acetaldehyde (CH3CHO) in 11 molecular clouds using SEST. Ethylene oxide and acetaldehyde were detected through multiple lines in the hot cores NGC 6334F, G327.3-0.6, G31.41+0.31, and G34.3+0.2. Acetaldehyde was also detected towards G10.47+0.03, G322.2+0.6, and Orion 3'N, and one ethylene oxide line was tentatively detected in G10.47+0.03. Column densities and rotational excitation temperatures were derived using a procedure which fits the observed line intensifies by finding the minimum chi 2-value. The resulting rotational excitation temperatures of ethylene oxide and acetaldehyde are in the range 16-38 K, indicating that these species are excited in the outer, cooler parts of the hot cores or that the excitation is significantly subthermal. For an assumed source size of 20", the deduced column densities are (0.6-1)x10(14) cm-2 for ethylene oxide and (2-5)x10(14) cm-2 for acetaldehyde. The fractional abundances with respect to H2 are X[c-C2H4O]=(2-6)xl0(-10), and X[CH3CHO]=(0.8-3)x10(-9). The ratio X[CH3CHO]/X[c-C2H4O] varies between 2.6 (NGC 6334F) and 8.5 (G327.3-0.6). We also detected and analysed multiple transitions of CH3OH, CH3OCH3, C2H5OH, and HCOOH. The chemical, and possibly evolutionary, states of NGC 6334F, G327.3-0.6, G31.41+0.31, and G34.3+0.2 seem to be very similar.     

Detection of a new interstellar molecular ion, H2COH+ (protonated formaldehyde)

A new interstellar molecular ion, H2COH+ (protonated formaldehyde), has been detected toward Sgr B2, Orion KL, W51, and possibly in NGC 7538 and DR21(OH). Six transitions were detected in Sgr B2(M). The 1(1,0)-1(0,1) transition was detected in all sources listed above. Searches were also made toward the cold, dark clouds TMC-1 and L134N, Orion (3N, 1E), and a red giant, IRC + 10216, without success. The excitation temperatures of H2COH+ are calculated to be 60-110 K, and the column densities are on the order of 10(12)-10(14) cm-2 in Sgr B2, Orion KL, and W51. The fractional abundance of H2COH+ is on the order of 10(-11) to 10-(9), and the ratio of H2COH+ to H2CO is in the range 0.001-0.5 in these objects. The values in Orion KL seem to be consistent with the "early time" values of recent model calculations by Lee, Bettens, & Herbst, but they appear to be higher than the model values in Sgr B2 and W51 even if we take the large uncertainties of column densities of H2CO into account. We suggest production routes starting from CH3OH may play an important role in the formation of H2COH+.     

Calculations concerning the HCO+/HOC+ abundance ratio in dense interstellar clouds

Calculations have been performed to determine the rate coefficients of several reactions involved in both the formation and depletion of interstellar HCO+ and HOC+. The abundance of HOC+ deduced from these calculations is consistent with the tentative identification of HOC+ in Sgr B2 by Woods et al. The large HCO+/HOC+ abundance ratio observed by Woods et al. is due at least in part to a more rapid formation rate for HCO+ and probably due as well as to a more rapid depletion rate for HOC+.     

Variations in the HCN/HNC abundance ratio in the Orion molecular cloud

We have used observations of the rare isotopes of HCN and HNC to determine the relative abundance of these two chemical isomers along the central ridge of the Orion molecular cloud. The abundance ratio [HCN]/[HNC] decreases by more than an order of magnitude from the relatively warm plateau and hot core sources toward the KL nebula to the colder, more quiescent clouds to the north and south. Even in the cooler regions, however, the ratio is an order of magnitude larger than that found in previous investigations of cold dark clouds. We determine the kinetic temperature in the regions we have studied from new observations of methylacetylene (CH3CCH), together with other recent estimates of the gas temperature near KL. The results suggest that the warmer portions of the cloud are dominated by different chemical pathways than those in the general interstellar cloud material.     

