Molecular rotation–vibration coupling by quantum wavepacket interference at potential energy curve crossings

Quantum wavepacket interference is shown to result in modulation of the ultrafast transient anisotropy of a diatomic molecule. The molecule is in a state comprising two bound electronic states at intermediate coupling strength and the anisotropy modulation enters via variations in the instantaneous contributions of the initial states to the total anisotropy. A necessary condition for the appearance of the modulation is that the involved rotational states possess different vibrational dynamics. The wavepacket interference mediates this coupling by imposing dynamical restrictions on the accessible vibrational phase space which depend on the rotational state.