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# Molecular line study of evolution in protostellar cloud cores

## 1 Introduction

To understand the first steps of the star-formation process, we must be able to follow the evolution of molecular cloud cores. One approach is to conduct spectral-line observations of molecular species whose abundances vary significantly with time. Conversely, combining such observations with other types of diagnostics of cloud evolution, the chemical models may be tested.

Examples of species that are believed to be useful for the aforementioned purposes are complex hydrocarbons and cyanopolyynes111Molecules with the generic form HC(2n+1)N where $`n=1,2,\mathrm{}`$. Their abundances are expected to peak at early stages of the evolution of dark clouds (e.g. Herbst & Leung (1989)). This is because their production requires a high abundance of free neutral carbon (C i); a condition that is satisfied at early times in the chemical evolution, whereas at later stages practically all free carbon has been exhausted in the production of CO. In contrast, molecules such as NH3 and SO increase in abundance with time, because their formation involves relatively slow neutral-neutral reactions (Suzuki et al. (1992); Hirahara et al. (1995); Nilsson et al. (2000)), or because they (e.g. SO) are destroyed by C i or C+.

The validity of these model predictions have, to date, been tested in a rather limited sample of dark cloud cores. Most observations have been confined to the Taurus Molecular Cloud 1 (TMC-1), L134A, and to a number of “Myers’ cores” (Pratap et al. (1997); Swade (1989); Myers & Benson (1983), Benson et al. (1998); for a review see van Dishoeck & Blake (1998)). However, for current chemistry models to be rigorously tested, the cloud sample needs to be more representative of the ISM. In the present paper we extend the sample of well-studied objects by two potentially very young molecular cloud cores.

The first core selected for this study is located in the region of the reflection nebula Cederblad 110 in the Chamaeleon dark cloud i. Reipurth et al. (1996) detected a strong 1.3mm dust continuum source towards this core, and designated it as Cha-MMS1. The core belongs to an extensive, northeast–southwest directed filament of dense gas near the centre of this cloud (Mattila et al. (1989)). The second core, CrA C (Harju et al. (1993)) is located in the southeastern ‘tail’ of the R Coronae Australis molecular cloud. The distances to the Chamaeleon i and the R Coronae Australis clouds are 150 and 170 pc, respectively (Knude & Høg (1998)). The smallest diameters of the C18O cores are 0.11 and 0.05 pc for CrA C and Cha-MMS1, respectively. The C18O column densities towards both cores are similar: $`N(\mathrm{C}^{18}\mathrm{O})\mathrm{2\hspace{0.17em}10}^{15}\mathrm{cm}^2`$, which corresponds to a molecular hydrogen column density of $`N(\mathrm{H}_2)10^{22}\mathrm{cm}^2`$ (Harju et al. (1993); Mattila et al. (1989)). The average H2 densities derived from these numbers assuming prolate geometries are $`\mathrm{3\hspace{0.17em}10}^4`$ and $`\mathrm{7\hspace{0.17em}10}^4`$ cm-3 for CrA C and Cha-MMS1, respectively. The kinetic temperature in CrA C is 10 K or less (Harju et al. (1993)), whereas in Cha-MMS1 the gas kinetic temperature as derived from ammonia observations is slightly elevated with respect to the typical dark cloud value, being $`14`$ K (Toth et al. 2000, in preparation).

Even though both cores are supposed to be young, they represent different stages of cloud evolution. Cha-MMS1 probably contains a Class 0 protostar (Reipurth et al. (1996)), which has been recently identified with a far-infrared source, designated Ced110 IRS 10, by Lehtinen et al. (2000). The core lies next to a small group of newly-born stars, the closest being Ced 110 IRS 4 (Prusti et al. (1991)) and the newly detected IRS 11 (Lehtinen et al. (2000)), which belong to the infrared source Class I. The core is associated with a compact, north-south oriented molecular outflow (Mattila et al. (1989); Prusti et al. (1991); Lehtinen et al. (2000)). Reipurth et al. (1996) suggested that Cha-MMS1 contains the driving source of the outflow and the Herbig-Haro objects HH 49/50 located some $`10\mathrm{}`$ south of the core.

CrA C shows no sign of star formation activity. The core appears to be surrounded by an extensive halo: it is located near the centre of a neutral atomic hydrogen ring with a diameter of $`40^{}`$ (Llewellyn et al. (1981)) which may represent the outer boundary of a massive H i to H2 conversion region. Observations of continuum emission at 100 $`\mu `$m and 200 $`\mu `$m wavelenghts with the ISOPHOT instrument on the Infrared Space Observatory (ISO) reveal a 200$`\mu `$m excess coinciding with the centre of CrA C (Heikkilä et al. 2000, in preparation), suggesting that a very cold clump is located inside this core.

Based on these facts, one could expect CrA C to exhibit the characteristics of ‘early time’ chemistry, e.g. high abundances of unsaturated carbon compounds, whereas Cha-MMS1 could be thought to have reached a more evolved stage. In order to test these ideas, we have estimated for these dense cores the column densities of several molecules which show significant time dependence in chemistry models.

The selected molecules are discussed in the next Section. In Sect. 3 we describe the observational procedure. In Sect. 4 the results from the observations are presented and these are further discussed in Sect. 5. Finally, in Sect. 6 we summarize our conclusions.

## 2 Observed molecules

We discuss here the spectroscopic and chemical properties of the molecules included in this study. Table 1 lists their chemical formulae, structure types (hfs means that the lines have hyperfine structure; o/p and $`A/E`$ that the molecule has ortho and para or $`A`$-symmetry and $`E`$-symmetry forms, respectively), permanent electric dipole moments ($`\mu _{\mathrm{electric}}`$) along the relevant molecular axises, and rotational constants ($`A`$, $`B`$ and $`C`$). The data were extracted mainly from the JPL catalogue222An updated version is available on the WWW at http://spec.jpl.nasa.gov. (Poynter & Pickett (1985)); exceptions are the CH3OH data (Sastry et al. (1981); Anderson et al. (1990)) and the value for the dipole moment of CCS (Murukami (1990)).

### 2.1 Spectroscopic properties

Carbon monosulphide, CS, is a linear molecule with a simple rotational spectrum; the states are denoted by the total angular momentum quantum number $`J`$. The simplicity of the spectrum is due to the facts that in the electronic ground state, the electrons in the CS molecule have paired spins and possess no orbital angular momentum. Hence, the ground state is denoted $`{}_{}{}^{1}\mathrm{\Sigma }`$. In addition, the C and S nuclei have no spin.

The dicarbon sulphide radical, CCS, and the sulphur monoxide radical, SO, have more complicated spectra than CS. The electrons in the electronic ground states of CCS and SO have no net orbital angular momentum, but the total spin is non-zero due to two electrons having unpaired spins. Thus, the spin quantum number is $`S=1`$ and the electronic ground state is denoted $`{}_{}{}^{3}\mathrm{\Sigma }`$ (e.g. Gordy & Cook (1970), Sect. 4.2). The electron spin is coupled to the weak magnetic field arising from the rotation of the molecule. Since $`S`$=1, for each molecular rotational level with the rotational angular momentum quantum number $`N>0`$, the total angular momentum quantum number, $`J`$, has three possible values: $`J=N1`$, $`J=N`$ or $`J=N+1`$. Consequently, the rotational levels $`N>0`$ are split into triplets, whereas for $`N`$=0 only one state ($`J_N=1_0`$) exists (e.g. Yamamoto et al. (1990)).

Hydrogen isocyanide, HNC, is a linear molecule. The nitrogen nucleus has a non-zero spin, and therefore possesses an electric quadrupole moment. This interacts with the electric field gradient of the molecule, which depends on the rotation. Consequently, the nuclear spin ($`I=1`$) is coupled to the molecular rotational angular momentum, $`J`$, to yield the total angular momentum, $`F`$ (Gordy & Cook (1970), Sect. 9.4). The resulting hyperfine splitting of the rotational lines of HNC is smaller than for its isomer HCN. For example, for the lowest rotational transition ($`J=10`$) the $`F=11`$ and $`F=01`$ components are separated from the main component $`F=21`$ by $`0.27`$ and $`+0.41`$ km s-1 respectively (Frerking et al. (1979)). Hence, the hyperfine structure is usually not resolved in observations due to Doppler broadening in the source and the insufficient spectral resolution of the spectrometers available.

Cyanoacetylene, HC3N, is also a linear molecule. Due to its high moment of inertia, it has a small rotational constant ($`B`$) and its rotational transitions $`JJ1`$ lie relatively closely in frequency. Many of these lines are located in the commonly observed frequency bands, and it is often used in multi-transition studies. Like HNC, it has hyperfine structure due to the nuclear spin of nitrogen. For higher $`J`$-values, however, the relative energy differences between different $`F`$-levels are very small, and so no hyperfine structure is seen in the spectra observed here.