Ion-molecule calculation of the abundance ratio of CCD to CCH in dense interstellar clouds

Laboratory measurements and calculations have been performed to determine the abundance ratio of the deuterated ethynyl radical (CCD) to the normal radical (CCH) which can be achieved in dense interstellar clouds via isotopic fractionation in the C2H2+ (HD) = C2HD+ (H2) system of reactions. According to this limited treatment, the CCD/CCH abundance ratio which can be attained is in the range 0.02-0.03 for the Orion molecular cloud and 0.01-0.02 for TMC-1. These ranges of numbers are in reasonable agreement with the observed values in Orion and TMC-1. However, the analysis of the CCD/CCH abundance ratio is complicated via the presence of competing fractionation mechanisms, especially in the low-temperature source TMC-1.     

Calculations of ion-molecule deuterium fractionation reactions involving HD

Gas-phase chemical models of deuterium fractionation in dense interstellar clouds utilize a small number of exothermic reactions to achieve fractionation. Although HD is a major repository of deuterium, it appears not to exchange deuterium with many molecular ions. Useful semiquantitative reasons have been given for the unusual lack of reactivity of exothermic ion-HD deuterium exchange systems, but quantum chemical studies are needed to understand these ideas in more detail and to determine if the lack of reactivity pertains at very low temperatures not studied in the laboratory, or whether tunneling can drive the reactions. Accordingly, the potential energy surfaces of three representative ion-molecule exchange reactions involving protonated ions (H3+, CH3+, HCO+) and HD have been investigated with ab initio quantum chemical techniques. Our results generally confirm the semiquantitative picture as to which reactions are likely to occur and show that tunneling at low temperatures is unlikely to alter this picture.     

A reanalysis of the HCO+/HOC+ abundance ratio in dense interstellar clouds

New theoretical and experimental results have prompted a reinvestigation of the HCO+/HOC+ abundance ratio in dense interstellar clouds. These results pertain principally but not exclusively to the reaction between HOC+ and H2, which was previously calculated by DeFrees, McLean, and Herbst to possess a large activation energy barrier. New calculations, reported here, indicate that this activation energy barrier is quite small and may well be zero. In addition, experimental results at higher energy and temperature indicate strongly that the reaction proceeds efficiently at interstellar temperatures. If HOC+ does indeed react efficiently with H2 in interstellar clouds, the calculated HCO+/HOC+ abundance ratio rises to substantially greater value under standard dense cloud conditions than in deduced via the tentative observation of HOC+ in Sgr B2.     

Ultra-high-resolution observations of CH in Southern Molecular Cloud envelopes

We present a mini-survey of ultrahigh-resolution spectroscopy (UHRS) of CH towards three southern molecular cloud envelopes. The sightlines are selected to probe physically similar gas in different Galactic environments. With a velocity resolution of ∼0.5 km s⁻¹  ( R =575 000)  these observations resolve most kinematic components of the absorption lines. We do, however, detect one line component in the Lupus region, which is not resolved and for which an upper limit of   b <0.3 km s^-1  is found. We find a correlation between distance of the absorbing gas from the Galactic mid-plane and the fractional abundance of CH. We show that this correlation can be explained as being a result of a fall-off in the ultraviolet radiation field intensity and propose that CH observations in carefully selected sightlines might allow a mapping of the variations in the interstellar radiation field.     

Refractory inclusions in the CH/CB‐like carbonaceous chondrite Isheyevo: I. Mineralogy and petrography

