Abstract

The intensity distributions in the overtones of resonance Raman spectra for I2 in liq. CCl4 and Xe are presented for several excitation energies in the bound part of the B 3P0u+ state. In liq. 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 z is inferred, in accordance with predissocn. to the a or a' states earlier proposed. The intensity distributions in liq. 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 predissocn. to the B\" 1P1u state within 40 fs in the range of internuclear distances between 2.78 and 2.85 .ANG. is obsd. which is less pronounced for large v'. The wave packet moves undistorted beyond the crossing with the B\" state up to 3 .ANG.. [on SciFinder (R)]

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