A&A 479, 493-501 (2008)
DOI: 10.1051/0004-6361:20078956
M. Agúndez1 - J. P. Fonfría1 - J. Cernicharo1 - J. R. Pardo1 - M. Guélin2
1 -
Departamento de Astrofísica Molecular e Infrarroja,
Instituto de Estructura de la Materia, CSIC, Serrano 121, 28006 Madrid, Spain
2 -
Institut de Radioastronomie Millimétrique, 300 rue de la Piscine, 38406 St. Martin
d'Hères and LERMA/École Normale Supérieure, 24 rue Lhomond,
75231 Paris, France
Received 29 October 2007 / Accepted 6 December 2007
Abstract
Aims. We report on the detection of vinyl cyanide (CH2CHCN), cyanomethyl radical (CH2CN), methylacetylene (CH3CCH), and thioformaldehyde (H2CS) in the C-rich star IRC +10216. These species, which are all known to exist in dark clouds, were detected for the first time in the circumstellar envelope around an AGB star.
Methods. The four molecules were detected through pure rotational transitions in the course of a 3 mm line survey carried out with the IRAM 30-m telescope. The molecular column densities were derived by constructing rotational temperature diagrams. A detailed chemical model of the circumstellar envelope is used to analyze the formation of these molecular species.
Results. We have found column densities in the range 5
1012-2
1013 cm-2, which translates to fractional abundances relative to H2 of several 10-9. The chemical model is reasonably successful in explaining the derived abundances through gas phase synthesis in the cold outer envelope. We also find that some of these molecules, CH2CHCN and CH2CN, are most probably excited through infrared pumping to excited vibrational states.
Conclusions. The detection of these species stresses the similarity between the molecular content of cold dark clouds and C-rich circumstellar envelopes. However, some differences in the chemistry are indicated by partially saturated carbon chains being present in IRC +10216 at a lower level than those that are highly unsaturated, while in TMC-1 both types of species have comparable abundances.
Key words: astrochemistry - stars: circumstellar matter - stars: AGB and post-AGB - stars: carbon - stars: individual: IRC +10216
The chemical complexity of circumstellar envelopes (CSEs) around carbon-rich AGB stars is illustrated by the well known object IRC +10216, where more than 60 different molecular species have been identified to date. Due to the carbon-rich nature of the gas, the vast majority are oxygen-deprived hydrocarbons with a very concrete structure consisting of a linear and highly unsaturated backbone of carbon atoms. Among these species are cyanopolyynes HC2n+1N, polyacetylenic radicals CnH, carbenes H2Cn, allenic radicals HC2nN, as well as sulphur and silicon-bearing carbon chains CnS, SiCn (Cernicharo et al. 2000). The synthesis of these molecules involves the photodissociation and photoionisation by interstellar UV photons of parent species out-flowing from the star and subsequent neutral-neutral and ion-molecule gas phase reactions in the cold outer envelope (e.g. Lafont et al. 1982; Nejad & Millar 1987; Millar et al. 2000; Millar & Herbst 1994). Thus, reactive molecules are distributed in circumstellar shells, as confirmed by interferometric observations (e.g. Guélin et al. 1993).
This type of chemistry resembles what is occurring in cold dense clouds, such as TMC-1, which are also rich in highly unsaturated carbon chain molecules. The unsaturated character is typically the result of low temperature non-equilibrium chemistry and reflects the low reactivity of H2 with most hydrocarbons at low temperatures. Dark clouds contain however a sizable fraction of partially saturated species, such as methylpolyynes CH3C2nH (n=1,2 Irvine et al. 1981; Walmsley et al. 1984), methylcyanopolyynes CH3C2n+1N (n=0,1,2 Snyder et al. 2006; Matthews & Sears 1983a; Broten et al. 1984), cyanomethyl radical CH2CN (Irvine et al. 1988), vinyl cyanide CH2CHCN (Matthews & Sears 1983b), cyanoallene CH2CCHCN (Lovas et al. 2006), and highly saturated hydrocarbons such as propylene CH2CHCH3 (Marcelino et al. 2007).