Methyl acetylene, CH3CCH, is a low dipole moment, symmetric top molecule. Its energy levels are described by two quantum numbers $`J`$ and $`K`$. The former represents the total angular momentum and the latter is the projection of $`J`$ on the symmetry axis of the molecule. The lowest energy state in each $`K`$-ladder is $`J`$=$`K`$. CH3CCH exists in two chemically different forms, the so called $`A`$ and $`E`$ symmetry species, depending on the relative orientations of the spins of the three hydrogen nuclei in the CH3 group. For the $`A`$-symmetry species, the $`K`$ quantum numbers are multiples of 3 (i.e. $`K=3n`$; $`n`$=0,1,2,…), while the $`E`$-symmetry species has $`K=3n+1`$ and $`3n+2`$; $`n`$=0,1,2,… . The ground-state energies for $`A`$ and $`E`$ CH3CCH differ by 8.02 K, $`E`$ lying higher in energy. There are no allowed electric dipole transitions between two states belonging to different $`K`$-ladders. Consequently, the relative populations of two $`K`$-ladders are determined by collisional transitions and therefore depend on the kinetic temperature. In fact, the so-called ‘rotational temperature’, which can be determined from a single observation of a $`JJ1,K`$multiplet (the lines lie closely in frequency), is considered to be a good approximation of the kinetic temperature (e.g. Bergin et al. (1994)).

Cyclo-propenylidene, c-C3H2, is one of the few cyclic molecules detected in interstellar space. It is a slightly asymmetric, almost oblate top. C3H2 has ortho\- and para-states originating from the two possible relative orientations of the spins of the two hydrogen nuclei (having $`I=\frac{1}{2}`$ each). In the ortho-state the spins are parallel ($`I=1`$), whereas in the para-state the spins are anti-parallel ($`I=0`$). Since the ortho- and para-forms cannot be interchanged in electric dipole transitions or easily in chemical reactions, they can be seen as two different chemical compounds. The ground-state of the ortho-form ($`J_{K_a,K_c}=1_{0,1}`$) lies 2.35 K higher than that of the para-form ($`J_{K_a,K_c}=0_{0,0}`$). The electric dipole transitions of c-C3H2 are of $`b`$-type. This means that the quantum numbers describing the projection of $`J`$ on the molecular $`a`$axes and $`c`$axes, $`K_a`$ and $`K_c`$, change according to the rule $`\mathrm{\Delta }K_a=\pm 1`$, $`\mathrm{\Delta }K_c=\pm 1`$ (see Vrtilek et al. (1987)).

Diazenylium, N2H+, is a linear molecular ion. Its rotational transitions have hyperfine structure due to the coupling of the spins of the two nitrogen nuclei ($`I_1`$,$`I_2`$) to the rotational angular momentum ($`J`$). The energy levels are labelled using the quantum numbers $`J`$, $`F_1`$ and $`F`$, where $`F_1=J+I_1`$ and $`F=F_1+I_2`$ (e.g. Caselli et al. (1995); Gordy & Cook (1970), Sect. 9.5). The $`J=10`$ transition observed here has seven well resolved hyperfine components.

Methanol, CH3OH, is a slightly asymmetric top (e.g. Townes & Schawlow (1975), chapters 4 & 12). It has a rather complicated rotational spectrum, since it exhibits so called hindered internal rotation: the hydroxyl (OH) group can rotate with respect to the methyl (CH3) group. This gives rise to two different forms of CH3OH between which both radiative and collisional transitions are forbidden: the $`A`$-symmetry and $`E`$-symmetry forms. Chemical reactions that might convert $`A`$ to $`E`$ or vice versa are believed to occur only on very long time scales. Therefore the two forms of CH3OH can be treated as chemically distinct species. The ground-state of the $`E`$-symmetry form ($`J_k=1_1E`$) lies 6.95 K higher than that of the $`A`$-symmetry form ($`J_k=0_0A^+`$). The relevant quantum numbers describing the rotational spectrum are $`J`$ and $`k`$, with $`k=K_aK_c`$. The electric dipole transitions observed here are of $`a`$-type, i.e. they obey the selection rule $`\mathrm{\Delta }k=0`$. Like other symmetric or slightly asymmetric tops, CH3OH may provide useful information about the gas temperature.

### 2.2 Chemistry

The buildup of cyanopolyynes proceeds mainly via reactions between complex hydrocarbon ions and nitrogen atoms (Herbst & Leung (1989)). HC3N is the simplest cyanopolyyne, and its abundance correlates well with heavier cyanopolyynes (e.g. Federman et al. (1990)). Due to its large dipole moment, as well as being chemically an early-time species, HC3N should be a useful probe of the conditions in pre-stellar cloud cores.

The main reactions leading to HC3N and CH3CCH involve either the C3H$`{}_{}{}^{+}{}_{2}{}^{}`$ or C3H$`{}_{}{}^{+}{}_{3}{}^{}`$ ions (Huntress & Mitchell (1979)). The neutral reactions involving C2H2 and CCH suggested recently by Turner et al. (1998) and Turner et al. (1999) do not change this fact, since these species are also derivatives of the aforementioned molecular ions. Therefore, HC3N and CH3CCH abundances are expected to be well correlated.

Reactions of nitrogen-bearing ions, such as HCNH+, with neutral hydrocarbons may also contribute to the production of cyanopolyynes (Herbst & Leung (1989)). Since HCNH+ is the precursor ion of HCN and HNC (Herbst (1978)), a correlation between these isomeric molecules and cyanopolyynes is possible. In this paper, we shall not address the as yet unresolved problem of the variation of the HNC/HCN abundance ratio from source to source (for a recent overview see e.g. Talbi & Herbst (1998)). We instead used HNC merely to survey the extension of the core CrA C, where HC3N was not detected. This should be as abundant as HCN but easier to detect due to the smaller hyperfine splitting,

In their survey towards dense cores of dark clouds, Suzuki et al. (1992) found a strong correlation between the CCS and HC3N column densities, and, using data from Cox et al. (1989), a weaker correlation between CCS and C3H2. They explained these correlations by the production of CCS in reactions between hydrocarbons and S+, which should be abundant in regions where also carbon-chain molecules are formed (Prasad & Huntress (1982)). The formation of CS also involves S+ and occurs in the very early stages of chemical evolution. Thereafter, CS is mainly recycled via the thioformyl ion, HCS+, and its abundance is considered to be rather constant in time (Nejad & Wagenblast (1999)).

The correlation between HC3N and CCS is due to fact that C3H dominates the production of both molecules. HC3N is related to C3H2 via the neutral-neutral reaction $`\mathrm{C}_3\mathrm{H}_2+\mathrm{N}\mathrm{HC}_3\mathrm{N}+\mathrm{H}`$ (Herbst & Leung (1989); Nejad & Wagenblast (1999)). On the other hand, complex carbon chain molecules and CCS show no correlation with ammonia, NH3 (e.g. Little et al. (1979); Suzuki et al. (1992)). This can be explained by the fact that the production of NH3 involves molecular nitrogen, N2, which is formed in neutral-neutral reactions and becomes abundant in the later stages of cloud evolution when carbon chain molecules have already been lost in reactions with ions such as He+, H+ and H$`{}_{}{}^{+}{}_{3}{}^{}`$ (Suzuki et al. (1992)). N2H+ is also formed from N2 by $`\mathrm{N}_2+\mathrm{H}_3^+\mathrm{N}_2\mathrm{H}^++\mathrm{H}_2`$ and its abundance has been found to follow closely that of NH3 (Hirahara et al. (1995); Nejad & Wagenblast (1999)). Therefore, if the CCS/NH3 abundance ratio can be used as an age indicator as suggested by Suzuki et al. (1992), the same should be true for CCS/N2H+. The depletion of CO onto grain surfaces further increases the N2H+ abundance by making H$`{}_{}{}^{+}{}_{3}{}^{}`$ available for non-carbon bearing species to react with (Nejad & Wagenblast (1999)).

SO is destroyed by neutral carbon and, like N2H+, it is formed in neutral-neutral reactions and benefits from the freezing-out of CO. Its abundance therefore increases slowly and probably remains low as long as the gas is rich in neutral atomic carbon. The SO abundance first increases when carbon is consumed in the production of CO, i.e. at late stages in the chemical evolution (Bergin & Langer (1997); Nejad & Wagenblast (1999)). The late peaking of SO and the stability of CS (until it too is frozen out) has led to the suggestion that the SO/CS abundance could be used as a chemical clock (Ruffle et al. (1999)). Nilsson et al. (2000) came to the same conclusion on the basis of pure gas phase chemistry models. However, the SO/CS ratio is also sensitive to the gas-phase O/C ratio. Thus, when observing the SO/CS ratio in two individual clouds, it is not easy to disentangle the effects of time evolution from those of the O/C ratio.

The precursor ion of CH3OH, CH3OH$`{}_{}{}^{+}{}_{2}{}^{}`$, is formed from the radiative association reaction between CH$`{}_{}{}^{+}{}_{3}{}^{}`$ and H2O (e.g. Herbst & Leung (1989)). The close relation to CH$`{}_{}{}^{+}{}_{3}{}^{}`$ makes CH3OH an early-time molecule, as long as gas phase reactions are considered. The large abundances of CH3OH in high-mass star-forming cores has been explained by evaporation from grain surfaces due to shock heating (e.g. Menten et al. (1988)).

## 3 Observations

The observations were made in February 1998 at the Swedish-ESO Submillimetre Telescope (SEST) on La Silla in Chile. The 100 and 150 GHz SIS receivers were used simultaneously. These were connected to a 2000 channel acousto-optical spectrometer (AOS), which was split in two bands of 43 MHz each. The resulting channel-separations are 0.13 km s-1 (at 100 GHz) and 0.09 km s-1 (at 150 GHz), respectively. Calibration was achieved by the chopper-wheel method. The pointing and focus of the telescope were checked at 3-4 hours intervals against the SiO($`v=1,J=21`$) maser line towards AH Sco, U Men and R Dor. The pointing accuracy was typically $`3\mathrm{}`$ (rms) in each coordinate.

