Molecular Free Electron Vortices in Photoionization by Polarization-Tailored Ultrashort Laser Pulses

Atomic and molecular free electron vortices (FEVs), characterized by their spiral-shaped momentum distribution, have recently attracted a great deal of attention due to their varied shapes and their unusual topological properties. Shortly after their theoretical prediction by the single-photon ionization (SPI) of He atoms using pairs of counterrotating circularly polarized attosecond pulses, FEVs have been demonstrated experimentally by the multiphoton ionization (MPI) of alkali atoms using single-color and bichromatic circularly polarized femtosecond pulse sequences. Recently, we reported on the analysis of the experimental results employing a numerical model based on the ab initio solution of the time-dependent Schrödinger equation (TDSE) for a two-dimensional (2D) atom interacting with a polarization-shaped ultrashort laser field. Here, we apply the 2D TDSE model to study molecular FEVs created by SPI and MPI of a diatomic molecule using polarization-tailored single-color and bichromatic femtosecond pulse sequences. We investigate the influence of the coupled electron-nuclear dynamics on the vortex formation dynamics and discuss the effect of CEP- and rotational averaging on the photoelectron momentum distribution. By analyzing how the molecular structure and dynamics is imprinted in the photoelectron spirals, we explore the potential of molecular FEVs for ultrafast spectroscopy.