Femtosecond dynamics of I2(B 3Π0u+) in liquids from resonance Raman spectra

Xu, J.; Schwentner, N.; Chergui, M.
November 1994
Journal of Chemical Physics;11/1/1994, Vol. 101 Issue 9, p7381
Academic Journal
The intensity distributions in the overtones of resonance Raman spectra for I2 in liquid CCl4 and Xe are presented for several excitation energies in the bound part of the B 3Π0u+ 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 Å 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‘ 1Π1u state within 40 fs in the range of internuclear distances between 2.78 and 2.85 Å is observed which is less pronounced for large v’. The wave packet moves undistorted beyond the crossing with the B‘ state up to 3 Å.


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