Most of the lines were observed in the frequency switching mode with a frequency throw of 6 MHz. Position switching was used for CH3CCH and N2H+ since the spectrometer band covers several of their lines.

The observations were started by mapping both sources in the HC3N($`J=109`$) and SO($`J_N=4_33_2`$) transitions simultaneously in the frequency switching mode. HC3N was not detected in CrA C, and therefore the map was repeated in the transition pair HNC($`J=10`$) & SO($`J_N=4_33_2`$). The rest of the observations were single position pointings towards the SO (in CrA C) or HC3N (in Cha-MMS1) line emission peaks in these maps. Table 2 lists the $`(0,0)`$ positions used in the mapping observations and the peak positions, towards which the single pointing observations were made in each core.

In Table 3 we give a summary of the observed lines and some telescope characteristics at the corresponding frequencies. The columns of this Table are: (1) the rest-frequency; (2) the molecule; (3) the transition; (4) the line strength of the transition ($`S_{ul}`$); (5) the energy of the upper level of the transition ($`E_u/k`$); (6) and (7) the half-power beam-width ($`\mathrm{\Theta }_{\mathrm{mb}}`$) and the main beam efficiency ($`\eta _{\mathrm{mb}}`$) of the antenna. Further details of the SEST are available e.g. on the WWW at http://www.ls.eso.org/lasilla/Telescopes/SEST.

## 4 Results

### 4.1 Maps

The velocity-integrated HC3N($`J=109`$) and SO($`J_N=4_33_2`$) line-intensity maps of Cha-MMS1 are presented in Fig. 1. The locations of the embedded infrared sources Ced 110 IRS2, IRS4 and IRS6 (Prusti et al. (1991)), and the peak position of the 1.3 mm radio continuum source Cha-MMS1 (Reipurth et al. (1996)) are also indicated. It is evident from the map that the HC3N distribution is compact and peaks close to the dust continuum maximum, some $`30\mathrm{}`$ south of it. A comparison with Fig. 1 of Reipurth et al. (1996) shows that the dust continuum emission and the HC3N line emission have similar sizes and shapes, and therefore conceivably originate from the same source, despite the slight shift in the peak positions. The infrared point sources lie near the northeastern edge of the molecular cloud core. SO line emission is present in the compact core, but shows no clear concentration. The maxima lie on its northern and southern sides, and are possibly related to a molecular outflow (see Sect. 5).

The integrated HNC($`J=10`$) and SO($`J_N=4_33_2`$) intensity maps of CrA C are shown in Fig. 2. In these maps, the situation is the opposite of that in the maps of the Cha-MMS1 core. HNC, which was chosen instead of the undetected HC3N, is weak and dispersed, whereas SO has a strong peak towards the offset $`(30\mathrm{},30\mathrm{})`$ from the centre of the map, and a weaker second maximum towards the offset $`(60\mathrm{},30\mathrm{})`$.

### 4.2 Spectra and line parameters

One location in each core was observed in several molecular transitions. In Cha-MMS1 this position lies towards the HC3N peak at the offset $`(60\mathrm{},60\mathrm{})`$, $`17\mathrm{}`$ southeast of the dust continuum peak. In CrA C the selected position lies close to the SO peak at the offset $`(30\mathrm{},60\mathrm{})`$ from the map centre, which has the highest SO line intensities. The spectra obtained towards these two locations are shown in Figs. 3 and 4.

In Cha-MMS1 all observed transitions except HC3N($`J=1514`$) were detected. The energy of the upper state of this transition is rather high (52 K) and so the non-detection of this line in a cold cloud is unsurprising. Since the SO lines were rather weak ($`T_\mathrm{A}^{}0.7`$ K) and showed no self-absorption features, 34SO was not observed. In CH3CCH, only the $`K=0`$ and $`K=1`$ components of the $`J=54`$ and $`J=87`$ transitions were clearly detected. The upper limits (3$`\sigma `$) for the $`K`$=2 and $`K`$=3 components are $`T_\mathrm{A}^{}`$=0.063 K ($`J=54`$) and $`T_\mathrm{A}^{}`$=0.045 K ($`J=87`$), respectively.

In CrA C, both of the observed SO transitions ($`J_N=3_22_1`$ and $`4_33_2`$) were bright ($`T_\mathrm{A}^{}>1.5`$ K). Only a tentative detection of HC3N($`J=109`$) was made at a level of $`T_\mathrm{A}^{}`$=0.05 K, and so ther transitions were not attempted. None of the CH3CCH lines were detected, and the rest of the lines, both from carbonaceous species as well as from N2H+, were weaker than in Cha-MMS1.

The common isotopomer HNC shows a broad, asymmetric profile. The fact that the peak is shifted with respect to the other lines, in particular that of HN13C, can be explained by absorption in the low density halo around the core. The larger width of this transition is partly due to the hyperfine structure discussed in Sect. 2.1. However, the broad wings visible on both sides of the line centre are not seen in any other line (including C18O). The presence of high velocity gas towards this location should be tested in other optically thick transitions.

In both clouds the C3H$`{}_{2}{}^{}(J_{K_a,K_c}=3_{12}2_{21}`$) spectra also contain the $`J_k=3_12_1E`$ and $`J_k=3_02_0A^+`$ lines of CH3OH. The former component appears in Figs. 3 and 4 as a negative spike due to the frequency switching procedure.

The observed line parameters (from fits of Gaussian line-profiles) in the selected positions are given in Table 4. We list the peak antenna temperatures ($`T_\mathrm{A}^{}`$), the radial velocities ($`v_{\mathrm{LSR}}`$), the full-width at half-maximum (FWHM) line-widths ($`\mathrm{\Delta }v`$), and the velocity-integrated line-intensities ($`T_\mathrm{A}^{}𝑑v`$) of the detected lines for both cores. For the undetected lines, the upper limits (3$`\sigma `$) for $`T_\mathrm{A}^{}`$ are given.

### 4.3 Column densities

The method used in the calculation of the excitation temperatures, optical depths, and column densities is described in Appendix A. The results of this analysis are summarized In Table 5. The columns of this Table are: (1) the molecule; (2) the transition; (3), (4) and (5) the excitation temperature ($`T_{\mathrm{ex}}`$) and the line-centre optical depth ($`\tau _{\nu _{ul}}`$) of the transition, and the total column density ($`N_{\mathrm{tot}}`$) of the molecule in Cha-MMS1; (6), (7) and (8) $`T_{\mathrm{ex}}`$, $`\tau _{\nu _{ul}}`$ and $`N_{\mathrm{tot}}`$ for the same molecule and transition in CrA C.

We have estimated the column densities of C18O towards the centres of CrA C and Cha-MMS1 using data from Harju et al. (1993) and Haikala et al. 2000 (in preparation). Assuming optically thin line emission and a uniform excitation of the energy levels with $`T_{\mathrm{ex}}=`$ 10 K, we obtained $`N(\mathrm{C}^{18}\mathrm{O})\mathrm{3\hspace{0.17em}10}^{15}`$ cm-2 in CrA C, and $`N(\mathrm{C}^{18}\mathrm{O})\mathrm{2.5\hspace{0.17em}10}^{15}`$ cm-2 in Cha-MMS1. The two sources thus appear to have very similar C18O column densities. The column densities of the observed molecules relative to C18O are presented in Table 6. The conversion of the ratios listed in this Table to fractional abundances relative to H2 is not trivial. The fractional CO abundance is expected and has also been observed to change from cloud to cloud. As discussed by Harjunpää & Mattila (1996) the fractional C18O abundances can be different in star forming and non-star forming regions. The relations they derived towards the R CrA and the Cha I clouds (assuming $`N(\mathrm{H}_2)/E(JK)=\mathrm{5.4\hspace{0.17em}10}^{21}`$ cm-2 mag-1) give $`\mathrm{2.4\hspace{0.17em}10}^{22}`$ cm-2 and $`\mathrm{1.2\hspace{0.17em}10}^{22}`$ cm-2 for $`N(\mathrm{H}_2)`$ in CrA C and Cha-MMS1, respectively. However, neither region studied by Harjunpää & Mattila (1996) in these complexes is actually close to our sources. The assumption that the relation they derived towards Coalsack is valid in the quiescent CrA C would result in an H2 column density of $`\mathrm{3.8\hspace{0.17em}10}^{22}`$ cm-2. In comparison, the relation between $`N(\mathrm{H}_2)`$ and $`N(\mathrm{C}^{18}\mathrm{O})`$ derived by Frerking et al. (1979) in Taurus yields $`N(\mathrm{H}_2)=\mathrm{1.9\hspace{0.17em}10}^{22}`$ cm-2 and $`N(\mathrm{H}_2)=\mathrm{1.6\hspace{0.17em}10}^{22}`$ cm-2 towards CrA C and Cha-MMS1, respectively. All these H2 column densities are similar within a factor of two for each source, and so the values presented in Table 6 may be converted to approximate fractional abundances by multiplying them by $`2\times 10^7`$, bearing in mind that for CrA C, the value $`1\times 10^7`$ is possibly more appropriate.

