Theoretical investigation of the interstellar CH3NC/CH3CN ratio

Calculations have been performed to determine the abundance ratio of the metastable isomer CH3NC to the stable isomer CH3CN in dense interstellar clouds. According to gas phase, ion-molecule treatments, these molecules are both synthesized via protonated ion precursors. We have calculated the ratio of the formation rates of the protonated precursor ions-- CH3NCH+ and CH3CNH+ --synthesized via the radiative association reaction between CH3+ and HCN, which is thought to the dominant formation process of the two isomeric ions. Our calculations, which involve both ab initio quantum chemistry and equilibrium determinations, lead to a predicted CH3NCH+/CH3CNH+ formation rate ratio between 0.1 and 0.4. If this ratio is maintained in the neutral species formed from the precursor ions, theory predicts a sizable abundance for methyl isocyanide (CH3NC) and lends credence to its tentative observation.     

Measurements in N2-CH4(C2H2) discharges of reaction rates and thermochemical constants for Titan atmosphere study

The kinetic reactions in N2-xCH4(C2H2) gas discharges with x less than 1% have been studied by emission spectroscopy in the afterglow of D.C. discharges and by mass spectroscopy from radiolysis ionization using alpha particles. The pressure range is from several Torr to 100 Torr. At the end of N2 D.C. discharges at room temperature, for a residence time of about 10(-2) s, the dominant active species are the N atoms with density of 10(14)-10(15) cm-3 for N2 density of about 10(17) cm-3 (3 Torr), the N2(X,V) vibrational molecules with for example [N2(X,V = 10)] approximately 10(14) cm-3 and the electronic metastable molecules N2(A 3 sigma u +) with a density of 10(12) cm-3. In such conditions, the following kinetic reactions have been studied: N2(A) + N2(A) --> N2(C,B,V') + N2(X), N2(A) + N2(X,V>5) --> N2(X) + N2(B,V') in pure N2 post-discharges and N2(A) + CH4 --> products, C + N + M2 --> CN(B,V') + M2, N2(X,V>4) + CN --> N2(X) + CN(B,A,V'), in N2-1% CH4 post-discharges. The clustering reactions of N2-(1-5%)CH4(C2H2) gas mixtures after radiolysis ionization have been studied for the H2CN+ nN2 ions and the equilibrium constants have been determined in the temperature range T = 140-300 K.     

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.     

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.     

Laboratory detection of a new interstellar free radical CH2CN(2B1)

An asymmetric-top free radical CH2CN, which as a 2B1 ground state, was detected for the first time by laboratory microwave spectroscopy. The radical was produced in a free-space absorption cell by a DC glow discharge in pure CH3CN gas. About 60 fine-structure components were observed for the N = 11-10 to 14-13 a-type rotational transitions in the frequency region of 220-260 GHz, and many hyperfine resolved components for the N = 4-3 and 5-4 transitions in the 80 and 100 GHz regions, respectively. The molecular constants, including the rotational constants, centrifugal distortion constants, and spin-rotation coupling constants with centrifugal distortion correction terms were determined from the fine-structure resolved transitions, and the hyperfine coupling constants due to the hydrogen and nitrogen nuclei were obtained from the low-N transitions. As a result we assigned U100602 and U80484 from Sgr B2, and U40240 and U20120 from TMC-1, to the N = 5-4, 4-3, 2-1, and 1-0 transitions with K-1 = 0 of the CH2CN radical.     

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.     

Cyanide Chemistry in Comet Hale-Bopp (C/1995 O1)

Observations of comet Hale-Bopp (C/1995 O1) have been carried out near perihelion (1997 March) at millimeter wavelengths using the NRAO 12 m telescope. The J=1-->0, 2-->1, and 3-->2 lines of HCN at 88, 177, and 265 GHz were measured in the comet as well as the J=3-->2 lines of H13CN, HC15N, and HNC. The N=2-->1 transition of CN near 226 GHz was also detected, and an upper limit was obtained for the J=2-->1 line of HCNH+. From the measurements, column densities and production rates have been estimated. A column density ratio of [HCN]/[HNC] = 7+/-1 was observed near perihelion, while it was found that [HCN]/[HCNH+] greater, similar 1. The production rates at perihelion for HCN and CN were estimated to be Q(HCN) approximately 1x1028 s-1 and Q(CN) approximately 2.6x1027 s-1, respectively, resulting in a ratio of [HCN]/[CN] approximately 3. Consequently, HCN is sufficiently abundant to be the parent molecule of CN in Hale-Bopp, and HCNH+ could be a source of HNC. Finally, carbon and nitrogen isotope ratios of 12C/13C = 109+/-22 and 14N/15N = 330+/-98 were obtained from HCN measurements, in agreement with previous values obtained from J=4-->3 data. Such ratios suggest that comet Hale-Bopp formed coevally with the solar system.     

