Cyanopolyyne chemistry in TMC-1

Using pseudo-time-dependent models and three different reaction networks, a detailed study of the dominant reaction pathways for the formation of cyanopolyynes and their abundances in TMC-1 is presented. The analysis of the chemical reactions show that for the formation of cyanopolyynes there are two major chemical regimes. First, early times of less than ～10⁴ yrs when ion-molecule reactions are dominant, the main chemical route for the formation of larger cyanopolyynes is $$C_n H^ + \xrightarrow{N}C_n N^ + \xrightarrow{{H_2 }}HC_n N^ + \xrightarrow{{H_2 }}H_2 C_n N^ + \xrightarrow{{e^ - }}HC_n N$$ wheren=5, 7, and 9. Second, at times greater than 10⁴ yrs, when neutral-neutral reactions become dominant, two major reaction routes for the formation of cyanopolyynes are (a), $$HCN\xrightarrow{{C_2 H}}HC_3 N\xrightarrow{{C_2 H}}HC_5 N\xrightarrow{{C_2 H}}HC_7 N\xrightarrow{{C_2 H}}HC_9 N$$ and (b) $$C_n H_2 + CN \to HC_{n + 1} N + H,{\text{ }}n = 4,6, and 8$$ depending on the reaction network used. The results indicate that for route (a) large abundances ofC ₂ H (fractional abundances of ～10^?7), and for route (b) large abundances ofC ₂ H ₂ are required in order to reproduce the observed abundances of cyanopolyynes. The calculated abundances of cyanopolyynes show great sensitivity to the value of extinction particularly att?5×10⁵ yrs (i.e. photochemical timescale). The effect of other physical parameters, such as the cosmic-ray ionization abundances are also examined. In general, the model calculations show that the observed abundances of cyanopolyynes can be achieved by pseudo-time-dependent models at late times of several million years.     

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.     

Shock waves and the chemical structure of interstellar clouds

In this paper we study the effect of shock waves on the chemical structure of the interstellar clouds. A model of molecular cloud has been assumed. The chemistry is investigated in a time dependent model. Our chemical network contains 56 species in 251 reactions to including molecules of the elements H, O, C, N, S, and Si.The results indicate that the calculated fractional abundance of the molecules NS, H₂O, CN, NH, CO, and SO agrees well with the observations. The molecules OH, H₂S, CS, H₂CS, HS, NO, SiO, CH, CH₂, CH₃, HCO, C₂, and HCN reach high post-shock abundances.     

Molecule searches in Comet Kohoutek (1973f) at microwave frequencies

Nine transitions of the possible parent molecules H₂O, NH₃, CH₃OH and N₂O as well as the OH radical were searched for in Comet Kohoutek (1973f) in the frequency range 22.2–25.2 GHz. These molecules were not detected, but the upper limits for the optical depth, mean column density and the production rate are derived for each of the molecules. These results are discussed and compared with the reported detections of HCN and CH₃CN emission and OH absorption.     

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.     

Gaseous Jets in Comet Hale-Bopp (1995 O1)

We report the identification of gas jets in comet Hale-Bopp in OH, NH, CN, C₂ and C₃. This is the first time OH and NH jets without an obvious optical dust jet counterpart have been identified in narrowband comet images. We also confirm the existence of CN jets as reported by Larson et al. (1997) and Mueller et al. (1998). Jet features can be seen in the March and April 1997 datasets, approximately a month before and after perihelion. Our results contribute to the understanding of both the chemical properties of the comet as well as the physical mechanisms necessary to produce these features. This revised version was published online in July 2006 with corrections to the Cover Date.     