Table 6 shows that the column densities of carbon chain molecules (CCS, HC3N, CH3CCH and C3H2) relative to C18O are much larger towards Cha-MMS1 than towards CrA C, for which upper limits only could be derived for all species other than CCS. The HC3N/C18O column density ratio towards Cha-MMS1 is almost 0.2, which implies that the fractional HC3N abundance is of order $`10^8`$, being several times larger than towards the cyanopolyyne maximum in TMC-1 (Pratap et al. (1997)). The SO/C18O abundance ratio is larger towards CrA C. Inspection of the intensity ratios of the 34SO and the normal isotope SO lines reveals that the latter are optically thick or even self-absorbed towards CrA C, and the derived SO column densities there are almost certainly lower limits (the terrestial 32S/34S isotope ratio is 22.5 and in the local interstellar medium values larger than 10 are normally assumed). On the other hand, the N2H+/C18O column density ratio is a few times larger towards Cha-MMS1 than CrA C. Two molecules which have similar column densities towards both cores are C34S and CH3OH. For the rest of the molecules, the column densities relative to C18O are so different in the two cores that despite the uncertainty concerning the $`N(\mathrm{H}_2)/N(\mathrm{C}^{18}\mathrm{O})`$ conversion factor, this issue may be discussed below in terms of differences in fractional abundances.

Chemical differences between the two cores are manifest in Table 7, where we list the column density ratios of several molecules. The difference is most marked in the HC3N/SO column density ratio, which is at least three orders of magnitude higher towards Cha-MMS1 than CrA C. The ratios HC3N/CCS and HC3N/N2H+ are more than a hundred times larger, and the C34S/34SO ratio is about 30 times larger towards Cha-MMS1 than towards Cra C. However, the CCS/N2H+ column density ratio is similar towards both cores.

## 5 Discussion

In the previous Section it became evident that carbon-chain molecules are considerably more abundant in Cha-MMS1 than in CrA C, whereas the opposite is true for SO. In particular, the HC3N/SO column density ratio is at least 2000 times higher in Cha-MMS1 than in CrA C. The fact that HC3N, CH3CCH, c-C3H2 and CCS were detected without difficulty in one of the cores, but were all very weak or undetected in the other, is in agreement with the common belief that these species thrive in the same regions. For CCS, the difference in the abundances towards the two cores is the smallest for carbon-chain molecules, being ‘only’ about one order of magnitude.

As discussed in Sect. 2.2, time-dependent models of gas-phase chemistry suggest that HC3N and other carbon-chain molecules reach their peak abundances at early stages of chemical evolution, whereas SO becomes abundant first at later times. Adopting this view, the HC3N/SO abundance ratios would indicate that Cha-MMS1 is chemically younger than CrA C. In addition, the CS/SO abundance ratio has been suggested to depend on the cloud age (Bergin & Langer (1997); Ruffle et al. (1999); Nilsson et al. (2000)). Indeed, the CS/SO ratio is clearly larger towards Cha-MMS1, which is mainly due to variation of the SO abundance, since the CS abundance is rather similar towards both cores.

On the other hand, it is difficult to understand in terms of pure gas-phase chemistry why CrA C has a higher SO abundance but a lower N2H+ abundance than Cha-MMS1: The production of N2H+ also increases first at later stages of chemical evolution. In particular, the fact that CCS/N2H+ column density ratio is similar towards both cores seems to contradict the expectation presented in Sect. 2.2 that this ratio could be usable as a chemical clock.

The inclusion of freezing-out of atoms, ions and molecules onto grain surfaces causes a complication for the time-dependence of molecular abundances. According to Ruffle et al. (1997), a second cyanopolyyne peak may occur when the depletion of gas-phase species becomes significant. The SO abundance also increases considerably at this time (Bergin & Langer (1997); Ruffle et al. (1999)). In the models of Ruffle et al. (1999), the SO peak comes slightly after the second HC3N peak (see their Figs. 1 and 2), probably because the C+ abundance is then lower. After the SO peak, the dominant species in the gas phase are CO, CS and SO, until they too are depleted. It is uncertain how comparable the models of Bergin & Langer (1997) and Ruffle et al. (1999) are, however, since the former do not predict any late cyanopolyyne maximum.

N2H+ is included in the models of Rawlings et al. (1992) and Bergin & Langer (1997), where depletion onto grains are taken into account. In both models N2H+ shows a late peaking, and two reasons for this peaking are given. First, N2, which contributes to the N2H+ production, is only loosely bound in grain surfaces and returns quickly to the gas phase. Second, the drop in the gas-phase abundances of CO, H2O and other neutral molecules with the advance of freezing-out decreases the destruction rate of N2H+, until the electron recombination starts to dominate its removal.

Finally, it should be noted that nearby or embedded young stars may revive the ion-molecule chemistry in a dense core. As discussed by Hartquist et al. (1996), an intensified desorption of molecules from grain surfaces, the subsequent fragmentation of molecules into atoms in the gas-phase, and finally the ionization of atoms in a star-forming core may lead to increased abundances of C and C+. These could then re-start the synthesis of complex molecules, and accordingly the chemistry would have an ‘early-time’ character.

We have seen that chemistry models, regardless of whether they take accretion onto grains into account or not, predict that SO and N2H+ peak at late stages of chemical evolution, and that SO peaks later than HC3N during the pre-stellar phase. Therefore, concerning the cores studied here, it is difficult to avoid the following conclusions: 1) CrA C has reached an advanced chemical stage. 2) Cha-MMS1 either represents the so called late-time cyanopolyyne peak or a later stage where the chemistry has been influenced by neighbouring young stars.

The latter conclusion is based on the large N2H+ abundance in Cha-MMS1. Moreover, the interpretation that a collapsing cloud core containing a protostar, as Cha-MMS1 probably does, has reached the second, ‘late-time’ cyanopolyyne peak seems more natural than that it would represent ‘early-time’ chemistry, since such a core should exhibit a high degree of depletion (Rawlings et al. (1992); Bergin & Langer (1997)). Possible outflows and radiation from the embedded protostar, IRS 10, or the other nearby protostars may have influenced the chemical composition of Cha-MMS1. Suzuki et al. (1992) found that NH3 tends to be abundant in star-forming regions, and it seems possible that the production of NH3, and therefore also that of N2H+ (see Sect. 2), somehow depend on desorption processes. On the other hand, little time has passed since the collapse began (which should be coincident with the second cyanopolyyne peak) because the duration of the Class 0 phase is very short ($`10^4`$ years), and it is questionable whether the chemistry has really changed significantly during this time.

According to the models of Ruffle et al. (1999) and Bergin & Langer (1997), where the chemical development is coupled to kinematical models, the compositions observed in Cha-MMS1 and CrA C correspond to times a few million years after the initial state, which in these studies has been defined as a state where hydrogen is molecular but all other species are found as atoms or atomic ions. If the physical characteristics of the two cores were similar, Cha-MMS1 would not need to be much younger than CrA C. The latter core, however, appears to have a lower average density, and therefore the chemical evolution has probably been slower there. The result is surprising, since star-forming cores of the type Cha-MMS1 are normally expected to be older than starless cores like CrA C. Furthermore, previous observations have shown that the carbon-chain molecules are less abundant in star-forming regions than in quiescent clouds (Suzuki et al. (1992)).

CrA C has been estimated to be gravitationally bound and therefore a potential site of star-formation (Harju et al. (1993)). The present results indicate, however, that CrA C has existed long enough to reach an advanced chemical stage, which according to chemistry models implies a minimum age of $`10^6`$ years. This longevity raises doubts about the star-formation capacity of the core.

In quiescent cores, star formation occurs due to the cloud’s self-gravity, which has to work against the thermal pressure and the pressure and tension of the magnetic fields. Line emission from molecules, especially CO (as long as it is abundant in the gas phase), and collisions between gas and dust particles, can keep a cloud nearly isothermal even when contracting, and the importance of the magnetic support in weakly ionized cores has been recognized as the dominant factor preventing the collapse within the free-fall time, which in the case of a dense core is of the order of $`10^5`$ years. The magnetic support eventually gives way in the central parts of a core due to ambipolar diffusion, resulting in gravitational instability and collapse (Spitzer (1978); Mouschovias (1979); Lizano & Shu (1987)). The density enhancement required for the gravitational collapse depends on the initial mass-to-magnetic-flux ratio. The rate at which the central density increases is related to the timescale of ambipolar diffusion (see e.g. Sect. 2 in Ciolek & Mouschovias (1993)). The timescale of ambipolar diffusion in a dense core is proportional to the fractional ionization, and is typically of the order of $`10^6`$ years (e.g. Spitzer (1978); Hartquist & Williams (1989)). This time is shorter than the time needed for reaching a chemical equilibrium in pure gas-phase models, but comparable with the depletion timescale in models in which accretion onto grain surfaces are taken into account. According to Hartquist & Williams (1989), depletion can influence the dynamical state of a core, and in the extreme case, even prevent it from collapsing by causing an increase in the fractional ionization and removing coolants. Furthermore, as pointed out by Ciolek & Mouschovias (1993, 1994,1995), the properties of dust grains can affect the ambipolar diffusion timescale and thus regulate the evolution of a core.

