Experiments are carried out to probe the competition between ionization and dissociation in highly excited small molecules. The analysis of data includes a calculation of statistical covariance between all the fragments (both ions and electrons), which allows identification of specific collision partners and the transition state of their parent molecular systems. Experiments are performed with long (15 ns) and short (10 ps) pulsed 193 nm radiation at power densities between 1 GW/cm2 and 100 TW/cm2. At the lower intensities, the effects of resonant bound and unbound intermediate states on this competition are studies. At higher intensities the details of Coulomb explosions and above threshold dissociation are studied in diatomic systems.
