| Abstract
| - Two series of small polyatomic ions, HxCO+ and HxN2+ (x = 1, 2, 3), were systematically characterizedusing three correlated theoretical techniques: density functional theory using the B3LYP functional, spin-restricted second-order perturbation theory, and singles + doubles coupled cluster theory with perturbativetriples. On the basis of thermodynamic data, the existence of these ions in inductively coupled plasma massspectrometry (ICP-MS) experiments is not surprising since the ions are predicted to be considerably morestable than their corresponding dissociation products (by 30−170 kcal/mol). While each pair of isoelectronicions exhibit very similar thermodynamic and kinetic characteristics, there are significant differences withineach series. While the mechanism for dissociation of the larger ions occurs through hydrogen abstraction, thetriatomic ions (HCO+ and HN2+) appear to dissociate by proton abstraction. These differing mechanismshelp to explain large differences in the abundances of HN2+ and HCO+ observed in ICP-MS experiments.
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