We report a comparative study of the features in dissociative double ionization by high energy electron impact of N2 and CO molecules. The ratio of cross-section of charge symmetric dissociative ionization to non-dissociative ionization (CSD-to-ND ratio) and the kinetic energy release (KER) spectra of dissociation are experimentally measured and carefully corrected for various ion transmission losses and detector inefficiencies. Given that the double ionization cross sections of these iso-electronic diatomics are very similar, the large difference in the CSD-to-ND ratios must be attributable to the differences in the evolution dynamics of the dications. To understand these differences, potential energy curves (PECs) of dications have been computed using multi-reference configuration interaction method. The Franck-Condon factors and tunneling life times of vibrational levels of dications have also been computed. While the KER spectrum of N2 (++) can be readily explained by considering dissociation via repulsive states and tunneling of meta-stable states, indirect dissociation processes such as predissociation and autoionization have to be taken into account to understand the major features of the KER spectrum of CO(++). Direct and indirect processes identified on the basis of the PECs and experimental KER spectra also provide insights into the differences in the CSD-to-ND ratios.

We calculate the isotope-independent Li + -Li potential energy curves for the electronic ground and first excited states. The scattering phase shifts and total scattering cross section for the 7 Li + -7 Li collision are calculated, with an emphasis on the ultralow-energy domain down to the s-wave regime. The effect of physically motivated alterations on the calculated potential energy curves is used to determine the bound of accuracy of the low-energy scattering parameters for the ion-atom system. It is found that the scattering length for the A 2 + u state, a u = 1325a 0 , is positive and has well-constrained bounds. For the X 2 + g state, the scattering length, a g = 20 465a 0 , has a large magnitude, as it is sensitive to the restrained change of the potential, due to the presence of a vibrational state in the vicinity of the dissociation limit.

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Dissociation of molecular ions from highly excited states is difficult to probe, so our knowledge of their dynamical evolution and the parameters governing the dissociation is limited. The main complication is due to the large density of high-lying states and crossing of states. The latter may change the kinematics of the fragments, but in general, the contributions from different states to the fragment kinetic energy distributions cannot be separated. Consequently, the exact nature of the evolution remains elusive. In the present work, we have performed kinematic analysis of the dissociation dynamics of di-cations of N 2 and CO formed by photoionization, aiming to probe their highly excited states. Correlated fragment ion momenta are measured in coincidence with energy-analyzed ejected electrons, allowing us to estimate energy of the transient molecular ions. These measurements bring out the differences in kinematics of the fragmentation of transient molecular ions having different internal energies. Our analysis indicates that highly excited states decay primarily to their own asymptotic limits with only weak coupling to states decaying to lower asymptotes.

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