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.     

Detection of a new interstellar molecule, H2CN

We have detected a new interstellar molecule, H2CN (methylene amidogen), in the cold, dark molecular cloud TMC-l. The column density of H2CN is estimated to be approximately 1.5 x 10(11) cm-2 by assuming an excitation temperature of 5 K. This column density corresponds to a fractional abundance relative to H2 of approximately 1.5 x 10(-11). This value is more than three orders of magnitude less than the abundance of the related molecule HCN in TMC-1. We also report a tentative detection of H2CN in Sgr B2(N). The formation mechanism of H2CN is discussed. Our detection of the H2CN molecule may suggest the existence of a new series of carbon-chain molecules, CH2CnN (n = 0, 1, 2,...).     

The relative abundance of ethane to acetylene in the Jovian stratosphere

The observed ratio of C2H6 to C2H2 in the Jovian stratosphere increases from approximately 55 at 2 mbar to approximately 277 at 12 mbar. In current photochemical models this ratio typically increases between 2 and 12 mbar by a factor of < or = 3. Recent laboratory kinetics studies on the reaction between C2H3 and H2 to form C2H4 suggest an efficient chemical mechanism for hydrogenation of C2H2 to C2H6. Inclusion of this scheme as part of a comprehensive updated model for hydrocarbon photochemistry in the atmosphere of Jupiter provides an explanation of the altitude variation of the C2H6/C2H2 ratio. The sensitivity of these results to uncertainties in the key rate constants at low temperatures is illustrated, identifying needs for additional laboratory measurements. Since the key reaction rate constants decrease with decreasing temperature, the hydrogenation of C2H2 as proposed predicts a qualitatively decreasing trend in the C2H6/C2H2 value with decreasing distance from the Sun. The observed variation between Jupiter and Saturn is consistent with this prediction.     

SiS in Orion-KL: evidence for "outflow" chemistry

SiS has been conclusively detected toward Orion-KL via its J = 6-5 and J = 5-4 rotational transitions at 91 and 109 GHz. Line profiles indicate that the species is present at an LSR velocity of 7.5 km s-1 with a half-width at zero power of 36 km s-1. Such characteristics associate SiS with the moderate velocity outflow (V approximately 18 km s-1) centered on IRc2 and observed in thermal SiO, the NH3 "plateau," and OH, H2O, and SiO masers. The column density estimated for SiS in this region is Ntot = 4 x 10(15) cm-2, corresponding to a fractional abundance of f approximately 4 x 10(-9). Such an abundance implies an SiO/SiS ratio of approximately 60 in the outflow material, remarkably close to the cosmic O/S ratio of approximately 40 and contrasting with the SiO/SiS value of > approximately 10(3) predicted by ion-molecule models. This difference is probably a result of the high temperatures and densities present in the outflow, which favor thermal equilibrium abundances similar to those observed in the circumstellar shells of late-type stars rather than "ion-molecule"-type concentrations. In addition to SiS, some twenty new unidentified lines near 91 and 109 GHz were detected toward KL, as well as transitions arising from HC5N, HC13CCN, HCC13CN, O13CS, and, possibly, CH3CH2OH, CH3CHO, and CH3OD.     

Time dependent chemical study of contracting interstellar clouds. I. Abundances of nitrogen- and carbon-bearing molecules

We have constructed a reaction system containing the chemical families of H, C, O, N, S, Si, Cl, metals (Me) and grains. A total of 104 species have been included and a network of 557 reactions has been studied. The chemical kinetic equations were integrated as a function of time by using gear program. The chemical reaction system was followed at low, intermediate and high cloud densities i.e. from 10–10⁷ particles cm^-3. The calculated fractional abundances of N₂, CN, HCN, and CH which are in good agreement with the results of observations and with those of previous theoretical studies.     