Chemical and physical properties of gas jets in comets: I. Monte Carlo model of an inner cometary coma

We describe a 3-dimensional, time-dependent Monte Carlo model developed to analyze the chemical and physical nature of a cometary gas coma. Our model includes the necessary physics and chemistry to recreate the conditions applicable to Comet Hale-Bopp when the comet was near 1 AU from the Sun. Two base models were designed and are described here. The first is an isotropic model that emits particles (parents of the observed gases) from the entire nucleus; the second is a jet model that ejects parent particles solely from discrete active areas on the surface of the comet nucleus, resulting in coma jets. The two models are combined to produce the final model, which is compared with observations. The physical processes incorporated in both base models include: (1) isotropic ejection of daughter molecules (the observed gases) in the parent's frame of reference, (2) solar radiation pressure, (3) solar insolation effects, (4) collisions of daughter products with other molecules in the coma, and (5) acceleration of the gas in the coma. The observed daughter molecules are produced when a parent decays, which is represented by either an exponential decay distribution (photodissociation of the parent gas) or a triangular distribution (production from a grain extended source). Application of this model to the analysis the OH, C₂ and CN gas jets observed in the coma of Comet Hale-Bopp is the focus of the accompanying paper [Lederer, S.M., Campins, H., Osip, D.J., 2008. Icarus, in press (this issue)].     

Chemical and physical properties of gas jets in comets: II. Modeling OH, CN and C2 jets in Comet C/1995 O1 (Hale-Bopp) one month after perihelion

We present an analysis of OH, CN, and C₂ jets observed in Comet Hale-Bopp during April 22-26, 1997. We conclude that an extended source, which peaks in productivity after a certain amount of time has passed after being released from the nucleus (8.5, 2.5, and 42.6×¹⁰⁴ s, respectively) is responsible for the observed coma jet morphology in all three species. Sub-micron organic grains are the favored explanation for the extended source. Our models indicate that this extended source produces approximately 40% of the OH, 50% of the C₂, and 75% of the CN. The balance for each species is created by a diffuse nuclear gas source. Compared with the nuclear gas source and normalized to the CN abundance, the composition of the extended source is depleted in OH by a factor of ∼6, and depleted in C₂ by a factor of ∼2. The existence of anti-sunward jets do not require production of radicals throughout the cometary night. Instead, our model demonstrates that active areas exposed to near-twilight conditions throughout the comet's rotational period can produce the observed anti-sunward morphology.     

Photographic photometry of the CN and C3 comae of Comet Halley

Two photographs of Comet Halley in CN were obtained in 1986 April 8 and 12, and two in C₃, on March 21 and May 5. Photometry led to mean brightness profiles of the CN and C₃ comae on these days. Using Haser's coma model, the scale-heights of these two molecules and of the parent molecules were derived.     

Spectroscopic Observations of Comet C/1996 B2 (Hyakutake) with the Caltech Submillimeter Observatory

The apparition of Comet C/1996 B2 (Hyakutake) offered an unexpected and rare opportunity to probe the inner atmosphere of a comet with high spatial resolution and to investigate with unprecedented sensitivity its chemical composition. We present observations of over 30 submillimeter transitions of HCN, H¹³CN, HNC, HNCO, CO, CH₃OH, and H₂CO in Comet Hyakutake carried out between 1996 March 18 and April 9 at the Caltech Submillimeter Observatory. Detections of the H¹³CN (4–3) and HNCO (16_0,16–15_0,15) transitions represent the first observations of these species in a comet. In addition, several other transitions, including HCN (8–7), CO (4–3), and CO (6–5) are detected for the first time in a comet as is the hyperfine structure of the HCN (4–3) line. The observed intensities of the HCN (4–3) hyperfine components indicate a line center optical depth of 0.9 ± 0.2 on March 22.5 UT. The HCN/HNC abundance ratio in Comet Hyakutake at a heliocentric distance of 1 AU is similar to that measured in the Orion extended ridge— a warm, quiescent molecular cloud. The HCN/H¹³CN abundance ratio implied by our observations is 34 ± 12, similar to that measured in giant molecular clouds in the galactic disk but significantly lower than the Solar System¹²C/¹³C ratio. The low HCN/H¹³CN abundance ratio may be in part due to contamination by an SO₂line blended with the H¹³CN (4–3) line. In addition, chemical models suggest that the HCN/H¹³CN ratio can be affected by fractionation during the collapse phase of the protosolar nebula; hence a low HCN/H¹³CN ratio observed in a comet is not inconsistent with the solar system¹²C/¹³C isotopic ratio. The abundance of HNCO relative to water derived from our observations is (7 ± 3) × 10⁻⁴. The HCN/HNCO abundance ratio is similar to that measured in the core of Sagittarius B2 molecular cloud. Although a photo-dissociative channel of HNCO leads to CO, the CO produced by HNCO is a negligible component of cometary atmospheres. Production rates of HCN, CO, H₂CO, and CH₃OH are presented. Inferred molecular abundances relative to water are typical of those measured in comets at 1 AU from the Sun. The exception is CO, for which we derive a large relative abundance of 30%. The evolution of the HCN production rate between March 20 and March 30 suggests that the increased activity of the comet was the cause of the fragmentation of the nucleus. The time evolution of the H₂CO emission suggests production of this species from dust grains.     

