Electronic spectroscopy of carbon chains and rings of astrophysical interest.

This perspective is concerned with laboratory measurements of the electronic spectra of carbon chains, rings, and their ions, including derivatives terminated by hydrogen and nitrogen atoms. The selected-species have relevance to astronomical observations through diffuse clouds, absorption features known as diffuse interstellar bands (DIBs). Two indications to decide which molecules should be studied are the observations of polar carbon chains in dense clouds by rotational spectroscopy and the knowledge that a certain number of these have electronic transitions in the DIB region. This information has been obtained initially by measurements of the electronic absorptions in 6 K neon matrixes using mass-selection. This was followed by the gas-phase observations using cavity ringdown and resonance enhanced techniques in combination with pulsed-supersonic discharge sources or via laser vaporization. The gas-phase spectra were then compared with DIB data, all with negative results, except for the detection of C3, but leading to upper limits of their column densities <10(12) cm–2. By reference to mm-wave absorption measurements in the diffuse medium, it is shown that, although species such as H2C3 are present there, the product of the expected column densities and oscillator strength of the transitions will lead to only very weak DIBs. The significant conclusion is that carbon chains and their derivatives containing hydrogen or nitrogen comprising up to a dozen atoms cannot be responsible for stronger DIBs. However, chains with an odd-number of carbon atoms, C17, C19, ···, have very intense transitions in the region above 4400 Å and remain attractive candidates. An uncertainty is the excited electronic state lifetime; if this is less than 70 fs, then the resulting absorptions would be too broad to be astronomically relevant. The electronic absorptions of some of the species studied bear a striking resemblance to DIB data. The two peaked rotational contour of the origin band in the electronic transition of dicyanoacetylene cation is superimposable on a DIB absorption when shifted by 1 Å. The band profiles of cyclic C18 at 100 or 20 K are similar to DIBs but differ in wavelength. This suggests that another set of potential candidates are the carbon rings of sizes up to a hundred of atoms, including ions and heavy atoms, with the requirement of a large oscillator strength. Observations on the absorptions of propadienylidene C3H2 and C60+ are discussed.