# Identification of SH Δ⁢𝑣=1 ro-vibrational lines in R And

## 1 Introduction

Chemistry of sulfur-containing species in space is especially interesting due to its chemical activity and relatively high abundance (Duley, Millar, & Williams, 1980). It is known that abundances of sulfur-bearing molecules are strongly influenced by the presence of shocks (Hartquist, Oppenheimer, & Dalgarno, 1980). So far, 14 sulfur-bearing species have been identified in space; CS, SO, NS, SiS, SO<sup>+</sup>, SH<sub>2</sub>, OCS, CCS, C<sub>3</sub>S, H<sub>2</sub>CS, HNCS, SO<sub>2</sub>, HCS<sup>+</sup>, and CH<sub>3</sub>SH. However, the simplest sulfur compound, SH, has not been detected in spite of radioastronomical searches using the $`\mathrm{\Lambda }`$-type doubling transitions (Meeks, Gordon, & Litvak, 1969; Heiles & Turner, 1971).

While sulfur chemistry in the circumstellar envelope of red giant stars has been studied extensively (e.g., Omont et al., 1993), that in the atmosphere has been regarded as in the thermal equilibrium state (Tsuji, 1964, 1973). In the atmosphere of oxygen-rich giants, SH is the molecule first formed from the sulfur atom, at the temperature of about 2000 K. The SH abundance decreases when temperature is below $`1500`$ K, and H<sub>2</sub>S and SiS become the dominant species. On the other hand, Yamamura et al. (1999a) report the detection of the $`\nu _3`$ infrared band of SO<sub>2</sub> in the spectra of oxygen-rich Mira variables obtained by the Short-Wavelength Spectrometer (SWS: de Graauw et al., 1996) on board the Infrared Space Observatory (ISO: Kessler et al., 1996). Their model analysis indicates that the molecules are located in the extended atmosphere, at about five stellar radii. The abundance of SO<sub>2</sub> is 5–10 orders of magnitude larger than the values in thermal equilibrium (Tsuji, 1973; Woitke et al., 1999). The result strongly suggests the presence of non-equilibrium processes in the extended atmosphere, probably related to shocks due to stellar pulsation (Beck et al., 1992; Duari, Cherchneff, & Willacy, 1999).

In this paper, we report the detection of SH ro-vibrational transition lines in the published high-resolution infrared spectrum of the S-type star, R And. We discuss the physical and chemical conditions of the SH layer in the star.

## 2 Identification of SH lines

The data used in this study were obtained with the Fourier-transform spectrometer at the Kitt Peak National Observatory 4 m telescope, and were published in Ridgway et al. (1984). R And is a Mira variable with a period of 409 days and a visual amplitude of 9.1 mag (Kholopov et al., 1988). The spectral type ranges in S3,5e–S8,8e. The observation of R And was performed at the optical variable phase of $`\varphi =0.82`$. Unfortunately, the reduced data were lost after several updates of archive formats at the observatory. Therefore, we re-digitized the data from the printed spectrum. The results may be as accurate as the original within $`0.02`$ cm<sup>-1</sup> in wavenumber and a few % in intensity. The spectrum was shifted by 5.2 km s<sup>-1</sup> to longer wavelengths to adjust the absorption minimum of HCl lines at their rest frequencies (Ridgway et al., 1984). No correction for terrestrial motion was applied. In their original paper, Ridgway et al. (1984) give identifications of OH, NH, CH, SiO, CS, HCl, and atomic lines. The spectrum of R And, especially in the wavelengths shorter than the SiO first-overtone bandheads, is dominated by HCl lines. OH and NH lines are detected, but much less prominently than in the oxygen-rich stars like $`\alpha `$ Ori and $`\alpha `$ Tau. There are many strong lines left unidentified. Figure Identification of SH $`\mathrm{\Delta }v=1`$ ro-vibrational lines in R And shows the spectrum of R And between 2700 and 2750 cm<sup>-1</sup>. The positions of SH and HCl ro-vibrational transitions are indicated. The frequencies are calculated from the molecular constants given by Ram et al. (1995) for SH, and are taken from HITRAN database 1996 edition (Rothman et al., 1992) for HCl. It is obvious that many unidentified strong lines are attributed to SH transitions. We assigned 39, 41, and 11 transitions in the $`v=10`$, $`21`$, and $`32`$ bands, respectively, between 2500 and 2778 cm<sup>-1</sup>. The lower state energies of these transitions are up to $`7000`$ cm<sup>-1</sup>, indicating that the molecules are highly excited. The isotope <sup>34</sup>SH may also be detected. The frequencies of <sup>34</sup>SH lines are estimated from the molecular constants of SH using the relation of reduced mass (Herzberg, 1950).