The question of why those partially saturated species are not detected in IRC +10216 is a critical one for the understanding of low-temperature non-equilibrium chemistry. We have thus embarked on a deep search for partially saturated organic molecules in IRC +10216. In this paper we present the detection of CH2CHCN, CH2CN and CH3CCH, which were observed for the first time in a CSE around an AGB star. The related species CH3CN has been already identified in this source by Johansson et al. (1984). Finally, we also report on the detection of thioformaldehyde in IRC +10216.
The four molecules in this paper (CH2CHCN, CH2CN, CH3CCH, and H2CS) were identified in space for the first time towards Sagittarius B2 (Gardner & Winnewisser 1975; Irvine et al. 1988; Snyder & Buhl 1973; Sinclair et al. 1973) by observation of rotational transitions. The microwave spectrum of all these species has been extensively studied in the laboratory so that their spectroscopic properties are accurately known; see a compilation in the JPL and Cologne databases for molecular spectroscopy (Pickett et al. 1998; Müller et al. 2005).
CH2CHCN is a planar asymmetric rotor with a- and b-type
allowed transitions (
= 3.815 D and
= 0.894 D; Stolze & Sutter 1985). All the transitions observed in IRC +10216 belong to the stronger a-type.
The radical CH2CN has two interchangeable hydrogen nuclei with
non zero spin which result in two distinct groups of rotational
levels: ortho (parallel spins) and para (antiparallel spins) with
relative statistical weights 3:1, between which both radiative and
collisional transitions are highly forbidden. The electronic
ground state is 2B1, thus, the quantum number
is even
for ortho levels and odd for para levels. The para ground state (11,1) lies 14.15 K above the ortho ground state (00,0). This assignment is reversed compared to more common species with a
1A1 electronic ground state (H2CO, H2CS, ...), where the
quantum number
is odd for ortho levels and even for para
levels, with the rotational ground state having para symmetry. Its
dipole moment is relatively large:
= 3.5 D (Ozeki et al. 2004).
The unpaired electron causes spin-rotation coupling which splits
each transition
-
into two components. Further hyperfine coupling of rotation with
the non-zero spin of 1H and 14N nuclei produces a myriad
of components whose frequencies have been precisely measured in
the laboratory (Ozeki et al. 2004).
Propyne (CH3CCH) is a prolate symmetric top molecule whose
rotational levels are divided into two different species, A-type
and E-type, not connected radiatively. Its dipole moment is
relatively small:
= 0.784 D (Burrell et al. 1980). The rotational
spectrum was first measured by Trambarulo & Gordy (1950) and is now known with
a high accuracy for its ground and some excited vibrational states
(Müller et al. 2002).
H2CS is an asymmetric rotor which, analogously to CH2CN, has
two interchangeable hydrogen nuclei so that its rotational levels
are grouped into ortho (
odd) and para (
even), with
statistical weights 3:1. The ortho ground state (11,1) lies
14.9 K above the para ground state (00,0). Its dipole moment
was measured by Fabricant et al. (1977) to be
= 1.647 D.
The observations shown in Fig. 1 were made with the
IRAM 30-m telescope during several sessions from 1990 to 2006,
most of them after 2002 in the context of a 3 mm line
survey of IRC +10216 (Cernicharo et al., in preparation). SIS receivers operating at 3 and 2 mm were tuned in single sideband
mode, with typical image rejections larger than 20 dB at 3 mm and
around 15 dB at 2 mm. We express intensities in terms of
,
the antenna temperature corrected for atmospheric absorption and
for antenna ohmic and spillover losses. The uncertainty in
due to calibration is estimated to be around 10%. Data were
taken in the standard wobbler switching mode with a beam throw of 4'. Pointing and focusing were checked by observing nearby planets
and the quasar OJ 287. The back end used was a filterbank with a
bandwidth of 512 MHz and a spectral resolution of 1.0 MHz. The
system temperature was 100-150 K at 3 mm and 200 K at 2 mm. On
source integration times ranged from 2 to 20 h, resulting in
rms noise levels of 1-3 mK in
.