In simulations by Vanhala & Cameron (1997), the state of a gas-cloud first becomes non-adiabatic (i.e. the cloud is allowed to collapse) when its temperature has risen to about 27 K, at which point the rotational levels of H2 become excited. Even though these authors use perhaps unrealistically low CO cooling efficiences (they neglect the cooling below 10 K) this model may be qualitatively valid for very cold cores with highly reduced abundances of heavier molecules. If the temperature is too low, then the excitation is insufficient to provide strong enough line-emission, and a thermal balance is established. Hence, it may be that such cores have a poorer star-formation ability than previously supposed. Furthermore, an elevated temperature possibly is a useful diagnostic of the onset of a collapse, and could be used to identify dense pre-stellar cores that are close to forming stars.

Inferring from its chemical composition, the development in CrA C seem to have been very slow indeed, or then the gravitational forces in the core are simply balanced by thermal and magnetic pressures. In the ambipolar diffusion model the slow dynamical evolution could be explained by 1) a low initial mass-to-magnetic-flux ratio in the surrounding cloud; or 2) a high degree of ionization or a high fraction of charged dust grains, which both would lengthen the ambipolar diffusion timescale. The fact that the N2H+ abundance is lower in CrA C than in Cha-MMS1 suggests that the fractional ionization is indeed higher in the former. An alternative reason for the slow progress is that the cooling rate is very low in this core. Independent determinations of the kinetic temperature, the degree of ionization, and the degree of depletion towards this core would certainly clarify this issue. Based on the results of coupled chemical and kinematical models (e.g. Rawlings et al. (1992); Bergin & Langer (1997)), the high degree of depletion inferred from the molecular abundances implies a very advanced stage of evolution, and if the core is going to collapse, then this has already begun, or will do so soon deep in its interior parts. A search for infalling motions towards CrA C could be therefore profitable.

According to Lehtinen et al. (2000), the region of Cha-MMS1 may be an example of sequential star-formation, in which the core collapse is assisted by external forces such as stellar-winds originating from nearby young stars. This would conform with a rapid development, and may reflect favourable initial conditions for contraction and gravitational collapse in the parental cloud. In order to judge whether the chemistry in Cha-MMS1 is controlled by desorption or depletion, it would be useful to observe molecules which are predicted to increase in abundance when desorption mechanisms are effective. Our tentative column density estimates of CH3OH (an example of such a molecule) did not, however, show any difference in relative abundances between CrA C and Cha-MMS1. Detailed chemistry models of the relative timing of the HC3N, SO and N2H+ peaks would therefore be valuable.

The tiny SO maxima lying symmetrically on both sides of the HC3N core in Cha-MMS1 (see Fig. 1) may be related to an outflow from the embedded protostar. These emission peaks and the Herbig-Haro object HH49/50 lie on the same line intersecting the centre of Cha-MMS1, and it seems that Cha-MMS1 can indeed be the driving source of HH49/50, as suggested by Reipurth et al. (1996). The stronger SO line emission towards the outflow axis may be understood in terms of an increased efficiency of neutral-neutral reactions involved in the formation of SO in shock-heated gas.

## 6 Conclusions

Comparison of observed molecular column densities and abundances in two dense cores, Cha-MMS1 and CrA C, reveal that they have very different chemical compositions, which according to time-dependent chemistry models can be interpreted as representing different stages of chemical evolution. Cha-MMS1, which is dynamically more evolved and contains a Class 0 protostar (Reipurth et al. (1996); Lehtinen et al. (2000)), has large abundances of carbon-chain molecules. This is normally interpreted as a signature of an early stage of chemical evolution. In contrast, CrA C, which we suspected to be virginal and therefore a likely fund of ‘early type’ molecules, has, to all appearances, reached chemical maturity. This result seems to contradict the common assumption that star-forming cores are (chemically) older than starless cores. The chemical difference between the two cores is particularly pronounced in the HC3N/SO abundance ratio, which is about 2000 times higher in Cha-MMS1 than in CrA C.

The fact that Cha-MMS1 has a large N2H+ abundance arouses doubts about its chemical youth, however. Namely, this molecular ion is formed from N2, which should become abundant only at later times. In fact, Cha-MMS1 probably represents the ‘late-time’ cyanopolyyne peak predicted by Ruffle et al. (1997), which occurs when the freezing-out of molecules onto grain surfaces begins to be significant. Alternatively, the characteristics of youthful chemistry in Cha-MMS1 could have developed due to outflows and ionizing radiation from the embedded protostar or the neighbouring newly born stars. It should be noted, however, that these two alternatives do not have to lie very much apart in time. A high degree of depletion should be coincident with the collapse of the core nucleus (e.g. Rawlings et al. (1992); Bergin & Langer (1997)), and Cha-MMS1 still contains a protostar in its main accretion phase. The fact that Cha-MMS1 is associated with a small cluster of young stars indicates a high star-formation efficiency in this region (Lehtinen et al. (2000)), which would be consistent with a rapid collapse.

We have detected distinct SO emission maxima on both sides of Cha-MMS1, which may indicate the presence of a north-south oriented bipolar outflow. The suggestion by Reipurth et al. (1996) that Cha-MMS1 contains the central source of the Herbig-Haro object HH49/50 is strongly supported by the fact the SO peaks, Cha-MMS1 and HH49/50 lie along the same line.

The situation observed in CrA C, i.e. low abundances of carbon chain molecules and the large SO and N2H+ abundances, correspond to final stages of pure gas-phase chemistry evolution or to the ‘SO peak’ which comes after the late cyanopolyyne peak in the model of Ruffle et al. (1999), in which gas-grain interactions has been taken into account. The lack of star-formation activity in the chemically ‘old’ core CrA C shows that the dynamical evolution has been slow there or that the core may have even reached an equilibrium. This may be due to a low mass-to-magnetic-flux ratio in the surrounding cloud, or a high degree of ionization or a high fraction of charged dust grains making the ambipolar diffusion time very long (e.g. Ciolek & Mouschovias (1994)). On the other hand, insufficient cooling efficiency due to freezing-out of heavy molecules may have increased the thermal support.

###### Acknowledgements.

We thank Lic. Päivi Harjunpää for discussions concerning the ‘LTE’ method applied here. We are grateful to Dr. Mark Rawlings, Dr. Malcolm Walmsley, Dr. Paola Caselli, and the referee, Dr. Glenn Ciolek, for very helpful comments on the manuscript. The work by S.K., J.H. and A.H. was supported by the Academy of Finland through grant No. 1011055. The Swedish-ESO Submillimetre Telescope is operated jointly by ESO and the Swedish National Facility for Radio Astronomy, Onsala Space Observatory at Chalmers University of Technology.

## Appendix A Formulae used in the excitation temperature and column density calculations

The excitation temperatures ($`T_{\mathrm{ex}}`$) and molecular column densities ($`N_{\mathrm{tot}}`$) were estimated using a local thermodynamic equilibrium (LTE) approach in the sense that we assume a uniformly excited and Boltzmann distributed population of the energy levels for the molecule question. However, we refrain from making any assumptions concerning the (line-centre) optical depths ($`\tau _{\nu _{\mathrm{ul}}}`$). Instead we derive an exact equation (A5 below) for a two-level system, from which $`T_{\mathrm{ex}}`$ can be determined numerically (see Nummelin et al. (2000) for an LTE treatment of the excitation of molecules with numerous observed lines with no a priori assumptions about the optical depths).

By assuming that $`\tau _{\nu _{\mathrm{ul}}}`$ has a gaussian velocity distribution, the formal definition of the optical depth leads to the following expression for its value at the line-centre:

$`\tau _{\nu _{\mathrm{ul}}}`$ $`=`$ $`10^{41}\sqrt{{\displaystyle \frac{\mathrm{ln}2}{\pi }}}{\displaystyle \frac{16\pi ^3}{3\mathrm{h}}}{\displaystyle \frac{\mu _{\mathrm{el}.}^2S_{\mathrm{ul}}g(I,K)N_{\mathrm{tot}}}{Q(T_{\mathrm{ex}})\mathrm{\Delta }v}}\times `$ (1)
$`\times \mathrm{exp}(E_\mathrm{u}/\mathrm{k}T_{\mathrm{ex}})\left(\mathrm{exp}(\mathrm{h}\nu _{\mathrm{ul}}/\mathrm{k}T_{\mathrm{ex}})1\right).`$
The factor $`10^{41}`$ stems from using Debye and km s-1 as the units for the electric dipole moment ($`\mu _{\mathrm{el}.}`$) and the FWHM line-width ($`\mathrm{\Delta }v`$), respectively. Quantities related to the observed transition are: the rest-frequency $`\nu _{\mathrm{ul}}`$ \[Hz\], the line-strength $`S_{\mathrm{ul}}`$, and the energy of the upper level $`E_\mathrm{u}`$. Furthermore, $`N_{\mathrm{tot}}`$ is the total column density \[cm-2\], $`Q(T_{\mathrm{ex}})`$ is the partition function, $`g(I,K)`$ is the statistical weight due to possible nuclear spin and $`K`$-degeneracy, and $`\mathrm{h}`$ and $`\mathrm{k}`$ are the Planck and Boltzmann constants (given in cgs-units), respectively.

