Ultrafast intramolecular and caging dynamics from resonance Raman spectroscopy of I2 in solutions

The resonance Raman overtone progressions of I2 in liq. Xe and in CCl4 following excitation in the bound and continuum parts of the B state are discussed and compared with theor. simulations. The intensity distribution of the Raman overtones yields information about the wave packet dynamics in the excited state. The Raman contribution from the bound part can be treated as that of an out going wave packet. This indicates damping within one recurrence due to predissocn. to the repulsive B, a and a' states. The curve crossing can be localized in space and time from the Raman data. The Landau-Zener formalism gives a consistent description and coupling matrix elements are deduced which are similar for I2 in liq. Xe and in CCl4. [on SciFinder (R)]