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Figure 1: Rotational lines of a) CH2CHCN, b) CH2CN, c) CH3CCH, d) CH3CN, and e) H2CS observed toward IRC +10216 with the IRAM 30-m telescope at a spectral resolution of 1 MHz. The frequency scale is computed for an LSR source velocity of -26.5 km s-1. For comparison purposes, the thick grey panels show spectra corresponding to CRL 618 (from Pardo et al. 2007). ``U'' means Unidentified line. |
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Table 1: Line parameters of CH2CHCN, CH2CN, CH3CCH, and H2CS in IRC +10216.
Figure 1 shows the observed spectra of IRC +10216
corresponding to the CH2CHCN, CH2CN, CH3CCH, and H2CS lines. The observational line parameters, obtained by using the SHELL fitting routine of the CLASS
package, are given in
Table 1. Linewidths have been fixed in
many cases due to limited signal-to-noise (S/N) ratio or due to
blending with other lines. The measured widths are consistent with
an expansion velocity
around 14.5 km s-1, in
agreement with most of the molecular lines arising from the
expanding envelope of IRC +10216 (Cernicharo et al. 2000). There are no
missing lines of CH2CN, CH3CCH or H2CS in the 3 mm
atmospheric window. However, some lines of CH2CHCN having
similar strengths and upper level energies to those reported in
Table 1 are not listed due to a complete
blending with a stronger line or due to a low sensitivity of the
spectra. For example the 110,11-100,10 transition at
103 575 MHz is blended with a strong component of the J= 21/2-19/2
doublet of C4H.
The line profiles can give us information on the spatial
distribution of the molecules. In a spherically expanding envelope
and for lines with a low optical depth, a double-peaked shape
indicates that the emitting species has a distribution with an
angular extent comparable or larger than the telescope beam (HPBW = 21''-31'' for IRAM 30-m at 3 mm), while a flat-topped
profile indicates that the emitting region is not spatially
resolved by the telescope beam. The lines of CH3CN in IRC +10216 have a double-peaked character (see Fig. 1), which indicates that this molecule has an extended distribution.
In the case of the four species with which we are concerned, the
low S/N ratio of most of the observed lines makes it difficult to
distinguish whether line profiles are predominantly double-peaked
or flat-topped for a given species. Therefore, any conclusion
about the spatial distribution of the molecules derived from the
line profiles must be taken with caution. We will, nevertheless,
consider that CH2CHCN, CH2CN, CH3CCH, and H2CS have an
extended distribution, based on chemical arguments (see Sect. 3.2 and
Fig. 3), which essentially fills the telescope beam.
Under such hypothesis, we have constructed rotational temperature
diagrams to derive beam averaged column densities.
For CH2CHCN (see Fig. 2) we derive a total column
density
= (5.5
1.5)
1012 cm-2and a rotational temperature of 46
16 K, which is within the
range of rotational temperatures derived for other
shell-distributed molecules in IRC +10216: 20-50 K (Cernicharo et al. 2000).
In the case of CH2CN, we have used all the observed lines - ortho and para - in a single rotational diagram (see Fig. 2). Given that the lines are detected with a low
S/N ratio, we do not aim at determining the O/P ratio although the
available data is consistent with the statistical value 3:1. We
derive a rotational temperature of 50
13 K and a total
column density of
= (8.6
1.4)
1012 cm-2, which is comparable to that of the related species CH3CN (see Table 2).
![]() |
Figure 2:
Rotational temperature diagrams of CH2CHCN and
CH2CN in IRC +10216.
![]() ![]() ![]() |
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The two CH3CCH lines detected are very likely a sum of the K = 0, 1 components, although the low S/N ratio does not allow us to clearly distinguish them. Assuming a rotational temperature of 30 K we tentatively derive a total column density of 1.8
1013 cm-2. This value is comparable to the column
density of CH3CN in IRC +10216, which is detected through lines
about 25 times stronger than those of CH3CCH due to its much
larger dipole moment (
= 3.925 D versus
= 0.780 D).
