Interstellar

It should be remembered that most of the discussion in this chapter is aimed at laboratory analysis under normal conditions. We assume that the selection rules are to be applied for molecules initially in the ground vibrational state in an IR spectrometer, so that Afoi is the important coupling factor and the symmetry of the initial state of the vibration excited by the IR radiation is always totally symmetric. This has led to the simple selection rule that a vibration must have a symmetry representation that matches one of the dipole moment operator components to be IR active. 

The H2 bands observed in the interstellar spectra are actually features of excitation from the electronic ground state for which the affect of vibrations can be seen in the fine structure. The primary excitation is electronic rather than vibrational, and so a different set of selection rules will apply. The origin of vibrational fine structure can be understood in terms of the Franck-Condon approach to electronic excitations discussed in Appendix 9. 

The vibrational fine structure of electronic transitions is also responsible for Raman spectra used in the laboratory. In the next section we discuss the appropriate selection rules for this particular analytical tool. 

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Gas-phase reactions play a fundamental role in nature, for example atmospheric chemistry [1, 2, 3, 4 and 5] and interstellar chemistry [6], as well as in many teclmical processes, for example combustion and exliaust fiime cleansing [7, 8 and 9], Apart from such practical aspects the study of gas-phase reactions has provided the basis for our understanding of chemical reaction mechanisms on a microscopic level. The typically small particle densities in the gas phase mean that reactions occur in well defined elementary steps, usually not involving more than three particles. 

At the limit of extremely low particle densities, for example under the conditions prevalent in interstellar space, ion-molecule reactions become important (see chapter A3.51. At very high pressures gas-phase kinetics approach the limit of condensed phase kinetics where elementary reactions are less clearly defined due to the large number of particles involved (see chapter A3.6). 

Herbst E 1987 Gas phase chemical processes in molecular clouds Interstellar Prooesses ed D J Hollenbach and H A Tronson (Dordrecht Reidel) pp 611-29... 

In this section, the wide diversity of teclmiques used to explore ion chemistry and ion structure will be outlined and a sampling of the applications of ion chemistry will be given in studies of lamps, lasers, plasma processing, ionospheres and interstellar clouds. 

Microwave spectra (giving pure rotational spectra) are especially usefiil for the detection of interstellar molecular ions (in some cases the microwave spectrum has first been observed in interstellar spectra ). 

Several instniments have been developed for measuring kinetics at temperatures below that of liquid nitrogen [81]. Liquid helium cooled drift tubes and ion traps have been employed, but this apparatus is of limited use since most gases freeze at temperatures below about 80 K. Molecules can be maintained in the gas phase at low temperatures in a free jet expansion. The CRESU apparatus (acronym for the French translation of reaction kinetics at supersonic conditions) uses a Laval nozzle expansion to obtain temperatures of 8-160 K. The merged ion beam and molecular beam apparatus are described above. These teclmiques have provided important infonnation on reactions pertinent to interstellar-cloud chemistry as well as the temperature dependence of reactions in a regime not otherwise accessible. In particular, infonnation on ion-molecule collision rates as a ftmction of temperature has proven valuable m refining theoretical calculations. 

The astrochemistty of ions may be divided into topics of interstellar clouds, stellar atmospheres, planetary atmospheres and comets. There are many areas of astrophysics (stars, planetary nebulae, novae, supemovae) where highly ionized species are important, but beyond the scope of ion chemistry . (Still, molecules, including H2O, are observed in solar spectra [155] and a surprise in the study of Supernova 1987A was the identification of molecular species, CO, SiO and possibly ITf[156. 157]. ) In the early universe, after expansion had cooled matter to the point that molecules could fonn, the small fraction of positive and negative ions that remained was crucial to the fomiation of molecules, for example [156]... 

Interstellar clouds of gases contain mostly H, H2 and He, but the minority species are responsible for the interesting chemistry that takes place, just as in the earth s atmosphere. Interstellar clouds are divided into two... 

Smith D and Spanel P 1995 Ions in the terrestrial atmosphere and in interstellar olouds Mass Spectrom. Rev. 14 255-78... 

Fox J L 1996 Aeronomy Atomic, Molecular, and Optical Physics Handbook ed G W F Drake (Woodbury, NY AlP) Geballe T R and Oka T 1996 Deteotion of Fl,+ in interstellar spaoe Nature 384 334-5... 

