Stability and Cooling of the C_{7}

We have studied the stability of the smallest long-lived all carbon molecular dianion (C_{7}^{2-}) in new time domains and with a single ion at a time using a cryogenic electrostatic ion-beam storage ring. We observe spontaneous electron emission from internally excited dianions on millisecond timescales and monitor the survival of single colder C_{7}^{2-} molecules on much longer timescales. We find that their intrinsic lifetime exceeds several minutes-6 orders of magnitude longer than established from earlier experiments on C_{7}^{2-}. This is consistent with our calculations of vertical electron detachment energies predicting one inherently stable isomer and one isomer which is stable or effectively stable behind a large Coulomb barrier for C_{7}^{2-}→C_{7}^{-}+e^{-} separation.

Spontaneous Electron Emission from Hot Silver Dimer Anions: Breakdown of the Born-Oppenheimer Approximation.

We report the first experimental evidence of spontaneous electron emission from a homonuclear dimer anion through direct measurements of Ag_{2}^{-}→Ag_{2}+e^{-} decays on milliseconds and seconds timescales. This observation is very surprising as there is no avoided crossing between adiabatic energy curves to mediate such a process. The process is weak, yet dominates the decay signal after 100 ms when ensembles of internally hot Ag_{2}^{-} ions are stored in the cryogenic ion-beam storage ring, DESIREE, for 10 s. The electron emission process is associated with an instantaneous, very large reduction of the vibrational energy of the dimer system. This represents a dramatic deviation from a Born-Oppenheimer description of dimer dynamics.

Plasmon excitation and subsequent isomerization dynamics in naphthalene and azulene under fast proton interaction.

The interaction of fast protons (velocity between 1.41 and 2.4 a.u.) with naphthalene and azulene is investigated as a model of an ion-polycyclic aromatic hydrocarbon interaction system. Production of various intact and fragment ions in coincidence with electron emission, electron transfer to projectile, or both is analyzed. The two targets being isomers, the rather obvious similarity in the fundamental ion-molecule collision energetics is quantitatively verified. The fast isomerization processes of cationic azulene are observed to be influencing its further dissociation channels such as C2H2 and H eliminations. A first ever attempt is presented here wherein single plasmon excitation in conjunction with isomerization dynamics is reported. Evidence from dication evaporation energetics is used to invoke the double plasmon excitation model. A model based on the multiplasmon resonance explains the observed proton velocity dependence of double to single ionization cross sections. Moreover an attempt is made to reinforce the proposition of double plasmon excitation by explaining the observed suppression of neutral H loss from dications as opposed to monocations.