Both CH3CN and CH3CCH have been also detected in the C-rich preplanetary nebula CRL 618 (Pardo & Cernicharo 2006; Cernicharo et al. 2001; Pardo et al. 2007; see also Fig. 1), which is in a evolutionary stage immediately following that of IRC +10216. However, the CH3CCH/CH3CN ratio is noticeably different in these two objects. In IRC +10216 both molecules are present with a similar abundance (CH3CCH/CH3CN = 0.6). In contrast, in CRL 618 methylacetylene is much more abundant than methyl cyanide (Pardo et al. 2007), not only in the region corresponding to the first post-AGB ejections (CH3CCH/CH3CN = 6) but also in the warm and dense inner regions where UV photons efficiently drive a rich C-based photochemistry (CH3CCH/CH3CN = 15). Such a stage has not yet been reached by IRC +10216.
The four lines of H2CS observed in IRC +10216 have similar
values, thus it is rather difficult to constrain the
rotational temperature. Assuming an statistical O/P ratio of 3:1
and a rotational temperature of 30 K we derive a total column
density
= 1.0
1013 cm-2 for
thioformaldehyde, which is almost twice larger than that of
formaldehyde (Ford et al. 2004; see Table 2).
In order to explain how the detected species are formed we have constructed a detailed chemical model of the outer envelope. The chemical network consists of 385 gas phase species linked by 6547 reactions, whose rate constants have been taken from Cernicharo (2004), Agúndez & Cernicharo (2006) and from the UMIST Database for Astrochemistry (Woodall et al. 2007). The temperature and density radial profiles as well as other physical assumptions are taken from Agúndez & Cernicharo (2006). The resulting abundance radial profiles for CH2CHCN, CH2CN, CH3CCH, H2CS and related species are plotted in Fig. 3. The model predicts that these four molecules would display an extended shell-type distribution with an angular radius of about 20''. The predicted and observed column densities are summarized in Table 2.
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Figure 3: Abundances of CH2CHCN, CH2CN, CH3CCH, H2CS (solid lines) and related species (dotted and dashed lines) given by the chemical model, as a function of radius ( bottom axis) and angular distance ( top axis) for an assumed stellar distance of 150 pc. |
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Vinyl cyanide results from the reaction between CN and ethylene,
the latter being found in the inner envelope with an abundance
relative to H2 of 2
10-8 (Goldhaber et al. 1987). This
reaction has been studied in the laboratory and found to be very
rapid at low temperature (Sims et al. 1993) yielding vinyl cyanide
(Choi et al. 2004):
![]() |
(1) |
Table 2: Column densities of selected molecules in IRC +10216.
The dissociative recombination (DR) of the ion CH3CNH+ is
the major pathway to form both CH2CN and CH3CN:
![]() |
(2) |
The related species CH3C3N is formed by the same sequence of
reactions that produces CH3CN, just replacing HCN by HC3N.
Its predicted column density is lower than that of CH3CN by
more than one order of magnitude. However, since our model
predicts less CH3CN than observed, the CH3+ ion is probably
underproduced, the column density of CH3C3N is most likely
underestimated. If CH3C3N were present with a column density
of several 1011 cm-2, the expected brightness
temperatures would be a few mK and therefore it could be
detectable. In fact, our IRAM 30-m line survey at 3 mm
of IRC +10216 (Cernicharo et al., in preparation) shows two
unidentified features with
2-3 mK at 86 756 MHz and
103 280 MHz that could correspond to the J = 21-20 and J =
25-24 transitions of CH3C3N respectively. The spectra
covering other 3 mm transitions of CH3C3N are not sensitive
enough to confirm or discard the presence of this species.
The synthesis of CH3CCH involves various ion-molecule reactions
with the dissociative recombination of the ions C3H5+ and
C4H5+ as the last step. The model underestimates the
observed CH3CCH column density by one order of magnitude,
probably due to uncertainties and/or incompleteness in the
chemical network. The heavier chain CH3C4H is predicted to
have a column density even higher than that of CH3CCH. The
smaller rotational constant B and larger rotational partition
function of CH3C4H makes it less favorable for being
observed at millimetre wavelengths. However its larger dipole
moment (
= 1.207 D versus
= 0.784 D) could result in line intensities similar to those of CH3CCH. Our IRAM 30-m
3 mm data shows an unidentified feature with
3 mK at 81 427 MHz that could be assigned to the
J = 20-19 transition of CH3C4H. As occurs with
CH3C3N, the detection of CH3C4H remains tentative
since our current spectra covering other 3 mm lines is not
sensitive enough.
