Interstellar reactions

Although the major interstellar reaction that occms on the surfaces of dust particles is the formation of molecular hydrogen, more complex molecules are also thought to be formed in this maimer. 

Petrie S, Herbst E. (1997) Some interstellar reactions involving electrons and neutral species Attachment and isomerization. Astrophys. J. 491 210-215. Giithe F, Tulej M, Pachkov MV, Maier JP. (2001) Photodetachment Spectrum of EC3H2H The Role of Dipole Bound States for Electron Attachment in Interstellar Clouds. Astrophys. J. 555 466-471. 

Patra SM, Mishra RK, Mishra BK (1997) Graph-theoretic study of certain interstellar reactions. Int J Quantum Chem 62 495-508... 

The methyl cation CHf is involved in the interstellar reaction C -I- —> CH+ -I- H2, under study in om- group... 

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). 

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. 

There is a very low cosmic abundance of boron, but its occurrence at all is surprising for two reasons. First, boron s isotopes are not involved in a star s normal chain of thermonuclear reactions, and second, boron should not survive a star s extreme thermal condition. The formation of boron has been proposed to arise predominantly from cosmic ray bombardment of interstellar gas in a process called spallation (1). 

The high stability of porphyrins and metalloporphyrins is based on their aromaticity, so that porphyrins are not only most widespread in biological systems but also are found as geoporphyrins in sediments and have even been detected in interstellar space. The stability of the porphyrin ring system can be demonstrated by treatment with strong acids, which leave the macrocycle untouched. The instability of porphyrins occurs in reduction and oxidation reactions especially in the presence of light. The most common chemical reactivity of the porphyrin nucleus is electrophilic substitution which is typical for aromatic compounds. 

The reactions of ground state atomic carbon, C(3Pj), with unsaturated hydrocarbons are another important class of reactions characterized by multiple pathways. These reactions, besides being of fundamental interest, are of great relevance in the chemistry of the interstellar medium and also in combustion.12,93-95... 

There are, however, still some unsolved, important questions103 about this fundamental reaction, of great relevance in dense interstellar clouds, where it could well be the source of the C3H and C3 species detected there. These unsolved questions are (a) what is the branching ratio for formation of the two isomeric C3H species, Z-C3H and C-C3H, and how does it vary with Ec (b) How do the detailed reaction dynamics and the branching ratio for C3H and C3 formation vary with Ec ... 

Free radicals are short-lived, highly-reactive transient species that have one or more unpaired electrons. Free radicals are common in a wide range of reactive chemical environments, such as combustion, plasmas, atmosphere, and interstellar environment, and they play important roles in these chemistries. For example, complex atmospheric and combustion chemistries are composed of, and governed by, many elementary processes involving free radicals. Studies of these elementary processes are pivotal to assessing reaction mechanisms in atmospheric and combustion chemistry, and to probing potential energy surfaces (PESs) and chemical reactivity. 

The first step in interstellar chemistry is the production of diatomic molecules, notably molecular hydrogen. Observations of atomic hydrogen in dense clouds show that this species cannot be detected except in a diffuse halo surrounding the cloud, so that an efficient conversion of H into H2 is necessary. In the gas phase this might be accomplished by the radiative association reaction,... 

The Hj ion, recently detected in the interstellar medium via infrared transitions,25 can subsequently react with a variety of neutral atoms present in the gas. The reaction with oxygen leads to a chain of reactions that rapidly produce the hy-dronium ion H30+ via well-studied H atom-transfer reactions ... 

The reactants in 20 can also produce the higher energy isomer HOC+, which is detected in dense interstellar clouds,37 albeit with a lower abundance than HCO+ due mainly to the catalytic reaction,... 

The above examples should suffice to show how ion-molecule, dissociative recombination, and neutral-neutral reactions combine to form a variety of small species. Once neutral species are produced, they are destroyed by ion-molecule and neutral-neutral reactions. Stable species such as water and ammonia are depleted only via ion-molecule reactions. The dominant reactive ions in model calculations are the species HCO+, H3, H30+, He+, C+, and H+ many of then-reactions have been studied in the laboratory.41 Radicals such as OH can also be depleted via neutral-neutral reactions with atoms (see reactions 13, 15, 16) and, according to recent measurements, by selected reactions with stable species as well.18 Another loss mechanism in interstellar clouds is adsorption onto dust particles. Still another is photodestruction caused by ultraviolet photons produced when secondary electrons from cosmic ray-induced ionization excite H2, which subsequently fluoresces.42... 

Recent studies with a crossed-beam apparatus not only show that the products shown above are the correct ones, but that both the linear and cyclic isomers, each of which is a detected interstellar molecule, are formed.47 Crossed-beam studies also show that other reactions between C atoms and unsaturated hydrocarbons proceed to form similar products 48... 

A second successful prediction is that many so-called metastable species (i.e. isomers) are abundant even if they are quite reactive in the laboratory.66 Perhaps the simplest interstellar molecule in this class is HNC, but large numbers of others can be seen in Table 1. It is assumed that most metastable species are formed in dissociative recombination reactions along with their stable counterparts at approximately equal rates, and that both are destroyed by ion-molecule reactions so that the laboratory reactivity, which is normally determined by reactions with neutral species, is irrelevant. Both HCN and HNC, for example, are thought to derive from the dissociative recombination reaction involving a linear precursor ion ... 

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