Abstract
Enthalpies of reaction for reactions involving diatomic sulfides and oxides have been calculated at the MP n/6–31G ∗∗ ( n = 2–4) and MP4SDTQ/6–311G(2df,2pd) levels. Enthalpies of formation and singlet-triplet and doublet-quartet energy splittings have also been obtained. The species investigated include ArS + , ArO + , NeS +, NeO +, ArCl + , NeCl +, HS and HS +. The reactions investigated include proton transfer, halogen atom transfer and charge transfer. In order to facilitate the study of reaction enthalpies, the reactions have been divided into four categories: (1) isogyric and the reactant and product pairs are isoelectronic; (2) isogyric and the reactant and product pairs are valence isoelectronic; (3) isogyric; (4) not even isogyric. The results from this study are compared to those from our earlier study. It is found that the MP4SDTQ/6–311G(2df,2pd) enthalpies of reaction reproduce the experimental enthalpies within 3.5 kcal mol −1 for all but nonisogyric reactions. MP n/6–31G ∗* results reproduce the higher level computational results and the experimental results consistently well only for reactions in category (1). There is also disagreement in the energy splittings obtained with the two basis sets. Finally, some suggestions are made to experimentalists about ion-molecule reactions that may produce the above ions.
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