In the dense interstellar medium characteristic of sites of star fonuation, for example, scattering of visible/UV light by sub-micron-sized dust grains makes molecular clouds optically opaque and lowers their internal temperature to only a few tens of Kelvin. The thenual radiation from such objects therefore peaks in the FIR and only becomes optically thin at even longer wavelengths. Rotational motions of small molecules and rovibrational transitions of larger species and clusters thus provide, in many cases, the only or the most powerfiil probes of the dense, cold gas and dust of the interstellar medium. 

To date, researchers have identified more than 100 different molecules, composed of up to 13 atoms, in the interstellar medium [16]. Most were initially detected at microwave and (sub)millimetre frequencies, and the discoveries have reached far beyond the mere existence of molecules. Newly discovered entities such as difhise mterstellar clouds, dense (or dark) molecular clouds and giant molecular cloud complexes were characterized for the first time. Indeed, radioastronomy (which includes observations ranging from radio to submillunetre frequencies) has dramatically changed our perception of the composition of the universe. Radioastronomy has shown that most of the mass in the interstellar medium is contained in so-called dense... 

Herbst E 1995 Chemistry in the interstellar medium Ann. Rev. Rhys. Chem. 46 27-53... 

Thaddeus P, MoCarthy M C, Travers M, Gottlieb C and Chen W 1998 New oarbon ohains in the laboratory and in interstellar spaoe Faraday See. Discuss. 109 121 -36... 

Collisional ionization can play an important role in plasmas, flames and atmospheric and interstellar physics and chemistry. Models of these phenomena depend critically on the accurate detennination of absolute cross sections and rate coefficients. The rate coefficient is the quantity closest to what an experiment actually measures and can be regarded as the cross section averaged over the collision velocity distribution. 

Sometimes a star explodes in a supernova cast mg debris into interstellar space This debris includes the elements formed during the life of the star and these elements find their way into new stars formed when a cloud of matter collapses in on itself Our own sun is believed to be a second generation star one formed not only from hydrogen and helium but containing the elements formed in earlier stars as well... 

The compound cyanoacetylene (HC=C—C=N) has been detected in interstellar space Make a molecular model or sketch the approximate geometry expected for this compound What IS the hybridization of nitrogen and each carbon" ... 

What a storyi Fullerenes formed during the ex plosion of a star travel through interstellar space as passengers on a comet or asteroid that eventually smashes into Earth Some of the fullerenes carry pas sengers themselves—atoms of helium and argon from the dying star The fullerenes and the noble gas atoms silently wait for 251 million years to tell us where they came from and what happened when they got here... 

Comparison with the empirical Equation (1.4) shows that = /re /S/z eg and that n" = 2 for the Balmer series. Similarly n" = 1, 3, 4, and 5 for the Lyman, Paschen, Brackett and Pfimd series, although it is important to realize that there is an infinite number of series. Many series with high n" have been observed, by techniques of radioastronomy, in the interstellar medium, where there is a large amount of atomic hydrogen. For example, the (n = 167) — ( " = 166) transition has been observed with V = 1.425 GFIz (1 = 21.04 cm). 

Interstellar molecules detected by their radiofrequency, microwave or millimetre wave spectra... 

Table 5.2 lists some of the molecules which have been detected. It is interesting to note that some of them, such as the linear triatomics C2H, HCO and N2H, were found in the interstellar medium before they were searched for and found in the laboratory. In all molecules, except OH and NH3, the transitions observed are rotational in nature. 

Identification of a molecule known in the laboratory is usually unambiguous because of the uniqueness of the highly precise transition frequencies. However, before frequencies detected in the interstellar medium can be compared with laboratory frequencies they must be corrected for the Doppler effect (see Section 2.3.2) due to the motion of the clouds. In Sagittarius B2 the molecules are found to be travelling fairly uniformly with a velocity of... 

Table 5.2 shows that quite large molecules, of which the cyanopolyacetylenes form a remarkable group, have been detected. The presence of such sizeable molecules in the interstellar medium came as a considerable surprise. Previously, it was supposed that the ultraviolet radiation present throughout all galaxies would photodecompose most of the molecules, and particularly the larger ones. It seems likely that the dust particles play an important part not only in the formation of the molecules but also in preventing their decomposition. 

The hydrogen atom and its spectrum are of enormous importance in astrophysics because of the large abundance of hydrogen atoms both in stars, including the sun, and in the interstellar medium. 

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