Lastly, as previously discussed by Agúndez & Cernicharo (2006), H2CS is
formed by the neutral-neutral reaction S + CH3 and the
dissociative recombination of H3CS+. The predicted column
density is
= 1.3
1012 cm-2, which is
a factor 7 lower than the value derived from observations. We note
that a significant fraction of both H2CO and H2CS could be
formed on grain surfaces by hydrogenation of CO and CS
respectively. It is remarkable that in IRC +10216 thioformaldehyde
is more abundant than formaldehyde, despite the cosmic abundance
of oxygen being 50 times larger than that of sulphur. The
carbon-rich character of the CSE makes oxygen-bearing species to
have a very low abundance.
The chemical model predicts that the molecules formed in the outer
envelope have their peak abundances between 3
1016 cm and 6
1016 cm, which corresponds to angular radii
of 13''-26'' for an assumed distance to IRC +10216 of 150 pc (see
Fig. 3). Interferometric observations at millimetre
wavelengths have located the molecular shell at about 15''(Lucas et al. 1995; Guélin et al. 1993; Audinos et al. 1994) although the exact value depends on the
molecule and transition mapped. At this distance the gas density
is a few 104 cm-3 and the gas kinetic temperature is lower
than 20 K (Skinner et al. 1999). We may ask ourselves how the rotational
levels are excited to result in rotational temperatures for
CH2CHCN and CH2CN of 40-50 K, well above the gas kinetic temperature.
Collisions with H2 molecules do not seem to be responsible of
such an excitation. For example, in the case of the cyanomethyl
radical the collision coefficients
for
CH2CN-H2 have not been measured or calculated but should be
similar to those calculated for CH3CN-H2 by Green (1986),
at least for the
= 0 ladder (see Turner et al. 1990, for more
details). Thus, adopting a deexcitation collision coefficient
= 10-10 cm3 s-1, typical for
J = -1,
K = 0 transitions of CH3CN, and an
Einstein coefficient for spontaneous emission of
= 5
10-5 s-1, the resulting critical density is
=
/
= 5
105 cm-3.
This value is larger than the gas density expected at a distance
of 4-5
1016 cm, so that the rotational levels are
not thermalized and collisional excitation by itself should result
in a rotational temperature lower than the gas kinetic
temperature. In the cases of molecules such as CH2CN, with a
relatively large dipole moment, i.e. whose rotational levels are
hardly thermalized in the outer envelope, and which have
rotational temperatures above the kinetic temperature of the gas,
the excitation is most probably dominated by a radiative mechanism.
Absorption of infrared photons and pumping into excited
vibrational levels followed by radiative decay to rotational
levels in the ground vibrational state has been invoked many years
ago as the main excitation mechanism for some circumstellar
molecules in IRC +10216 (Morris 1975). As a matter of fact,
several molecules present in the outer envelope have been detected
in excited vibrational states, e.g. C4H = 1, 2 (
= 131 cm-1; Yamamoto et al. 1987; Guélin et al. 1987), HC3N
= 1
(
= 223 cm-1; Cernicharo et al. 2000), l-C3H
= 1
(
= 28 cm-1; Cernicharo et al. 2000), and SiC2
= 1
(
= 160 cm-1; Cernicharo et al. 2000; Gensheimer & Snyder 1997). Radiative
transfer calculations have also evidenced the importance of
infrared pumping in exciting molecules such as HC5N
(Deguchi & Uyemura 1984) and H2O (Agúndez & Cernicharo 2006) in IRC +10216. For this
process to be efficient, the molecules must have vibrational modes
active in the infrared, sufficiently strong and with a frequency
at which the central object emits a high flux. The spectrum of IRC +10216 as seen by ISO peaks at a wavelength of
10
m (Cernicharo et al. 1999) and the flux is very large within a wide wavelength
range (see below). In fact, the excited vibrational states of
C4H, HC3N, l-C3H, and SiC2 detected have wavelengths
between 45 and 357
m.
