Polarization dependent femtosecond pump-probe spectra display characteristic vibrational wave packet dynamics of ClF in Ar (isotropic cage and small fragment size) and in Kr (cylindrical cage and large fragments). The intensity ratio of the signals for pumping with parallel versus crossed polarization with respect to the probe pulse is close to the value 1/3, as expected for full photoselection immediately after excitation. For ClF this ratio depolarizes to unity within showing the ultrafast randomization of the orientation of the molecular bond due to fragment scattering off the matrix cage. The direction of the bond is geometrically fixed by the Kr matrix and the ratio remains constant.
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