Cage motions induced by electronic and vibrational excitations: Cl2 in Ar.

Femtosecond dynamics of molecular vibrations as well as cage motions in the B←X transition of Cl₂ in solid Ar have been investigated. We observed molecular vibrational wave-packet motion in experimental pump-probe spectra and an additional oscillation with a 500 fs period which is assigned to the zone-boundary phonon of the Ar crystal. The cage motion is impulsively driven by the B←X transition due to the expansion of the electronic cloud of the chromophore. To clarify the underlying mechanism, we performed simulations based on the diatomics-in-molecules method which takes into account the different shapes of the Cl₂ electronic wave function in the B and X states as well as the anisotropic interaction with the matrix. The simulation results show that Ar atom motion in the (100) plane is initiated by the electronic transition and that only those Ar atoms oscillate coherently with an ∼500 fs period which are essentially decoupled from the molecular vibration. Their phase and time evolution are in good agreement with the experimentally observed oscillation, supporting the assignment as a displacive excitation of coherent phonons. [ABSTRACT FROM AUTHOR]