Abstract— –The CH/CB‐like chondrite Isheyevo consists of metal‐rich (70–90 vol% Fe,Ni‐metal) and metal‐poor (7–20 vol% Fe,Ni‐metal) lithologies which differ in size and relative abundance of Fe,Ni‐metal and chondrules, as well as proportions of porphyritic versus non‐porphyritic chondrules. Here, we describe the mineralogy and petrography of Ca,Al‐rich inclusions (CAIs) and amoeboid olivine aggregates (AOAs) in these lithologies. Based on mineralogy, refractory inclusions can be divided into hibonite‐rich (39%), grossite‐rich (16%), melilite‐rich (19%), spinel‐rich (14%), pyroxene‐anorthite‐rich (8%), fine‐grained spinel‐rich CAIs (1%), and AOAs (4%). There are no systematic differences in the inclusion types or their relative abundances between the lithologies. About 55% of the Isheyevo CAIs are very refractory (hibonite‐rich and grossite‐rich) objects, 20–240 μm in size, which appear to have crystallized from rapidly cooling melts. These inclusions are texturally and mineralogically similar to the majority of CAIs in CH and CB chondrites. They are distinctly different from CAIs in other carbonaceous chondrite groups dominated by the spinel‐pyroxene ± melilite CAIs and AOAs. The remaining 45% of inclusions are less refractory objects (melilite‐, spinel‐ and pyroxene‐rich CAIs and AOAs), 40–300 μm in size, which are texturally and mineralogically similar to those in other chondrite groups. Both types of CAIs are found as relict objects inside porphyritic chondrules indicating recycling during chondrule formation. We infer that there are at least two populations of CAIs in Isheyevo which appear to have experienced different thermal histories. All of the Isheyevo CAIs apparently formed at an early stage, prior to chondrule formation and prior to a hypothesized planetary impact that produced magnesian cryptocrystalline and skeletal chondrules and metal grains in CB, and possibly CH chondrites. However, some of the CAIs appear to have undergone melting during chondrule formation and possibly during a major impact event. We suggest that Isheyevo, as well as CH and CB chondrites, consist of variable proportions of materials produced by different processes in different settings: 1) by evaporation, condensation, and melting of dust in the protoplanetary disk (porphyritic chondrules and refractory inclusions), 2) by melting, evaporation and condensation in an impact generated plume (magnesian cryptocrystalline and skeletal chondrules and metal grains; some igneous CAIs could have been melted during this event), and 3) by aqueous alteration of pre‐existing planetesimals (heavily hydrated lithic clasts). The Isheyevo lithologies formed by size sorting of similar components during accretion in the Isheyevo parent body; they do not represent fragments of CH and CB chondrites.     

Shock chemistry in the molecular clouds associated with SNR IC 443

Several interstellar molecules have been detected toward the highly perturbed B and G clouds associated with the supernova remnant IC 443 via their 3 mm transitions, including N2H+, SiO, SO, CN, HNC, and H13CO+. The (J, K) = (1, 1) and (2, 2) inversion lines of metastable ammonia have also been observed, as well as the J = 3-2 transition of HCO+ at 1.2 mm. Analysis of the (1, 1) and (2, 2) inversion lines of NH3 indicates minimum gas kinetic temperatures of TK = 70 K toward cloud B, and TK = 33 K in cloud G. Modeling of the J = 1-0 and J = 3-2 transitions of HCO+ implies densities greater than 10(5) cm-3 toward both positions. These data clearly show that hot and dense material is present in IC 443, and they suggest the presence of shocks in both regions. A careful analysis of the HCO+ lines indicates that the HCO+ abundance is at most enhanced by factors of a few over that found in cold, quiescent gas. This conclusion contradicts past claims of HCO+ abundance enhancements of several orders of magnitude in the perturbed regions. The N2H+ abundance was also found to be similar to that in cold gas, suggesting that there is no increase in ionization in the clouds. The abundances of SO and CS, as well as CN and NH3, do not appear to differ significantly from those found in cold dark clouds, although chemistry models predict sulfur-containing species to undergo high-temperature enhancements. SiO, however, is found to have an abundance in the perturbed gas 100 times larger than the upper limits observed in the dark cloud TMC 1, a result in agreement with high temperature chemistry models. In addition, the HNC/HCN ratio in both IC 443 B and G was found to be approximately 0.1--far from the ratio of 1 predicted by low-temperature ion-molecule chemistry, but similar to the values observed in clouds where elevated temperatures are present.     

Identification of the interstellar cyanomethyl radical (CH2CN) in the molecular clouds TMC-1 and Sagittarius B2

We report the astronomical identification of the cyanomethyl radical, CH2CN, the heaviest nonlinear molecular radical to be identified in interstellar clouds. The complex fine and hyperfine structures of the lowest rotational transitions at about 20.12 and 40.24 GHz are resolved in TMC-1, where the abundance appears to be about 5 x 10(-9) relative to that of H2. This is significantly greater than the observed abundance of CH3CN (methyl cyanide) in TMC-1. In Sgr B2 the hyperfine structure is blended in the higher frequency transitions at 40, 80, and 100 GHz, although the spin-rotation doubling is clearly evident. Preliminary searches in other sources indicate that the distribution of CH2CN is similar to that for such carbon chain species as HC3N or C4H.     

