Organic chemistry in Titan's upper atmosphere and its astrobiological consequences: I. Views towards Cassini plasma spectrometer (CAPS) and ion neutral mass spectrometer (INMS) experiments in space

The discovery of carbocations and carbanions by Ion Neutral Mass Spectrometer (INMS) and the Cassini Plasma Spectrometer (CAPS) instruments onboard the Cassini spacecraft in Titan's upper atmosphere is truly amazing for astrochemists and astrobiologists. In this paper we identify the reaction mechanisms for the growth of the complex macromolecules observed by the CAPS Ion Beam Spectrometer (IBS) and Electron Spectrometer (ELS). This identification is based on a recently published paper (Ali et al., 2013. Planet. Space Sci. 87, 96) which emphasizes the role of Olah's nonclassical carbonium ion chemistry in the synthesis of the organic molecules observed in Titan's thermosphere and ionosphere by INMS. The main conclusion of that work was the demonstration of the presence of the cydopropenyl cation - the simplest Huckel's aromatic molecule - and its cyclic methyl derivatives in Titan's atmosphere at high altitudes. In this study, we present the transition from simple aromatic molecules to the complex ortho-bridged bi- and tri-cyclic hydrocarbons, e.g., CH2+ monosubstituted naphthalene and phenanthrene, as well as the ortho- and pen-bridged tri-cyclic aromatic ring, e.g., perinaphthenyl cation. These rings could further grow into tetra-cyclic and the higher order ring polymers in Titan's upper atmosphere. Contrary to the pre-Cassini observations, the nitrogen chemistry of Titan's upper atmosphere is found to be extremely rich. A variety of N-containing hydrocarbons including the N-heterocycles where a CH group in the polycyclic rings mentioned above is replaced by an N atom, e.g., CH2+ substituted derivative of quinoline (benzopyridine), are found to be dominant in Titan's upper atmosphere. The mechanisms for the formation of complex molecular anions are discussed as well. It is proposed that many closed-shell complex carbocations after their formation first in Titan's upper atmosphere, undergo the kinetics of electron recombination to form open-shell neutral radicals. These radical species subsequently might form carbanions via radiative electron attachment at low temperatures with thermal electrons. The classic example is the perinaphthenyl anion in Titan's upper atmosphere. Therefore, future astronomical observations of selected carbocations and corresponding carbanions are required to settle the key issue of molecular anion chemistry on Titan. Other than earth, Titan is the only planetary body in our solar system that is known to have reservoirs of permanent liquids on its surface. The synthesis of complex biomolecules either by organic catalysis of precipitated solutes "on hydrocarbon solvent" on Titan or through the salvation process indeed started in its upper atmosphere. The most notable examples in Titan's prebiotic atmospheric chemistry are conjugated and aromatic polycyclic molecules, N-heterocycles including the presence of imino > C=N-H functional group in the carbonium chemistry. Our major conclusion in this paper is that the synthesis of organic compounds in Titan's upper atmosphere is a direct consequence of the chemistry of carbocations involving the ion-molecule reactions. The observations of complexity in the organic chemistry on Titan from the Cassini-Huygens mission dearly indicate that Titan is so far the only planetary object in our solar system that will most likely provide an answer to the question of the synthesis of complex biomolecules on the primitive earth and the origin of life. (C) 2015 Elsevier Ltd. All rights reserved.