Energetics of Formation of Cyclacenes from 2,3-Didehydroacenes and Implications for Astrochemistry.

The carriers of the diffuse interstellar bands (DIBs) are still largely unknown although polycyclic aromatic hydrocarbons, carbon chains, and fullerenes are likely candidates. A recent analysis of the properties of n-acenes of general formula C4n+2 H2n+4 suggested that these could be potential carriers of some DIBs. Dehydrogenation reactions of n-acenes after absorption of an interstellar UV photon may result in dehydroacenes. Here the reaction energies and barriers for formation of n-cyclacenes from 2,3-didehydroacenes (n-DDA) by intramolecular Diels-Alder reaction to dihydro-etheno-cyclacenes (n-DEC) followed by ejection of ethyne by retro-Diels-Alder reactions are analyzed using thermally assisted occupation density functional theory (TAO-DFT) for n=10-20. It is found that the barriers for each of the steps depend on the ring strain of the underlying n-cyclacene, and that the ring strain of n-DEC is about 75 % of that of the corresponding n-cyclacene. In each case, ethyne extrusion is the step with the highest energy barrier, but these barriers are smaller than CH bond dissociation energies, suggesting that formation of cyclacenes is an energetically conceivable fate of n-acenes after multiple absorption of UV photons.

Molecular gas in the host galaxy of a quasar at redshift z = 6.42.

Observations of molecular hydrogen in quasar host galaxies at high redshifts provide fundamental constraints on galaxy evolution, because it is out of this molecular gas that stars form. Molecular hydrogen is traced by emission from the carbon monoxide molecule, CO; cold H2 itself is generally not observable. Carbon monoxide has been detected in about ten quasar host galaxies with redshifts z > 2; the record-holder is at z = 4.69 (refs 1-3). Here we report CO emission from the quasar SDSS J114816.64 + 525150.3 (refs 5, 6) at z = 6.42. At that redshift, the Universe was only 1/16 of its present age, and the era of cosmic reionization was just ending. The presence of about 2 x 1010 M\circ of H2 in an object at this time demonstrates that molecular gas enriched with heavy elements can be generated rapidly in the youngest galaxies.