Dissociation dynamics of molecular ions in very high charge states

Abstract

An attempt is made to relate the dissociation dynamics of highly charged molecular ions (possessing charges in excess of 2+) to molecular structure. High-level, ab initio configuration-interaction calculations are carried out of the potential energy functions of N₂^q+, for q = 2-12, and predictions are made of the values of the kinetic energies released upon unimolecular dissociation of such ions. The calculated values are found to be significantly lower than those expected from simple Coulombic considerations. Electron density distributions of highly charged molecules are calculated and, on the basis of these, a long-lived state of a diatomic tri-cation, CS³⁺, is predicted. Mass spectrometric evidence is produced which confirms these predictions.