In the case of CH2CHCN, there exists a large number of
vibrational modes, the strongest of which are the bending modes
and
at 972 cm-1 (10.3
m) and 954 cm-1 (10.5
m) respectively (Khlifi et al. 1999; Cerceau et al. 1985).
For CH2CN the only available experimental information concerns
the
mode at 664 cm-1 (15.1
m; Sumiyoshi et al. 1996).
In order to give a quantitative estimate of how important is the
infrared pumping compared to excitation by collisions, we may
evaluate the rates of both processes. The excitation by infrared
pumping operates through absorption of an infrared photon and
promotion of a molecule from a given rotational level in the
ground vibrational state (v0, J'') to another rotational
level in an excited vibrational state (v1, J), from which it
decays spontaneously to a different rotational level of the ground
vibrational state (v0, J') through either a single transition
or a radiative cascade process. The rate at which the latter level (v0, J') is populated is then governed by the rate of the
absorption process: v0, J''
v1, J, which
is given by:
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(3) |
The rate at which the rotational level (v0, J') is populated
by collisions with H2 molecules is given by:
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(4) |
To estimate the infrared flux in the outer envelope we have used
the radiative transfer model described in Fonfría et al. (2007) and the
ISO observations of IRC +10216 (Cernicharo et al. 1999). The best fit to the
observed continuum between 7 and 27
is shown in the lower
panel of Fig. 4. The SiC band at 11.3
m is
correctly reproduced. At long wavelengths the model seems to
underestimate the absolute observed flux, which is nevertheless
affected by the uncertainties in the multiplicative calibration
factors applied in the data reduction (Swinyard et al. 1998).
The model has been used to calculate the radiation field at a
distance of r = 5
1016 cm (20'') from the star
(see upper panel in Fig. 4). The calculated
spectral energy distribution can be approximated by a blackbody
with a radius
= 13 R* and a temperature
= 550 K (see upper panel in Fig. 4), so that we may use the Planck function for such a blackbody to evaluate
4
and see whether the rate for infrared pumping
exceeds or not the collisional excitation rate. The radiative over
collisional ``excess'' (
/
)
may be evaluated as:
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(5) |
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(6) |
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Figure 4:
Spectral energy distribution of IRC +10216 at infrared
wavelengths. The lower panel shows the fit to the continuum
observed by ISO. Most of the discrepancies between model and
observations in the 7-20 ![]() ![]() ![]() ![]() |
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Figure 5:
Abundances of carbon chain molecules in IRC +10216 and
TMC-1. The diagram is an extension of that published by
Cernicharo et al. (1987). The fractional abundances relative to H2 are
computed from the molecular column densities and the total H2 column density. We use N(H2) = 1022 cm-2 in TMC-1 (Cernicharo & Guélin 1987) and N(H2) = 2 ![]() ![]() ![]() |
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The detection in IRC +10216 of the partially saturated organic molecules reported in this Paper invites for a comparison to TMC-1, the other Galactic source that displays, together with IRC +10216, the largest wealth in unsaturated carbon chain molecules. For that purpose we have represented in Fig. 5 the fractional abundances of carbon chains in these two sources as a function of the number of heavy atoms.
Chemistry proceeds in a different way in these two objects. In IRC +10216 interstellar UV photons drive the chemistry by photodissociating the closed shell molecules flowing out from the inner envelope. In TMC-1 the gas is well shielded against the interstellar UV field and the built-up of molecules is driven by ionisation by cosmic rays. This introduces a sharp difference in the time scales of the processes being at work. In IRC +10216 the gas travels throughout the CSE during a few thousands of years and the chemical processes take place in shorter time scales. In TMC-1 the built-up of molecules has time scales of the order of millions of years and the depletion from the gas of some species, due to condensation on grains, is a major issue at late times. A consequence of this is the lower level at which molecules are present in TMC-1 compared to IRC +10216. As an example we see in Fig. 5 that the most abundant carbon chains in both sources are those with a highly unsaturated character, cyanopolyynes and polyyne radicals, the abundances of which are larger in IRC +10216 than in TMC-1 by more than one order of magnitude.