Chemistry of the organic-rich hot core G327.3-0.6

We present gas-phase abundances of species found in the organic-rich hot core G327.3-0.6. The data were taken with the Swedish-ESO Submillimetre Telescope (SEST). The 1-3 mm spectrum of this source is dominated by emission features of nitrile species and saturated organics, with abundances greater than those found in many other hot cores, including Sgr B2 and OMC-1. Population diagram analysis indicates that many species (CH3CN, C2H3CN, C2H5CN, CH3OH, etc.) have hot components that originate in a compact (~2") region. Gas-phase chemical models cannot reproduce the high abundances of these molecules found in hot cores, and we suggest that they originate from processing and evaporation of icy grain mantle material. In addition, we report the first detection of vibrationally excited ethyl cyanide and the first detection of methyl mercaptan (CH3SH) outside the Galactic center.     

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.     

Studies of some diatomic molecules in the F- and early G-type dwarf stars

A critical analysis of CH, NH, OH, C₂, and CN molecules/radicals has been made in twenty-four F- and early G-type dwarfs at different effective temperature as well as in new constructed model atmosphere. Molecular indices of bandheads ofA-X system of CH, NH, OH, C₂, and CN have been obtained by using the data available in the literature (thirteen-colour and eight-colour photometry).Besides, some interesting plots of the molecular indices vs _eff, molecular abundances and molecular indices vs dissociation energy, reduced equivalent widths and FCF's vs dissociation energy for respective molecules have also been enumerated. It is found that the molecular indices at bandheads ofA-X system of CH, NH, OH, C₂, and CN are approximately constant (5810–6570 K). It is to be noted that the molecular indices decrease in the order OH, NH, CH, C₂, and CN at a given temperature.The dissociation equilibrium of CH, NH, OH, C₂, and CN is considered at 5810, 6570, and 7160 K phases in model atmosphere. At standard scale of abundance the molecular abundance and molecular index decrease in the order OH, NH, CH, C₂, and CN at any given phase, however, CN abundance and index increase (_eff=0.867-0.767). The amplitude of abundance and index variation decrease in the order NH, OH, CH, C₂, and CN (_eff=0.767-0.704).The reduced equivalent width decrease in the order OH, NH, CH, and C₂ and FCF's decrease in the order CH, OH, NH, CN, and C₂.The confrontation of models and observations of spectra of F- and early G-type dwarfs of parent molecules is of primary importance to investigate the physical conditions within atmospheres. Reliable excitation models are also requisite for interpreting spectroscopic observations of parent molecules and deriving molecular abundances.     

Why HOC+ is detectable in interstellar clouds: the rate of the reaction between HOC+ and H2

The recent confirmation by Ziurys and Apponi of the detection of HOC+ toward Sgr B2 (OH), and their identification of the ion in Orion-KL and several other sources show that HOC+ is far more abundant than predicted by previous ion-molecule models. In these models, the reaction HOC(+) + H2 --> HCO(+) + H2 is assumed to rapidly destroy HOC+, based on the results of a prior calculation. We have recalculated the rate of this reaction as a function of temperature using a new ab initio potential surface and a phase space approach to the dynamics which includes tunneling. The newly calculated rate is small (< or = 1 x 10(-10) cm3 s-1) at temperatures under 100 K.     

Multifrequency radio observations of coronal holes,filaments and cavities on RATAN–600

On the basis of multifrequency solar radio observations made on RATAN–600 radiotelescope with high spatial resolution at nine wavelengths in the 2–32–wavelength range is shown that filaments and cavities are well detected on the solar scans at short centimeter wavelengths as the regions of low radio brightness with angular dimensions of 25′–80′ in E—W direction. The tendency of decreasing radio sizes for cavities and filaments from 2.0 to 8.0 cm is observed. The coronal hole (CH) is more contrast in the range of 8–32 cm. The radio size of CH in E—N direction increases from 2′ (at 8.2) to 5′.0 (at 31.6 cm). The spectra of the brightness temperature of CH and the quiet Sun are obtained. The brightness temperature of CH is twice lower than that of the quiet Sun at wavelength of 31.6 cm.     

