DISSOCIATION DYNAMICS OF MOLECULAR-IONS IN VERY HIGH CHARGE STATES

An attempt is made to relate the dissociation dynamics of highly charg ed molecular ions (possessing charges in excess of 2+) to molecular st ructure. High-level, ab initio configuration-interaction calculations are carried out of the potential energy functions of N-2(q+), for q=2- 12, and predictions are made of the values of the kinetic energies rel eased upon unimolecular dissociation of such ions. The calculated valu es are found to be significantly lower than those expected from simple Coulombic considerations. Electron density distributions of highly ch arged molecules are calculated and, on the basis of these, a long-live d state of a diatomic tri-cation, CS3+, is predicted. Mass spectrometr ic evidence is produced which confirms these predictions.