Temporal and spatially resolved imaging of the correlated nuclear-electronic dynamics and of the ionized photoelectron in a coherently electronically highly excited vibrating LiH molecule.

Few-cycle ultrashort IR pulses allow excitation of coherently coupled electronic states toward steering nuclear motions in molecules. We include in the Hamiltonian the excitation process using an IR pulse of a definite phase between its envelope and carrier wave and provide a quantum mechanical description of both multiphoton excitation and ionization. We report on the interplay between these two processes in shaping the ensuing coupled electronic-nuclear dynamics in both the neutral excited electronic states and the cationic states of the diatomic molecule LiH. The dynamics is described by solving numerically the time-dependent Schrodinger equation at nuclear grid points using the partitioning technique with a subspace of ten coupled bound states and a subspace of discretized continuous states for the photoionization continua. We show that the coherent dynamics in the neutral subspace is strongly affected by the amplitude exchanges with the ionization continua during the pulse, as well as by the onset of nuclear motion. The coupling to the cation and the resulting ionization do not preclude the control of the motion in the neutral through control of the carrier-envelope phase. Our methodology provides visualization in space and in time not only of the entangled vibronic wave packet in the neutral states but also of the wave packet of the outgoing photoelectron. Thereby, we can spatially and temporally follow the dynamics of the outgoing and bound electrons during the pulse and the nuclear motion in the bound subspace while moving through nonadiabatic coupling regions after the pulse.