A second expression for $`\tau _{\nu _{\mathrm{ul}}}`$ is obtained from the “antenna equation”:

$$T_\mathrm{R}=\frac{\mathrm{h}\nu _{\mathrm{ul}}}{\mathrm{k}}\left[F(\nu _{\mathrm{ul}},T_{\mathrm{ex}})F(\nu _{\mathrm{ul}},T_{\mathrm{bg}})\right]\left[1\mathrm{exp}(\tau _{\nu _{\mathrm{ul}}})\right]$$
(2)
where

$$F(\nu _{\mathrm{ul}},T)=\frac{1}{\mathrm{exp}\left(\mathrm{h}\nu _{\mathrm{ul}}/\mathrm{k}T\right)1}.$$
(3)
$`T_\mathrm{B}`$ is the brightness temperature calculated from the observed $`T_\mathrm{A}^{}`$ by correcting for relevant beam-efficiencies and beam-filling factors. In the analysis of the observational data, we used the main-beam brightness temperature ($`T_{\mathrm{mb}}`$=$`T_\mathrm{A}^{}/\eta _{\mathrm{mb}}`$), assumed the beam-filling to be one for all lines, and did not introduce any corrections due to different beam sizes.. $`T_{\mathrm{bg}}`$ is the temperature of the background radiation (here taken as a black-body at a temperature of 2.728 K).

Eqs.(A2 and A3) yield:

$$\tau _{\nu _{\mathrm{ul}}}=\mathrm{ln}\left[\frac{\left[F(\nu _{\mathrm{ul}},T_{\mathrm{ex}})F(\nu _{\mathrm{ul}},T_{\mathrm{bg}})\right]}{\left[F(\nu _{\mathrm{ul}},T_{\mathrm{ex}})F(\nu _{\mathrm{ul}},T_{\mathrm{bg}})\right]\frac{\mathrm{k}T_\mathrm{B}}{\mathrm{h}\nu _{\mathrm{ul}}}}\right].$$
(4)
Combining the Eqs. (A1 and A4) and re-arranging the terms leads to an expression, which besides $`T_{\mathrm{ex}}`$ contains only known constants or observed quantities. By applying this to two spectral lines of the same molecule, and taking the ratio of the resulting expressions, the final equation for $`T_{\mathrm{ex}}`$ reads:

$`{\displaystyle \frac{\mathrm{ln}\left[\frac{\left[F(\nu _2,T_{\mathrm{ex}})F(\nu _2,T_{\mathrm{bg}})\right]}{\left[F(\nu _2,T_{\mathrm{ex}})F(\nu _2,T_{\mathrm{bg}})\right]\frac{\mathrm{k}T_{\mathrm{B},2}}{\mathrm{h}\nu _2}}\right]}{\mathrm{ln}\left[\frac{\left[F(\nu _1,T_{\mathrm{ex}})F(\nu _1,T_{\mathrm{bg}})\right]}{\left[F(\nu _1,T_{\mathrm{ex}})F(\nu _1,T_{\mathrm{bg}})\right]\frac{\mathrm{k}T_{\mathrm{B},1}}{\mathrm{h}\nu _1}}\right]}}{\displaystyle \frac{F(\nu _2,T_{\mathrm{ex}})}{F(\nu _1,T_{\mathrm{ex}})}}\mathrm{exp}({\displaystyle \frac{E_{\mathrm{u},2}E_{\mathrm{u},1}}{\mathrm{k}T_{\mathrm{ex}}}})`$
$`={\displaystyle \frac{\mathrm{\Delta }v_1S_{\mathrm{ul},2}}{\mathrm{\Delta }v_2S_{\mathrm{ul},1}}}.`$ (5)
The subscripts “1” and “2” refer to “line 1” and “line 2”, respectively. Terms involving $`T_{\mathrm{ex}}`$ have been collected on the left hand side of this expression. We solved Eq.(A5) for given observed line parameters by searching through a sufficiently large $`T_{\mathrm{ex}}`$ interval. When applying this equation to the observed data, we found that in addition to the case with a single unique solution, there are also cases where no solution exists, as well as cases where two solutions are present. The lack of solutions indicates that the assumption of a uniform $`T_{\mathrm{ex}}`$ for both transitions has been violated or that the beam-filling factors of the two transitions are different; in this case we have chosen the point where we have the least deviation from a solution as the value for $`T_{\mathrm{ex}}`$. The case with two solutions manifestates itself by giving one solution with a low $`T_{\mathrm{ex}}`$ and high $`\tau _{\nu _{\mathrm{ul}}}`$, the second solution having a higher $`T_{\mathrm{ex}}`$ and lower $`\tau _{\nu _{\mathrm{ul}}}`$. In the analysis we have chosen to use the low $`T_{\mathrm{ex}}`$ \- high $`\tau _{\nu _{\mathrm{ul}}}`$ alternative.

Once $`T_{\mathrm{ex}}`$ was estimated, $`\tau _{\nu _{\mathrm{ul}}}`$ was calculated from Eq.(A4) and subsequently $`N_{\mathrm{tot}}`$ was derived from Eq.(A1).

In cases where we have only one observed transition, we have assigned a $`T_{\mathrm{ex}}`$ close to that of a species with similar excitation requirements. $`N_{\mathrm{mol}}`$ is then obtained, assuming optically thin emission, from the formula:

$$N_{\mathrm{tot}}=\frac{1.6710^{23}\mathrm{exp}\left(E_\mathrm{u}/\mathrm{k}T_{\mathrm{ex}}\right)Q(T_{\mathrm{ex}})I_{\mathrm{line}}}{\left(1\frac{F(T_{\mathrm{bg}})}{F(T_{\mathrm{ex}})}\right)\nu \mu _{\mathrm{el}.}^2S_{\mathrm{ul}}g(I,K)}.$$
(6)
Here $`I_{\mathrm{line}}`$=$`T_\mathrm{B}dv`$ is the velocity-integrated line-intensity \[K km s-1\].

In the calculation of the column densities the partition functions need to be evaluated. For linear rotors ($`{}_{}{}^{1}\mathrm{\Sigma }`$) we used the following formula (e.g. Townes & Schawlow (1975), chapter 1):

$$Q\frac{\mathrm{k}T_{\mathrm{ex}}}{\mathrm{h}B}+\frac{1}{3}$$
(7)
where $`B`$ is the rotation constant.

For CCS and SO we made a direct summation over the energy levels with $`E_\mathrm{i}/\mathrm{k}<575`$ K:

$$Q=\underset{i}{}g_i\mathrm{exp}\left(E_\mathrm{i}/\mathrm{k}T_{\mathrm{ex}}\right)$$
(8)
where $`g_i`$ is the statistical weigth, $`2J_i+1`$, with the relevant $`J_i`$ used.

We would like to emphasize that the evaluation of the partition function through direct summation is essential in the case of SO and CCS. For example for SO, the “usual” integral approximation of the partition function ($`3\frac{\mathrm{k}T_{\mathrm{ex}}}{\mathrm{h}B}1`$) overestimates $`Q`$ by a factor of 1.1 to 1.85 in the temperature range 2–70 K; the largest discrepancy occurs at $`T_{\mathrm{ex}}5`$ K. Thus for SO this simple approximation can be used only for temperatures above 80 K or so. A better analytical approximation for $`Q`$ at temperatures below 80 K can be obtained by treating each of the three $`N`$ ladders as separate rigid rotors and integrating over $`J`$. Note that only one of the ladders ($`J=N1`$) has $`J`$=0 as its lowest level; the two other ladders begin with $`J`$=1. The resulting partition functions are:

$$Q_{J=N1,\mathrm{ladder}}\frac{\mathrm{k}T_{\mathrm{ex}}}{\mathrm{h}B}+\frac{1}{3}$$
(9)
$$Q_{J=N,\mathrm{ladder}}\left(\frac{\mathrm{k}T_{\mathrm{ex}}}{\mathrm{h}B}\frac{2}{3}\right)\mathrm{exp}(\mathrm{\Delta }E_1/kT_{\mathrm{ex}})$$
(10)
$$Q_{J=N+1,\mathrm{ladder}}\left(\frac{\mathrm{k}T_{\mathrm{ex}}}{\mathrm{h}B}\frac{2}{3}\right)\mathrm{exp}(\mathrm{\Delta }E_2/kT_{\mathrm{ex}})$$
(11)
where $`\mathrm{\Delta }E_1`$ is the energy difference between the lowest levels in the $`J=N`$ and $`J=N1`$ ladders, and $`\mathrm{\Delta }E_2`$ the corresponding difference between the $`J=N+1`$ and $`J=N1`$ ladders. The lowest states in these ladders are $`J_N`$=$`0_1`$ (the ground-state), $`1_1`$, and $`1_0`$, respectively.

The total partition function is then:

$$Q=Q_{J=N1,\mathrm{ladder}}+Q_{J=N,\mathrm{ladder}}+Q_{J=N+1,\mathrm{ladder}}.$$
(12)
For SO, this approximation overestimates the true partition function by less than 15% for temperatures between 3 and 80 K, the error being less than 5% for $`T_{\mathrm{ex}}>25`$ K. The values for $`\mathrm{\Delta }E_1`$ and $`\mathrm{\Delta }E_2`$ are 15.18 K and 1.44 K (SO); 9.33 K and 0.53 K (CCS), respectively.

