THE CHEMISTRY OF PAH AND FULLERENE MOLECULES IN INTERSTELLAR CLOUDS

Recent laboratory data on the ion-neutral chemistry of PAH and fullerene ions and molecules have been incorporated into chemical kinetic models of interstellar clouds. The laboratory data show that the-second ionization potentials of many complex molecules are less than the first ionization potential of helium. Thus collisions between He+, generated by cosmic ray ionization, and PAH and fullerene neutrals produce doubly charged cations. I find that these cations, and also protonated neutrals, are abundant in dark clouds. If the recombination of electrons with doubly charged cations, which releases typically 14 eV of energy, is dissociative in nature, then PAH and fullerene species are destroyed m both diffuse and dense clouds on astronomically significant time-scales.

CHEMICAL PROCESSES IN DARK INTERSTELLAR CLOUDS - THE EFFECTS OF CNO DEPLETION

We have investigated the effects of depletion of the elements C, N and O on the chemical composition of dark clouds, using both isothermal and isochoric cloud models. Our work differs from previous approaches in that we have considered a much larger range of CNO depletions. We have included the chemistry of the ortho-and para-forms of H2 and the exothermic reaction between N+ and ortho-H2, which synthesizes NH3. In the isothermal models, the ortho:para ratio is very small at large depletions, but NH3 formation is still efficient owing to reactions between He+ and CN or HCN. In the isochoric models, the equilibrium temperature of the gas is larger, and a thermal ortho:para ratio, which is large enough to drive NH3 formation, results. In all cases, the fractional abundance of NH3 is close to 10(-8) and this may help to explain the puzzling observation that, in dark clouds, the column density of NH3 is always close to 10(15) cm-2.

PROTONATED HCN IN MOLECULAR CLOUDS

Observations of protonated HCN (HCNH+) in a selection of galactic molecular clouds are reported. This species plays a key role in understanding the chemistry of the important high density tracer HCN. HCNH+ has been detected in the nearby cold dust cloud TMC-1 with an ratio relative to HCN of [HCNH+]/[HCN] between 0.015 and 0.26 (preferred value 0.03) and tentatively in DR21(OH) with a ratio of approximately 0.01. This is about 100 times higher than the ratio of protonated carbon monoxide to CO [HCO+]/[CO], but comparable to the [HCS+]/[CS] ratio. Possible explanations of these high abundance ratios are discussed in the light of model calculations.

PHOSPHORUS CHEMISTRY IN DENSE INTERSTELLAR CLOUDS

I have used recent laboratory studies on the reactions of the phosphorus hydride ions, PH(n)+ (n = 0-4) to construct a new model of phosphorus chemistry in interstellar clouds. I find that the non-detection of PN in cold, dark clouds in consistent with the chemical models only if the depletion of phosphorus in large, approximately 10(4) in TMC-1. Although the laboratory studies indicate that organo-phosphorus chains C(n)P can be formed, this large depletion precludes the detection of any phosphorus-bearing moleclues in cold clouds. However, in warm clouds associated with star formation, the depletion of phosphorus may be reduced. In this case one can reproduce the PN abundance toward Orion KL with a depletion factor of about 300. Interestingly, if the organo-phosphorus species are not destroyed by O atoms, I predict fractional abundances in Ori KL of between 10(-11) and 10(-10) for C(n)P (n = 2-4) and HCCP.