## 3 Modeling

We analyze the observed SH line profiles with a simple model. The SH (and also HCl) lines in R And show inverse P-Cygni profiles, indicating that the molecular layer is moving inward to the star due to stellar pulsation. We, therefore, apply a spherical shell model with a constant infall velocity. The molecules in front of the star cause absorption, while those extended in the blank sky contribute as emission. Considering that the shell may be in the atmosphere, we adopt an exponential density law, $`n(r)\mathrm{exp}(r/r_0)`$, where $`r_0`$ is the scale height. The star is assumed to be a 3000 K blackbody. For simplification, a constant excitation temperature is adopted, and the energy population of the molecule is calculated by assuming local thermodynamic equilibrium (LTE). This may be justified if the molecular shell is thin and in the high density region near the photosphere. The line intensity of SH is calculated based on Benidar et al. (1991), which takes account of the Herman-Wallis effect. The spectrum is normalized by the stellar continuum. No smoothing is applied.

The excitation temperature can be determined from the relative intensities of the lines at different energy levels; higher temperatures excite the molecules to higher energy levels and increase the line strength from these levels. We find that 2200 K is most reasonable for the present case. A turbulent velocity of 6 km s<sup>-1</sup> and infall velocity of $`9`$ km s<sup>-1</sup> reproduce the line profiles. The model spectrum is shifted by $`14`$ km s<sup>-1</sup>. Considering the terrestrial velocity of $`2.7`$ km s<sup>-1</sup> at transit of the observation, and the shift applied by Ridgway et al. (1984), $`+5.2`$ km s<sup>-1</sup>, a radial velocity of $`16.5`$ km s<sup>-1</sup> is obtained. The inner radius and the scale height of the SH shell is 1.0 and 0.08 times the stellar radius, respectively. The SH column density in the shell is $`4.0\times 10^{20}`$ cm<sup>-2</sup>. The uncertainties of the parameters, which changes the model spectrum by about 10 %, are $`\pm 100`$ K for excitation temperature, a factor of two for column density, $`\pm 0.01`$ R for scale hight, and $`\pm 1`$ km s<sup>-1</sup> for the velocities. The radial velocity has an error of $`\pm 2`$ km s<sup>-1</sup> due to the re-digitization process. The model spectrum is compared with the observation in Figure Identification of SH $`\mathrm{\Delta }v=1`$ ro-vibrational lines in R And. The wavelength regions are selected so that the contamination of other spectral lines is minimal, and that a wide range of energy levels is covered. Strong lines in Figure Identification of SH $`\mathrm{\Delta }v=1`$ ro-vibrational lines in R And are listed in Table 1. The fit is satisfactory in most of the lines. Fitting of <sup>34</sup>SH lines results in an isotopic abundance ratio of 5–10 %. We note that the same parameters also give reasonable fits for the HCl lines with a column density of $`3.0\times 10^{19}`$ cm<sup>-2</sup>.