Carbon dioxide on planetary bodies: Theoretical and experimental studies of molecular complexes

An absorption band at ∼4.26 μm wavelength attributed to the asymmetric stretching mode of CO in CO₂ has been found on two satellites of Jupiter and several satellites of Saturn. The wavelength of pure CO₂ ice determined in the laboratory is 4.2675 μm, indicating that the CO₂ on the satellites occurs either trapped in a host material, or in a chemical or physical complex with other materials, resulting in a blue shift of the wavelength of the band. In frequency units, the shifts in the satellite spectra range from 3.7 to 11.3 cm⁻¹. We have performed ab initio quantum chemical calculations of CO₂ molecules chemically complexed with one, two, and more H₂O molecules and molecules of CH₃OH to explore the possibility that the blue shift of the band is caused by chemical complexing of CO₂ with other volatile materials. Our computations of the harmonic and anharmonic vibrational frequencies using high levels of theory show a frequency shift to the blue by 5 cm⁻¹ from pure CO₂ to CO-H₂O, and an additional 5 cm⁻¹ from CO₂-H₂O to CO₂-2H₂O. Complexing with more than two H₂O molecules does not increase the blue shift. Complexes of CO₂ with one molecule of CH₃OH and with one CH₃OH plus one H₂O molecule produce smaller shifts than the CO₂-2H₂O complex. Laboratory studies of CO₂:H₂O in a solid N₂ matrix also show a blue shift of the asymmetric stretching mode.     

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.     

Radioastronomical observations of comets IRAS-Araki-Alcock (1983d) and Sugano-Saigusa-Fujikawa (1983e)

Detections and upper limits to the continuum emission (1 ≤ λ ≤6 cm) and spectral line emission (OH, CO, CS, HCN, HCO⁺, CN, CH₃CN, CH₃C₂H, NH₃, H₂O, HC₃N, CH₃CH₂CN) are reported from radio observations of Comets 1983d and 1983e. Comparison is made with observations of CN at optical wavelengths. These results may be useful in planning future cometary observations.     

Ion chemistry in the cometary atmosphere

Dirty ice of a second kind (major components, H₂O, CO, and N₂; minor components less than several percents, NH₃, CH₄, and other organic substances such as HCN, CH₃CN etc.) is assumed for the composition of volatiles in the cometary nucleus. The consistency with the observations of molecular ions and daughter molecules in the cometary atmosphere is argued by taking into account various ion-molecular reactions and dissociative recombinations. There is a satisfactory agreement for the second kind of dirty-ice model, but the presence of large amounts of CH₄ and NH₃ is found to be rather in contradiction with observational evidence. A velocity of 8 km s^?1 for the hydrogen atoms, derived from analysis of the hydrogen Lyman-alpha corona around comets, is found from the dissociative recombination of H₃O⁺, the dominant constituent of cometary ionosphere, in accordance with H₃O⁺+e ^?→OH+H+H.     