For c-C3H2 we used:

$$Q2\sqrt{\frac{\pi \mathrm{k}^3T_{\mathrm{ex}}^3}{\mathrm{h}^3ABC}}2.450T_{\mathrm{ex}}^{3/2}.$$
(13)
The contributions from both ortho- and para-states have been accounted for by taking into account their different statistical weigths: 3 for ortho and 1 for para.

For CH3OH we used:

$$Q2\sqrt{\frac{\pi \mathrm{k}^3T_{\mathrm{ex}}^3}{\mathrm{h}^3ABC}}1.232T_{\mathrm{ex}}^{3/2}.$$
(14)
The (equal) contributions from both the $`A`$\- and the $`E`$-symmetry species have been accounted for.

For CH3CCH it is common to use the expression:

$$Q\frac{8}{3}\sqrt{\frac{\pi \mathrm{k}^3T_{\mathrm{ex}}^3}{\mathrm{h}^3ABC}}4.177T_{\mathrm{ex}}^{3/2}.$$
(15)
where the contributions from both the $`A`$\- and the $`E`$-symmetry species have been accounted for by taking into consideration the spin statistics of the various levels (see e.g. Townes & Schawlow (1975), chapter 3).

However, Eq.(A15) is valid only at high enough temperatures. Since the lines observed by have low excitation temperatures, we derived a more accurate approximation for temperatures below 30 K. Each $`K`$-ladder was treated as a linear rotor and the integration was performed over $`J`$. Note that $`J`$=$`K`$ is the lowest level of a specific $`K`$-ladder. By taking into account only the three first ladders ($`K`$=0, 1, 2) we have:

$$Q_{K=0,\mathrm{ladder}}\frac{\mathrm{k}T_{\mathrm{ex},J}}{\mathrm{h}B}+\frac{4}{3}$$
(16)
$$Q_{K=1,\mathrm{ladder}}\left(\frac{\mathrm{k}T_{\mathrm{ex},J}}{\mathrm{h}B}\frac{8}{3}\right)\mathrm{exp}(\mathrm{\Delta }E_3/kT_{\mathrm{ex},K})$$
(17)
$`Q_{K=2,\mathrm{ladder}}`$ $``$ $`({\displaystyle \frac{\mathrm{k}T_{\mathrm{ex},J}}{\mathrm{h}B}}{\displaystyle \frac{8}{3}}12\mathrm{exp}(\mathrm{\Delta }E_3/kT_{\mathrm{ex},J}))\times `$ (18)
$`\times \mathrm{exp}(\mathrm{\Delta }E_4/kT_{\mathrm{ex},K})`$
where $`\mathrm{\Delta }E_3/\mathrm{k}7.20`$ K and $`\mathrm{\Delta }E_4/\mathrm{k}28.80`$ K are the energy differences between the lowest levels of the $`K`$=1 and $`K`$=2 ladders, respectively, relative to the $`K`$=0 ladder. $`T_{\mathrm{ex},J}`$ is the excitation temperature along a specific $`K`$-ladder (i.e. $`K`$ fix, $`J`$ varies), and $`T_{\mathrm{ex},K}`$ is the excitation temperature between different $`K`$-ladders (i.e. $`K`$ varies, $`J`$ fix).

The resulting expression for the total partition function for CH3CCH, which in the indicated temperature range underestimates the result from a direct summation by less than 10%, is given by:

$$QQ_{K=0,\mathrm{ladder}}+Q_{K=1,\mathrm{ladder}}+Q_{K=2,\mathrm{ladder}}$$
(19)


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# Phase Transitions in liquid Helium 3

## Abstract

The phase transitions of liquid $`{}_{}{}^{3}He`$ are described by truncations of an exact nonperturbative renormalization group equation. The location of the first order transition lines and the jump in the order parameter are computed quantitatively. At the triple point we find indications for partially universal behaviour. We suggest experiments that could help to determine the effective interactions between fermion pairs.

preprint: HD-THEP-00-39

The low temperature phase transitions and the superfluid phases of liquid Helium 3  can be described  by a field theory for complex $`3\times 3`$ matrices $`A`$ representing fermion pairs. An approximation based on quartic polynomials in $`A`$, including the renormalization group running of the coupling constants , can account for the rough phase structure but not for details of the transitions. We will be concerned with the transitions from the normal liquid to superfluidity in vanishing external magnetic field. In a mean-field treatment those transitions are of second order, whereas early RG-calculations  found hints for them to be fluctuation induced first order transitions. The BCS weak-coupling theory estimates the critical region where fluctuations invalidate the mean-field approximation to extend over a temperature interval $`\mathrm{}T10^8K`$. Based on experiments on zero sound absorption  it has been conjectured, however, that the critical region might be up to a thousand times larger . The theoretical answers therefore hinge on two problems: first, the “microphysical” effective interactions at the scale of the fermion pairs ($`\mathrm{\Lambda }^1120\AA `$) are poorly known and second, the transition from the microphysical interactions to the macrophysics of the phase transitions (i.e. the thermodynamic potentials) is very complex. Only if the second problem can be solved, the experimental observations of the macrophysics (phase structure, jump in the order parameter, etc.) can be used to constrain the microphysical interactions. In this letter we propose a quantitatively reliable mapping of the microphysics onto the properties of the free energy density. This is effected by means of extended truncations to an exact nonperturbative renormalization group equation , in contrast to largely uncontrolled approximations used earlier .

The different phases of $`{}_{}{}^{3}He`$ are characterized by expectation values $`<A>`$ (order parameters) in different directions: the BW-state, $`A_1=1`$, the ABM-state, $`A_2=\sqrt{\frac{3}{8}}(\lambda _7+i\lambda _6+\lambda _4i\lambda _5)`$, and the planar state, $`A_3=\sqrt{\frac{3}{2}}i\lambda _2`$ represent the phases of the mean-field diagram. The $`\lambda _i`$ are the Gell-Mann matrices. Additionally, we examine the direction $`A_4=\sqrt{\frac{3}{4}}(\lambda _3i\lambda _1)`$. Here, $`<A>`$ corresponds to the minimum of the effective potential $`U(A)`$ for spatially homogeneous fields. Our main aim is therefore the computation of $`U(A)`$ for a given microscopic effective action (at the scale $`\mathrm{\Lambda }`$) for which we assume the conventional form

$$\mathrm{\Gamma }_\mathrm{\Lambda }=d^3x\{Tr\stackrel{}{}A^{}\stackrel{}{}A+m\rho +\underset{i=0}{\overset{4}{}}b_iI_i+aK_D\}$$
(1)
with $`\rho =TrA^{}A`$ and $`I_i`$ the invariants to fourth order allowed by the symmetry group $`G=SO(3)\times SO(3)\times U(1)`$:

$`I_0=\rho ^2`$, $`I_1=|TrA^TA|^2`$, $`I_2=Tr(A^TA)(A^TA)^{}`$, $`I_3=Tr(A^{}A)^2`$ and $`I_4=Tr(A^{}A)(A^{}A)^{}`$.

We include the dipole interaction

$$K_D=TrA^{}TrA+Tr(A^{}A)$$
(2)
as a symmetry breaking perturbation arising from the spin-orbit coupling of the atoms in a Cooper pair and neglect the strain gradient terms . All quantities are in units of a characteristic critical temperature $`T_c=2.6mK`$ and $`m(T)=m(T_c)+\frac{TT_c}{T_c}+\mathrm{}`$ reflects the temperature dependence. In the paramagnon theory the quartic couplings $`b_i`$ are given by

$$b_0=c(2+.2\delta ),b_1=c(1+.1\delta ),b_2=c(2.05\delta ),$$

$$b_3=c(2.55\delta ),b_4=c(2+.7\delta )$$
(3)
with $`c=0.001`$ and $`\delta `$ parametrizing the pressure dependence. We study a pressure regime of $`2<\delta <1.8`$. For $`\delta >1.9`$ the microscopic potential becomes unbounded from below. This will be compared to a calculation where the couplings are ten times as strong.

Our approach is based on the effective average action $`\mathrm{\Gamma }_k[A(x)]`$ which interpolates between the microphysics ($`k=\mathrm{\Lambda }`$) and the macrophysics ($`k=0`$) by means of an exact flow equation . We truncate the most general functional dependence on $`A(x)`$ by

$$\mathrm{\Gamma }_k=d^3x\{Z_kTr\stackrel{}{}A^{}\stackrel{}{}A+U_k(A)+a_kK_D\}$$
(4)
where $`U_k(A)`$ is a function of the eighteen real fields $`\phi _y`$ in $`A`$ respecting the symmetry group $`G`$. We can compute the effective potential $`U(A)U_0(A)`$ by a numerical integration of the flow equation

$$_tU_k(A)=\frac{1}{2}\frac{d^3q}{2\pi ^3}_tR_kTr((Z_kq^2+R_k)+M_k^2(A))^1$$
(5)
Here, $`t=\mathrm{ln}k`$. The infrared cut-off

$$R_k(q)=Z_kq^2(1e^{\frac{q^2}{k^2}})^1$$
(6)
makes the flow equation ultraviolet and infrared finite. We need the mass matrix of second derivatives of $`U`$, $`M_{y,z}^2=\frac{^2U}{\phi _y\phi _z}`$. The flow equation for the wave function renormalization $`Z_k`$ can be found in .