The origin of the CN radical in comets: A review from observations and models

The origin of CN radicals in comets is not completely understood so far. We present a study of CN and HCN production rates and CN Haser scale lengths showing that: (1) at heliocentric distances larger than 3 AU, CN radicals could be entirely produced by HCN photolysis; (2) closer to the Sun, for a fraction of comets CN production rates are higher than HCN ones whereas (3) in the others, CN distribution cannot be explained by the HCN photolysis although CN and HCN production rates seem to be similar. Thus, when the comets are closer than 3 AU to the Sun, an additional process to the HCN photolysis seems to be required to explain the CN density in some comets.The photolysis of HC₃N or C₂N₂ could explain the CN origin. But the HC₃N production rate is probably too low to reproduce CN density profile, even if uncertainties on its photolysis leave the place for all possible conclusions. The presence of C₂N₂ in comets is a reliable hypothesis to explain the CN origin; thus, its detection is a challenging issue. Since C₂N₂ is very difficult to detect from ground-based observations, only in situ measurements or space observations could determine the contribution of this compound in the CN origin.Another hypothesis is a direct production of CN radicals by the photo- or thermal degradation of complex refractory organic compounds present on cometary grains. This process could explain the spatial profile of CN inside jets and the discrepancy noted in the isotopic ratio ¹⁴N/¹⁵N between CN and HCN. Laboratory studies of the thermal and UV-induced degradation of solid nitrogenated compounds are required to model and validate this hypothesis.     

New Molecular Species in Comet C/1995 O1 (Hale-Bopp) Observed with the Caltech Ssubmillimeter Observatory

We present millimeter-wave observations of HNCO, HC₃N, SO, NH₂CHO, H¹³CN, and H₃O⁺ in comet C/1995 O1 (Hale-Bopp)obtained in February–April, 1997 with the Caltech Submillimeter Observatory (CSO). HNCO, first detected at the CSO in comet C/1996B2 (Hyakutake), is securely confirmed in comet Hale-Bopp via observations of three rotational transitions. The derived abundance with respect to H₂O is (4-13) × 10^-4. HC₃N, SO, and NH₂CHO are detected for the first time in a comet. The fractional abundance of HC₃N based on observations of three rotational lines is (1.9 ± 0.2) × 10^-4. Four transitions of SO are detected and the derived fractional abundance, (2-8) ×10^-3, is higher than the upper limits derived from UV observations of previous comets. Observations of NH₂CHO imply a fractional abundance of (1-8) × 10^-4. H₃O is detected for the first time from the ground. The H¹³CN (3-2)transition is also detected and the derived HCN/H¹³CN abundance ratio is 90 ± 15, consistent with the terrestrial¹²C/¹³C ratio. In addition, a number of other molecular species are detected, including HNC, OCS, HCO⁺, CO⁺, and CN(the last two are first detections in a comet at radio wavelengths). This revised version was published online in July 2006 with corrections to the Cover Date.     

Ab initio characterization of MgCCH, MgCCH+, and MgC2 and pathways to their formation in the interstellar medium

A study of Mg-bearing compounds has been performed in order to determine molecular properties which are critical for planning new astronomical searches and laboratory studies. The primary focus of the work is on MgCCH, MgCCH+, and the isomers of MgC2. Only MgCCH has been identified in laboratory studies. Additional calculations have been carried out on MgH, MgNC, MgCN, and their cations in an effort to evaluate pathways to the formation of MgCCH and MgCCH+ in the interstellar medium (ISM) or in circumstellar envelopes. Correlated ab initio methods and correlation-consistent basis sets have been employed. Properties including structures, rotational constants, dipole moments, and harmonic frequencies are reported. A transition state between linear MgCC and cyclic MgC2 has been characterized and was found to yield a minimal barrier (approximately 0.5 kcal mole-1), indicating easy interconversion to the cyclic form. Direct reactions in the ISM between Mg or Mg+ and HCCH are precluded by energetic considerations, but a number of ion-molecule or neutral-neutral exchange reactions between CCH and various Mg-containing species offer plausible pathways to MgCCH or MgCCH+. Weakly bound MgH may react with CCH to form MgCCH, but MgH has not been detected. Both MgNC and MgCN have been observed, but reactions with CCH are slightly endothermic by 1-3 kcal mole-1. Although MgH+, MgNC+, and MgCN+ have not been detected, their reactions with CCH to form MgCCH+ are all exothermic. With only a small barrier separating linear MgCC and cyclic MgC2, the dissociative recombination of MgCCH+ with an electron is expected to yield cyclic MgC2 and regenerate Mg and CCH. New astronomical searches for MgCCH, MgCCH+, cyclic MgC2, MgNC+, and MgCN+ will provide further insight into organo-magnesium astrochemistry.