A search for HCCN in molecular clouds

We have conducted a deep search for HCCN towards the dark cloud TMC-l and several GMC's via its N(J) = 1(2)-->0(1) transition. HCCN was not detected in any of these sources. Towards TMC-l, assuming optically thin emission, the total column density upper limit is NHCCN < or = 2 x 10(12) cm-2, which corresponds to a fractional abundance upper limit with respect to molecular hydrogen of fHCCN < or = 2 x 10(-10). We find the abundance ratio of HCN:HCCN:HCCCN in TMC-l to be l : <0.01 : 0.3, which suggests that carbon-chain growth by the addition of single carbon atoms may not be efficient under dark cloud conditions. The HCCN abundance limit also places constraints on the branching ratio for the products of the dissociative electron recombination H3C2N+ + e.     

Mass spectrometric study of three-body ion-molecule clustering reactions of CpHq+ ions with N2 or CH4 in N2-CH4 mixtures

Thermochemical data for several ion-molecule clustering of hydrocarbon ions with N2 or CH4 were obtained from clustering equilibria studies in gas mixtures irradiated by alpha-particles. High-pressure mass spectrometry was used to determine the enthalpy and entropy changes of clustering (delta H0 and delta S0, respectively) for the reactions X+(N2)n-1 + 2N2 <==> X(+)(N2)n + N2 with X = CH5, n = 1-2; X = C2H5, n = 1-4; and X = C3H7, n = 1. For X = CH5, the values (delta H0; delta S0) are found to be (-6.8 kcal mol-1; -19.7 cal mol-1 K-1) for n = 1, and (-5.3 kcal mol-1; -15.9 cal mol-1 K-1) for n = 2. For X = C2H5, (delta H0; delta S0) = (-6.9 kcal mol-1; -18.2 cal mol-1 K-1), for n = 1, and (-4.6 kcal mol-1; -20.8 cal mol-1 K-1) for n = 2. From the equilibrium measurements at 129 K, estimates of the thermochemical values could be obtained for n = 3-4. The results obtained for the free energy, delta G0, were -1.4 kcal mol-1 for n = 3, and -1.1 kcal mol-1 for n = 4. For X = C3H7 we found delta G0 = -0.7 kcal mol-1 at 213 K. The association reactions X+ + 2CH4 <==> X+(CH4) + CH4 with X = CH5, C2H5, C2H7, and C3H7 were also studied, resulting in free energy values at 206 K of -3.1, -1.9, -0.5 and -1.3 kcal mol-1, respectively. The results for CH5, C2H5 and C3H7 are compared with previously reported measurements.     

Condensation and vaporization studies of CH3OH and NH3 ices: major implications for astrochemistry

In an extension of previously reported work on ices containing H2O, CO, CO2, SO2, H2S, and H2, we present measurements of the physical and infrared spectral properties of ices containing CH3OH and NH3. The condensation and sublimation behavior of these ice systems is discussed and surface binding energies are presented for all of these molecules. The surface binding energies can be used to calculate the residence times of the molecules on grain surfaces as a function of temperature. It is demonstrated that many of the molecules used to generate radio maps of and probe conditions in dense clouds, for example CO and NH3, will be significantly depleted from the gas phase by condensation onto dust grains. Attempts to derive total column densities solely from radio maps that do not take condensation effects into account may vastly underestimate the true column densities of any given species. Simple CO condensation onto and vaporization off of grains appears to be capable of explaining the observed depletion of gas phase CO in cold, dense molecular cores. This is not the case for NH3, however, where thermal considerations alone predict that all of the NH3 should be condensed onto grains. The fact that some gas phase NH3 is observed indicates that additional desorption processes must be involved. The surface binding energies of CH3OH, in conjunction with this molecule's observed behavior during warm up in H2O-rich ices, is shown to provide an explanation of the large excess of CH3OH seen in many warm, dense molecular cores. The near-infrared spectrum and associated integrated band strengths of CH3OH-containing ice are given, as are middle infrared absorption band strengths for both CH3OH and NH3.