Journal of Chemical Physics, Vol.101, No.9, 7381-7387, 1994
Femtosecond Dynamics of I-2(B (3)-Pi(0U)+) in Liquids from Resonance Raman-Spectra
The intensity distributions in the overtones of resonance Raman spectra for I-2 in liquid CCl4 and Xe are presented for several excitation energies in the bound part of the B 3 Pi(0u)(+) state. In liquid CCl4, the decrease in intensity with v" is monotonous and for all excitation energies similar to that of a free wave packet in the gas phase. A dephasing time shorter than the round trip time of 300 fs and a dephasing process which occurs beyond 3 Angstrom is inferred, in accordance with predissociation to the a or a’ states earlier proposed. The intensity distributions in liquid Xe contain a fast decay and a plateau and the strength of both contributions varies with excitation energy. For low v’ in the B state a predissociation to the B" 1 Pi(1u) state within 40 fs in the range of internuclear distances between 2.78 and 2.85 Angstrom is observed which is less pronounced for large v’. The wave packet moves undistorted beyond the crossing with the B" state up to 3 Angstrom.
Keywords:INFRARED ABSORPTION-SPECTRUM;HIGH-PRESSURES;IODINE;TIME;I2;PREDISSOCIATION;SCATTERING;PHOTODISSOCIATION;FEMTOCHEMISTRY;EXCITATION