Formation of molecules in bright meteors

We calculated equilibrium chemical composition of a mixture of meteoritic vapor and air during fireball events, i.e. during penetration of large meteoroids into terrestrial atmosphere. Different types of fireballs were considered, and calculations were performed for wide ranges of temperatures and pressures. Chemical composition at the quenching point was estimated by comparison of hydrodynamic and chemical reaction time scales. For the typical fireball temperatures of 4000-5000 K, most elements are expected to be in the form of atoms and ions. Notable exceptions are Si and C, which are expected to be mainly in the form of SiO and CO. Other molecules abundant at these temperatures are N₂ and NO. Metal monoxides are most abundant at 2000-2500 K and are formed during the cooling phase. Conditions for formation of other molecules such as , CN, C₂ and OH were also considered. The composition of freshly ablated meteoroid material was studied using the MAGMA code.     

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.     

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.     

Reactions of nitriles in ices relevant to Titan, comets, and the interstellar medium: formation of cyanate ion, ketenimines, and isonitriles

Motivated by detections of nitriles in Titan's atmosphere, cometary comae, and the interstellar medium, we report laboratory investigations of the low-temperature chemistry of acetonitrile, propionitrile, acrylonitrile, cyanoacetylene, and cyanogen (CH₃CN, CH₃CH₂CN, CH₂CHCN, HCCCN, and NCCN, respectively). A few experiments were also done on isobutyronitrile and trimethylacetonitrile ((CH₃)₂CHCN and (CH₃)₃CCN, respectively). Trends were sought, and found, in the photo- and radiation chemical products of these molecules at 12-25 K. In the absence of water, all of these molecules isomerized to isonitriles, and CH₃CN, CH₃CH₂CN, and (CH₃)₂CHCN also formed ketenimines. In the presence of H₂O, no isonitriles were detected but rather the cyanate ion (OCN⁻) was seen in all cases. Although isonitriles, ketenimines, and OCN⁻ were the main focus of our work, we also describe cases of hydrogen loss, to make smaller nitriles, and hydrogen addition (reduction), to make larger nitriles. HCN formation also was seen in most experiments. The results are presented in terms of nitrile ice chemistry on Titan, in cometary ice, and in the interstellar medium. Possible connections to prebiotic chemistry are briefly discussed.     

On the photochemical formation of CN,C2, and C3 radicals in cometary comae

The formation of cometary CN, C₂ and C₃ radicals is investigated in a photochemical reaction scheme. From an analysis of the observed brightness profiles of these radicals, it is shown that CN is formed as a primary product in the photolysis of its parent molecules, whereas C₂ and C₃ are formed via two-step photodissociation of their parents. We suggest that major parent of C₂ is different species from those of CN and C₃ on the basis of the difference of the variation with heliocentric distance of the sublimation rate of the parents of these radicals. Parent molecules and reaction schemes for the formation of these radicals are discussed.     

The 1995–2002 Long-Term Monitoring of Comet C/1995 O1 (HALE–BOPP) at Radio Wavelength

The bright comet Hale–Bopp provided the first opportunity to follow the outgassing rates of a number of molecular species over a large range of heliocentric distances. We present the results of our observing campaign at radio wavelengths which began in August 1995 and ended in January 2002. The observations were carried out with the telescopes of Nançay, IRAM, JCMT, CSO and, since September 1997, SEST. The lines of nine molecules (OH, CO, HCN, CH₃OH, H₂CO, H₂S, CS, CH₃CN and HNC) were monitored. CS, H₂S, H₂CO, CH₃CN were detected up to r_h= 3–4 AU from the Sun, while HCN and CH₃OH were detected up to 6 AU. CO, which is the main driver of cometary activity at heliocentric distances larger than 3–4 AU, was last detected in August 2001, at r_h= 14 AU. The gas production rates obtained from this programme contain important information on the nature of cometary ices, their thermal properties and sublimation mechanisms.Line shapes allow to measure gas expansion velocities, which, at large heliocentric distances, might be directly connected to the temperature of the nucleus surface. Inferred expansion velocity of the gas varied as r_h ^-0.4 within 7 AU from the Sun, but remained close to 0.4 km s^-1 further away. The CO spectra obtained at large r_hare strongly blueshifted and indicative of an important day-to-night asymmetry in outgassing and expansion velocity. The kinetic temperature of the coma, estimated from the relative intensities of the CH₃OH and CO lines, increased with decreasing r_h, from about 10 K at 7 AU to 110 K around perihelion.