Tracking molecular wave packets in cesium dimers by coherent Raman scattering

We explore wave-packet dynamics in the ground X 1 � + and excited B 1 � u states of cesium dimers (Cs2). In particular, we study the dependence of the wave-packet dynamics on the relative timing between femtosecond pump, Stokes, and probe pulses in a nondegenerate BOXCARS beam geometry, which are commonly used for coherent anti-Stokes Raman scattering (CARS) spectroscopy. The experimental results are elucidated by theoretical calculations, which are based on the Liouville equations for the density matrix for the molecular states. We observe oscillations in CARS signals as functions of both Stokes and probe pulse delays with respect to the pump pulse. The oscillation period relates to the wave-packet motion cycle in either the ground or excited state of Cs2 molecules, depending on the sequence of the input laser pulses in time. The performed analysis can be applied to study and/or manipulate wave-packet dynamics in a variety of molecules. It also provides an excellent test platform for theoretical models of molecular systems.