Interstellar molecules, carbon atom reactions

A much more detailed and time-dependent study of complex hydrocarbon and carbon cluster formation has been prepared by Bettens and Herbst,83 84 who considered the detailed growth of unsaturated hydrocarbons and clusters via ion-molecule and neutral-neutral processes under the conditions of both dense and diffuse interstellar clouds. In order to include molecules up to 64 carbon atoms in size, these authors increased the size of their gas-phase model to include approximately 10,000reactions. The products of many of the unstudied reactions have been estimated via simplified statistical (RRKM) calculations coupled with ab initio and semiempirical energy calculations. The simplified RRKM approach posits a transition state between complex and products even when no obvious potential barrier... 

Model calculations that include at least some of the reactions we have discussed for the syntheses of complex molecules have been performed in the last several years. Both steady-state and chemical time dependent models have been published. Unfortunately, as models include more and more complex species, they become more and more sensitive in their predictions to small changes. As an example, consider two models that in their predictions of the abundances of one-carbon-atom hydrocarbons differ by a factor of 3. This factor is not considered to be a major one in the field of interstellar chemistry. However, since the two-carbon-atom hydrocarbons are formed by reactions between one-carbon atom species, the model will differ in their predictions for the abundances of the larger hydrocarbons by a factor of 9. As one can easily discern, the situation becomes worse as the size of the hydrocarbons increase. Given this extreme sensitivity, modelers should attempt to make sure that at each stage of molecular complexity, they consider all depletion mechanisms and do not overestimate the abundances of the complex molecules that are intermediates in the formation of still more complex species. Unless this is done, models can become in our view overly optimistic about the growth of complexity in the interstellar medium. 

What effect do shocks have on the gas phase synthesis of complex interstellar molecules This question has been investigated at least for hydrocarbons through six carbon atoms in complexity by Mitchell (1983, 1984). He has found that if a shock passes through a dense cloud where much of the carbon is already in the form of carbon monoxide, complex hydrocarbons are not formed in high abundance. However, if a shock passes through a diffuse cloud, of density approximately 103 cm-3, where much of the cosmic abundance of carbon is in the form of C+ and to a lesser extent C, a different scenario is present. As the shock cools, the C+ and C, which remain in appreciable abundance for up to 10s yrs after the shock passage, react via many of the reactions discussed above as well as others to produce a rich hydrocarbon chemistry. The net effect is that large abundances of hydrocarbons build up as the cloud cools and eventually reaches a gas density of 3 x 104 cm-3. Do these results bear any relation to the results obtained from ambient gas phase models In both types of calculations, hydrocarbon chemistry appears to require the presence of C+ and/or C both to synthesize one-carbon hydrocarbons such as methane and then, via insertion reactions, to produce more complex hydrocarbon species. Condensation reactions do not appear to be sufficient. 

Kaiser, R.I. Ochsenfeld, C. Head-Gordon, M. Lee, Y.T. Suits, A.G. A combined experimental and theoretical study on the formation of interstellar C3H isomers. Science 1996, 274, 1508-1511. Kaiser, R.L Ochsenfeld, C. Head-Gordon, M. Lee, Y.T. Neutral-neutral reactions in the interstellar medium. IL Isotope effects in the formation of linear and cyclic C3H and C3D radicals in interstellar environments. Astrophys. J. 1999, 510, 784—788. Kaiser, R.L Ochsenfeld, C. Head-Gordon, M. Lee, Y.T. The formation of HCS and HCSH molecules and their role in the collision of comet Shoemaker-Levy 9 with Jupiter. Science 1998, 279, 1181-1184. Kaiser R.L Stranges D. Lee Y.T. Suits A.G. Neutral-neutral reactions in the interstellar medium. 1. Formation of carbon hydride radicals via reaction of carbon atoms with unsaturated hydrocarbons. Astrophys. J. 1997, 477, 982-989. 

Clary DC, Haider N, Husaia D, Kabir M. (1994) Interstellar carbon chemistry Reaction rates of neutral atomic carbon with organic molecules. Astrophys. J. 422 416-4 22. 

On the other hand, the fundamental problem associated with grain production, the return of molecules to the interstellar gas is caused by the low grain temperatures and is certainly not facilitated for complex molecules. On the contrary, the vapour pressure of molecules usually decreases with with increasing molecular complexity as is the case for carbon chain molecules. overcomes this problem and both CO and also have sufficient vapour pressure to prevent them from freezing out entirely onto grains. Both molecules serve therefore as reservoirs for atoms and ions through charge transfer reactions discussed earlier. 

Figure 10.5 illustrates the chemical structure of a plane parallel PDR by giving the relative abundances of C+, C and CO as a function of the penetration depth into the model cloud [11]. We assumed a kinetic equilibrium and determined the relative abundances from a chemical network consisting of 38 different species formed and destroyed in 434 reactions. The PDR is illuminated from the left by the mean interstellar radiation field and extends from the predominantly atomic surface region to the point where almost all carbon is bound into CO. One of the difficulties in calculating the chemical and thermal structure of a PDR arises from the effect of self-shielding. Molecules already formed absorb UV photons which are able to dissociate the respective molecule. In other words they cast a shadow into the cloud which enhances the further formation of the respective molecule. This effects becomes especially important for the formation of key molecules like O2, H2 and CO. Our current research addresses the question under which physical conditions an instability due to shadowing effects could occur. Another difficulty concerns the effects of small-scale fluctuations of the UV radiation field on the chemical network. 

Recently many propositions have been made in the field of astronomical science. Herbst et al. proposed plausible mechanisms for converting molecular hydrogen and atomic carbon in interstellar clouds into hydrocarbon molecules via sequences of ion-neutral reactions [21]. These mechanisms have been incorporated into IMR... 

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