Molecules in Space & Laboratory, Paris, 2007

J.L. Lemaire & F. Combes (eds)

THE MOLECULAR OPACITY PROBLEM FOR MODELS OF COOL STARS AND BROWN DWARFS
Jonathan Tennyson 1
Abstract. The spectra of cool stars are completely dominated by very complicated patterns of molecular absorptions. Models of these stars thus require large amounts of data to characterise this behaviour. Progress on providing molecular opacities for such models is discussed with particular emphasis on the calculation of extensive line lists of vibration-rotation transitions for polyatomic molecules such as water. Examples of applications of these line lists to other astrophysical problems are given.

Introduction

It is widely believed that the study of astrophysical molecules involves the study of molecules at low temperatures. While this may be true in the vast molecular clouds out of which stars form it is completely untrue in cool stars themselves. The atmosphere, structure and evolution of cool stars and sub-stellar objects at 3000 K and below are determined by molecular processes many of which remain poorly characterised. The starlight that reaches earth has its origins in the nuclear reactions and gravitational processes which generate energy in these stars but in detail it reects the temperature and composition of the outer layer of the stars atmosphere. For stars hotter than the Sun the systematic calculation of all processes involving atoms and atomic ions (Seaton 1987, Seaton & Badnell 2004) has led to the construction of reliable opacity functions which allow the transport of light through the interior and atmospheres of such stars. For stars cooler than the Sun, and even in sunspots (Polyansky et al. 1997), molecule formation becomes increasingly important. The absorption spectra of molecules are fundamentally dierent to those of atoms in that the wealth of vibrational and rotational levels leads to band structures comprising large numbers of individual transitions. Particularly at temperatures of 1000 3000 K these bands absorb light over a signicant wavelength ranges meaning that the resulting stellar spectra do not have an obvious temperature-dependent prole. Under such circumstances even determining the temperature of a star requires detailed stellar modelling which places a huge burden on laboratory data. To determine the opacity of cool stars requires the consideration of a variety of physical process. In approximate order of the number of transitions involved the
1

Department of Physics and Astronomy, University College London, London WC1E 6BT, UK c Observatoire de Paris & Universit de Cergy-Pontoise e

Molecules in Space & Laboratory

rst class of problems is atomic processes: the absorption by alkali metals often give prominent features and the photo-detachment of H gives and important continuum opacity source. The second class is the rotation-vibration transitions of stable diatomic species such as hydrogen, carbon monoxide and SiO. These species are generally well characterised by laboratory spectra although their study can yield important information on cool stars (Jones et al. 2005). The third class are electronic transitions of open shell diatomic molecules containing a transition metal such as TiO, FeH, CrH. These species have very rich spectra because of the presence of many low-lying electronic states which lead to a complicated set of absorptions which are hard to model, see (Plez 1998, Schwenke 1998, Allard et al. 2000, Pavlenko et al. 2007) for example, which so far have been characterised using a mixture of laboratory and ab initio studies. The fourth class of problems are the vibration-rotation spectra of stable polyatomic molecules such as water, ammonia and methane. At the temperatures of cool stars these molecules contain far to many transitions (hundreds of millions or more) for it to be possible to completely characterise their spectra in their spectra in the laboratory. Methods for solving that problem are discussed further below. Finally it also necessary to consider non-line process such as continuum induced absorption which is really only important for hydrogen (Jorgensen et al. 2000) and absorption by dust (Alexander et al. 1997), which becomes important for stars cooler than about 2000 K. 2 Calculations of molecular opacity

With the exception of HeH+ and its isotopologues (Harris et al. 2004, Engel et al. 2005), the opacities considered by my group at UCL have been those concerned with the vibration-rotation spectrum of triatomic molecules. We have published opacities for water (Barber et al. 2006), H+ (Neale et al. 1996) and HCN (Harris et al. 2002, 3 Harris et al. 2006). Other systems including C3 and HDO are currently be considered (Tennyson et al. 2007). Calculating the high temperature absorption of triatomic systems requires solving the vibration-rotation nuclear motion problem for a given potential energy surface and then using these solutions with a dipole surface to give transition intensities. For high lying states the use of methods based on the variational principle to treat the nuclear motion have been demonstrated to give much the most reliable results. Our recent calculations have been performed using the grid based discrete variable representation as implemented in the DVR3D program suite (Tennyson et al. 2004), although earlier calculations (Allard et al. 1994) used more a conventional basis set expansion method (Tennyson et al. 1993). The calculation of the rotation-vibration energy levels can also yields the partition functions which are often very poorly known at temperatures of importance for cool stars (Neale & Tennyson 1995, Harris et al. 1998, Vidler & Tennyson 2000, Barber et al. 2002). It is now possible to achieve high convergence for nuclear motion calculations on triatomics and the accuracy of such calculations is largely governed by the quality of the underlying potential energy surface plus any allowance that might be made for the Born-Oppenheimer approximation (Polyansky et al. 2003). Only for two electron systems such as H+ or HeH+ is it currently possible to get completely ab initio 3 potential energy surfaces which gives transition frequencies with the required accuracy (Polyansky & Tennyson 1999, Engel et al. 2005). There are two possible strategies for