Another important difference between these two sources could lie in the C/O ratio. In IRC +10216, the processes of dredge-up related to the AGB phase have resulted in a photospheric C/O ratio higher than 1. This controls the chemistry in the outer envelope: almost all the oxygen keeps locked into CO during most of the expansion while the carbon in excess can participate in a rich carbon chemistry. In TMC-1 it is not clear whether the C/O ratio is higher or lower than 1. The large number of carbon chains found argues in favor of a C/O ratio >1, which is unusual for a dense cloud, and some chemical models have used it because a better agreement with observations is achieved (Smith et al. 2004). On the other hand, oxygen is cosmically more abundant than carbon and TMC-1 contains a substantial number of O-bearing molecules (Ohishi & Kaifu 1998), which points toward a C/O ratio <1. If the latter is true, then the carbon chemistry would be limited due to the presence of atomic oxygen which tends to destroy the chemical complexity (Herbst et al. 1994), something that does not happen in IRC +10216 due to the unavailability of free atomic oxygen (Millar & Herbst 1994). This could also explain the systematically lower abundances of carbon chains in TMC-1 compared to IRC +10216.
If we focus on partially saturated species, such as methylpolyynes, methylcyanopolyynes, CH2CN or CH2CHCN, then we note that in IRC +10216 they are present at a lower level than the highly unsaturated species, while in TMC-1 partially saturated and highly unsaturated molecules have abundances in many cases comparable; e.g. compare the ratio of the abundances of CH2CN and HC3N in both sources. Thus, chemistry seems to favor the presence of species with a higher degree of saturation in dark clouds than in C-rich circumstellar envelopes. The recent detection of the highly saturated hydrocarbon propylene in TMC-1 (Marcelino et al. 2007) supports this point.
In IRC +10216 the UV field which drives the chemistry is mostly photodissociating but not ionising, so that the dominant reactions are neutral-neutral rather than ion-molecule. In TMC-1, the chemistry is triggered by cosmic rays ionisation, and ion-molecule reactions do greatly participate in the built-up of molecules. Note that chemical models have traditionally explained the formation of molecules in interstellar clouds by means of ion-molecule reactions. However, since it was discovered that some neutral-neutral reactions are very rapid at low temperatures, it is now thought that these latter reactions dominate the formation of highly unsaturated carbon chains such as cyanopolyynes (Herbst et al. 1994). That is, in general terms we may state that ``current gas phase chemical models form highly unsaturated carbon chains mostly by neutral-neutral reactions while partially saturated molecules are generally formed by ion-molecule reactions''. Therefore, ion-molecule reactions could be, ultimately, the responsible of the higher degree of saturation observed in TMC-1 compared to IRC +10216. Grain surface reactions, which are very efficient in producing highly saturated molecules, could also play a role in the peculiar chemistry of TMC-1. However, it is not clear how these mantle species would be desorbed to the gas phase at the low temperatures prevailing in these regions.
In summary, we have shown that apart from the abundant highly unsaturated cyanopolyynes and polyyne radicals, analogous molecules with a higher degree of saturation are also present in IRC +10216. In this paper we have presented the detection of CH2CHCN, CH2CN, CH3CCH, and also of thioformaldehyde. The relatively high rotational temperatures, 40-50 K, derived for CH2CHCN and CH2CN suggest that these species are excited in the circumstellar envelope through radiative pumping to excited vibrational states.
The formation of partially saturated organic molecules in IRC +10216 resembles that occurring in cold dense clouds and stresses the similarity between the chemistry in these two types of sources. However, unlike in TMC-1, their abundances are much lower than those of highly unsaturated molecules, like cyanopolyynes and polyyne radicals, which reflects the differences in the chemical processes at work in dark clouds and C-rich circumstellar envelopes.
Acknowledgements
We acknowledge comments and suggestions from the referee. This work has been supported by Spanish MEC through grants AYA2003-2785, ESP2004-665 and AYA2006-14876, by ``Comunidad de Madrid'' under PRICIT project S-0505/ESP-0237 (ASTROCAM) and by the European Community's human potential Programme under contract MCRTN-CT-2004-51230 (The Molecular Universe). MA also acknowledges funding support from Spanish MEC through grant AP2003-4619.