## 4 Discussion

Why are SH lines so prominent in R And, an S-type star? S-type stars are characterized by their chemical anomaly of similar carbon and oxygen abundances. This leaves few C and O atoms for further chemical processes, after formation of CO molecules at 4–5000 K. SH should be quite abundant in the atmosphere of oxygen-rich stars, but a minor product in a carbon-rich environment (Tsuji, 1973). Since we do see SiO lines, but no CS line, in the spectrum of R And, the star is slightly oxygen-rich. Nevertheless, it is not expected that SH is much more abundant in S-type stars than O-rich stars. This also holds for HCl, which is the most abundant Cl-bearing molecule in an oxygen-rich environment, although the absolute abundance is by one order of magnitude lower than SH. Ridgway et al. (1984) suggested that the atmosphere of S-type stars is more transparent than O-rich stars, so that the lines of minor species could be stronger due to larger path length. We especially emphasize the contribution of the H<sub>2</sub>O molecules. In the same paper, Ridgway et al. reported that an enormous number of lines heavily blanket the 2400–2800 cm<sup>-1</sup> region of the $`o`$ Cet spectrum. They suspected that these are highly excited water lines. This is supported by the ISO/SWS observation of $`o`$ Cet (Yamamura et al., 1999b). Despite the relatively poor resolution of the SWS spectrum, they demonstrate that the star shows highly excited H<sub>2</sub>O lines in the 3.5–4.0 $`\mu `$m region, arising from hot (2000 K) and optically thick molecular layer. Probably, in O-rich stars, SH (and HCl) lines are weaker because of the shorter path length, and also heavily contaminated by the hot water lines. On the other hand, H<sub>2</sub>O molecules are not favored in the atmosphere of S-type stars. The thermal equilibrium abundance of H<sub>2</sub>O in S-type stars is 3–4 orders lower than in O-rich stars (Tsuji, 1964).

The derived infall velocity and the excitation temperature of the SH layer are consistent with the measurement of CO $`\mathrm{\Delta }v=3`$ lines by Hinkle, Scharlach, & Hall (1984) at $`\varphi =0.80`$, indicating that the SH molecules are in the same region as hot CO near the photosphere. Comparison with the CO column density, $`2.6\times 10^{24}`$ cm<sup>-2</sup>, given by Hinkle, Scharlach, & Hall (1984), leads to SH/H $`=1\times 10^7`$. In thermal equilibrium at the temperature of 2200 K and gas pressure of $`\mathrm{log}(P_g)=1.0`$, the SH abundance is $`2\times 10^7`$ (Tsuji, 1973, 1999). This value is insensitive to the C/O ratio as long as C/O $`<1`$. The present estimate of SH abundance in R And, although it is rather crude, is consistent with this calculated value. The sulfur chemistry in SH layer still follows thermal equilibrium, because of its high density and high temperature.

We see no clear evidence of distinct velocity and/or different temperature component of SH lines in the spectrum. This implies that the SH molecules are distributed only in a thin layer in the atmosphere. In thermal equilibrium, SH is most abundant around 1800 K, and then is rather quickly transformed to H<sub>2</sub>S or SiS below $`1500`$ K (Tsuji, 1973). Otherwise, non-equilibrium chemical reactions may lead to completely different compositions in the extended atmosphere, e.g. the enhancement of SO<sub>2</sub> in oxygen-rich stars (Yamamura et al., 1999a; Beck et al., 1992). We could not find any clear indications of H<sub>2</sub>S or SO<sub>2</sub> in the spectrum of R And. The upper limit of the H<sub>2</sub>S column density is at least a factor of 10 larger than the observed amount of SH. A dioxide molecule SO<sub>2</sub> may not be abundant in the atmospheres of S-type stars. Other possible candidates, SO or SiS, have no transition in the present wavelength coverage.

The authors are grateful to Prof. T. Tsuji for his suggestion on thermal equilibrium chemistry and calculations of SH abundance. I.Y. acknowledges financial support from a NWO PIONIER grant.