The molecular opacity problem

using laboratory data for improving on such ab initio calculations. The rst strategy, which have employed for the HCN/HNC isomerising system, is to perform the initial calculations with a high quality ab initio surface (van Mourik et al. 2001) and then subsequently adjust the energy levels of the system using measured laboratory values (Harris et al. 2006). The second technique is to use a potential energy surface that has been adjusted so that it reproduces the laboratory data (Shirin et al. 2003). The second strategy has been used for water (Partridge & Schwenke 1997, Barber et al. 2006). Indeed, given that even the adjusted potential energy surfaces do not yield precisely the measured transition frequencies, it is possible to adopt both approaches. The nal ingredient for the calculations is a dipole moment surface. Experience has shown that the most reliable surfaces are obtained from ab initio electronic structure calculations (Lynas-Gray et al. 1995), and such surfaces have been used in all our studies. Indeed in the case of H+ all interpretation of observed astronomical 3 spectra rely on ab initio intensity calculations since there are no available laboratory measurements of absolute transition intensities for this species. Given the above ingredients the calculation of the opacity is straightforward but far from trivial because of the exceptionally large number of transitions that need to be considered. Thus the recent BT2 water opacity contains over 500 million separate lines (Barber et al. 2006). It is hard to believe that all these lines are important but experience has shown that it is dangerous to neglect lines. For example H+ 3 transitions with Einstein A coecients more than 1012 smaller than the strongest lines were found to play a crucial role in the lifetime of excited rotational states of H+ 3 (Kreckel et al. 2004); however these transitions were omitted from our H+ opacity line 3 list for being too weak to matter (Neale et al. 1996). The rotational trapping caused by this eect has also been found to be astrophysically signicant (Oka et al. 2005). 3 Sample astronomical applications

The most straightforward application of the calculation of molecular opacities is for models of cool stars (Jones et al. 1995) and brown dwarfs (Sharp & Burrows 2007). An obvious extension of this work is giant planets (Sharp & Burrows 2007), especially the rapidly expanding class of hot Jupiters that are being detected orbiting other stars. Indeed the BT2 water opacity proved to crucial in the recent detection of water on the extra solar planet HD 189733b (Tinetti et al. 2007), the rst rm detection of a molecule on a planet outside our solar system. However it is becoming increasingly apparent that accurate and extensive line lists can be used for other tasks than simply modelling the opacity of cool stars and sub-stellar objects. Within such objects they can be used for spectral identication (Tennyson et al. 2007). For example the HCN/HNC line list has been used to identify HNC in the atmosphere of cool carbon stars for the rst time (Harris et al. 2003). Given the sensitivity of the HCN to HNC ratio to temperature in the 2000 3000 K region (Barber et al. 2002), the observation of HNC has potential to provide a simple thermometer for these species. Line identications within sunspots have also been made using extensive line lists (Polyansky et al. 1997). Comets are cold species and therefore spectroscopically very dierent from cool stars. However cometary coma are bathed in sunlight and therefore are non-thermal environments. The BT2 lines list (and its precursor) has been used to model uorescence spectra of optically pumped water allowing both the rotational and nuclear spin

Molecules in Space & Laboratory

temperatures to be determined (Dello Russo et al. 2004, Dello Russo et al. 2005). The nuclear spin temperature is found to be consistently lower for reasons that remain the subject of conjecture (Limbach et al. 2006). Recently observations of the Deep Impact event with comet Temple 1 have revealed a new set of previously unobserved water uorescence lines (Barber et al. 2007). These lines, which could be assigned with BT2, are vibrationally hotter than those observed previously but are also rotationally cold. 4 Conclusions

Molecular line list calculated using variational nuclear motion calculations are beginning to make a signicant impact not only for the astrophysics of cool stars but also in other areas. However to successfully model stellar opacities requires complete sets of data. For many important cases this data is far from available. In particular there are no extensive line lists available for species larger than triatomics. Key polyatomic molecules include methane, ammonia and acetylene. Treating these systems represents a major challenge but is essential if there is every to be a solution to the molecular opacity problem as complete as that already available for the atomic opacities. Acknowledgement It is a pleasure to acknowledge the members of my group who have collaborated on the work discussed above: in particular Bob Barber, Greg Harris, Santina La Delfa and Boris Voronin. References
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