Ab initio investigations of the C3+ cation and of its role during the reactions of C3+ ions against atomic sulfur.
Accurate ab initio calculations are performed in order to characterize the most stable isomers of empirical formula C3S+ and the role of C3S+ during the ion-molecule reactions between the C3+ triatomic molecular ions and S atoms. The linear form l-C C-C-S+ (X2sigma+) is found to be the most stable isomer followed by a three-membered carbon ring with an external S {c-C3S+ (X2A1)}. The ion-molecule reactions are investigated by doing suitable 1-D cuts of the 6-D potential energy functions (PEFs) of the lowest electronic states of C3S+. After its formation, the C3S+ intermediate may dissociate leading, in addition to the charge transfer products, to C, C+, C2, C2+, CS, CS+, C2S and C2S+ species. Generally, the dynamics of these reactions are found to involve several electronic states of C3S+ and their mutual couplings, including Renner-Teller couplings, spin-orbit interactions and vibronic interactions. These couplings can take place before and/or after intramolecular isomerisation processes.
Theoretical Chemistry Group, University of Marne-La-Vallée, Champs sur Marne, F-77454 Marne-la-Vallée, France.
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