In a first investigation we have used a sixth order polynomial approximation for $`U_k`$ and searched for minima in all the fifteen directions with different residual symmetries given in . In this scheme we found a phase transition into the direction $`A_4`$ for large $`\delta `$. We have convinced ourselves, however, that polynomial approximations do not allow reliable statements about the phase diagram. This is why we deal with an arbitrary dependence of $`U_k`$ on the field in a given direction $`A=\xi A_n`$ for which we write $`U_k(\xi A_n)=V_k^{(n)}(\rho )`$ with $`\rho =3\xi ^2`$. We assume, that the directions $`n`$ include the absolute minimum of $`U_k`$. We get the flow equation for $`V_k^{(n)}`$ by evaluating (5) at points on the line $`\xi A_n`$. To do so, we need to know the second derivatives of $`U_k`$ with respect to all fields, however. That is why we include in our truncation four coupling functions $`b_i^{(n)}(\rho )`$ multiplying all fourth order invariants other than $`\rho ^2`$:

$$U(\xi A_n+ϵ)=\{V^{(n)}(\rho )+\underset{i=1}{\overset{4}{}}b_i^{(n)}(\rho )(I_if_i^{(n)}\rho ^2)\}|_{\xi A_n+ϵ}$$
(7)
The numbers $`f_i^{(n)}`$ are chosen such that the invariants $`I_if_i^{(n)}\rho ^2`$ do not contribute on the line $`\xi A_n`$. Here $`ϵ`$ denotes fields orthogonal to $`\xi A_n`$ and we expect that this truncation gives a good approximation to the true potential in a neighborhood of the line $`\xi A_n`$.

The flow equations of the coupling functions $`b_i^{(n)}(\rho )`$ are derived by forming appropriate linear combinations of second and third derivatives of (5) with respect to certain fields. At the origin we need to take fourth derivatives to extract the couplings from our potential truncation. We have computed these flow equations for the four field directions $`A_n`$. The resulting equations are very long, altogether about 4000 lines. They all derive, however, from compact expressions, namely field derivatives of (5), which can be evaluated by a computer. We consider this structural simplicity to be one of the major strengths of our formalism.

We have integrated the resulting equations numerically by laying the potentials and coupling functions on grids of ten points each. In a first run, we detected truncation errors in the quantities $`\frac{V^{(n)}}{\rho }|_{A=0}`$. They originate in an insufficient treatment of the symmetry constraints. We fight this problem in two steps. First, we infer the first potential derivatives at the origin from the term $`m\rho `$ and integrate a separate flow equation for $`m`$. Second, for the higher orders we employ for small $`|t|`$ a mixed truncation of the form

$$U(\xi A_n+ϵ)=\{m\rho +\underset{i=0}{\overset{4}{}}b_iI_i+\underset{j=0}{\overset{10}{}}c_jJ_j+\rho ^4w^{(n)}(\rho )$$

$$+\underset{i=1}{\overset{4}{}}\rho ^2B_i^{(n)}(\rho )(I_if_i^{(n)}\rho ^2)\}|_{\xi A_n+ϵ}$$
(8)
Here $`J_j`$ are the eleven invariants of sixth order. $`w^{(n)}`$ and $`B_i^{(n)}`$ describe the deviation from a sixth order polynomial approximation. The symmetry is manifestly respected up to sixth order. We have estimated the accuracy of the sixth order polynomial approximation by calculating $`_tU(\xi A_n)`$ to fourth and sixth order in $`\xi `$ in two ways: from the flow of the couplings in the polynomial part of truncation (8) and directly by equation (5). The discrepancy stays smaller than $`20\%`$ as long as the flow parameter $`|t|`$ is not too big, $`t>5`$. It grows to a few hundred percent, however, until the phase transition occurs at $`t8`$. This is due to terms of eighth and higher order that are truncated in the flow equations for the couplings $`b_i`$ and $`c_j`$ in (8). We conclude, that with a polynomial truncation of the free energy to realistic order, no conclusive statements can be obtained about the phase diagram. As soon as the errors exceed $`20\%`$, we switch to the truncation (7). The truncation error in the quantities $`_tV^{(n)}`$ at the potential minima is estimated by comparing truncation (7) with a truncation in which we extract the orthogonal masses from the polynomial truncation in the origin. The errors induced by the inaccuracies of $`\frac{V^{(n)}}{\rho }|_{A=0}`$ are of the order of magnitude of the truncation errors and both are not bigger than a few percent. This truncation should therefore allow us to compute the phase structure reliably.

First, we study the case of large couplings, $`c=0.01`$. We neglect the spin-orbit coupling, which is justified in this case, the other masses being much bigger. By computing the temperature dependence of the renormalization of the fourth order couplings, we find a width of the critical region of about $`10^6K`$, in good agreement with the Ginzburg criterion. The resulting phase diagram is shown in figure 1. In a pressure regime of $`0.26<\delta <0.46`$ a beak of A-phase between the symmetric and the B-phase is stabilized by the fluctuations of the order parameter. In the middle of this pressure interval the temperature width of this wedge is about $`10^6K`$.

Towards the upper end it rises, however, to $`10^5K`$ at $`\delta =0.41`$. All transitions are of the first order. The potentials at the transitions look qualitatively like figure 5.

Figure 2 shows the pressure dependence of the correlation length, given by the inverse of the renormalized mass at the potential minimum, and the discontinuity of the NMR-frequency shift at the phase transition. The latter quantity is related to the jump in the order parameter squared $`\mathrm{}\rho `$ by

$$\mathrm{}\nu ^26c10^{10}Hz\mathrm{}\rho $$
(9)
which follows from the mean-field temperature dependence of $`\mathrm{}\nu `$ given in . We observe a substantial increase of the correlation length as we approach the triple point $`\delta =0.26`$. This observation nourishes first hope for a fixed point in the vicinity of this point in parameter space which would give rise to universal behaviour of the system. Accurate predictions could then be made despite the uncertainty of our knowledge of the microscopic theory. Also an examination of the flow of the couplings at the origin looks promising for the triple point. We observe strong renormalization of the fourth order couplings $`b_i`$. For example, $`\frac{b_{4_\mathrm{\Lambda }}}{b_{4_0}}8`$, whereas analogous ratios away from the triple point, say, at $`\delta =0`$, grow no larger than $`1.5`$ at the phase transition .

Figure 3 shows the dimensionless renormalized couplings $`b_{i_r}`$. We cannot find a true fixed point behaviour. However, ratios of couplings seem to tend to constant values, such as $`\frac{b_{1_r}}{b_{4_r}}=1`$, corresponding to a partial fixed point.

The qualitative features for smaller couplings $`c=0.001`$ look similar, with correspondingly smaller $`\mathrm{}T=10^8K`$. In this case, however, the dipole term should be included ($`a_\mathrm{\Lambda }=210^6`$) which we do next. Figure 4 shows the phase diagram with first order transition lines. The considerations in  are confirmed by our calculation. The width of the stripe of planar phase stabilized by the dipole interaction is about $`210^9K`$ as it was expected from mean-field considerations. We have not inspected the phase structure much further than $`10^9K`$ away from the transition line. We expect the same features we found above: stabilization of a wedge of A phase with a temperature width of about $`10^8K`$ by the fluctuations.

Tuning the temperature to the transition from the symmetric to the planar phase we find a potential $`U_{k_f}`$ (figure 5) which shows clearly that the transition is of first order. (Fluctuations with momenta smaller than $`k_f`$ make the potential convex without much influence on the equation of state .) From figure 5 we can easily infer the order parameter jump: $`\mathrm{}\rho 810^5`$. This turns out to be almost independent of the pressure in the regime examined by us. It corresponds to a discontinuity in the NMR-frequency shift at the transition of about $`50Hz`$. It was suggested in  that this should be experimentally observable.

Let us finally ask how experiments may constrain the size of the couplings. We have seen that large couplings lead to a widening of the critical region $`\mathrm{}T`$. It should be possible to exploit this fact by measuring the width of the critical region. Varying the temperature at a pressure right under the triple point, one should be able to observe two distinct phase transitions . The width of the intermediate phase relates to the coupling strength via the Ginzburg criterion. By the described experiment one could also measure the pressure corresponding to the values $`\delta =0.26`$ and $`\delta =0.46`$. An approximate form of the relation $`p(\delta )`$ could be obtained then by linearization. Strictly speaking, these arguments hold only if the dipole term can be neglected. However, the temperature range for the planar phase, $`10^9K`$, is so narrow, that it would probably not even show up in experiments with realistic temperature resolution.

Also the order parameter jump depends strongly on the coupling strength. With the larger couplings $`c=0.01`$ we find $`\mathrm{}\rho 0.01`$ for the jump into the B-phase at the triple point. This leads to a discontinuity in the frequency shift of about $`2000Hz`$ as opposed to e.g. $`370Hz`$ for $`c=0.002`$. We think, that it would be even easier to infer the size of the critical region from measuring this order parameter jump. At least, this way it should be possible to get upper bounds for the coupling strength that are rather close to the range discussed in this article. To facilitate the interpretation of such NMR-experiments, we calculated the jump of $`\mathrm{}\nu `$ for various other values of the coupling strength c at $`\delta =0.15`$. We show the result in figure 6.

In conclusion, our quantitative description of the phase diagram of $`{}_{}{}^{3}He`$ should permit to extract reliable information about the system’s microphysical interactions from future experiments.