Perfect Control of Photoelectron Anisotropy for Randomly Oriented Ensembles of Molecules by XUV REMPI and Polarization Shaping.

We report two schemes to generate perfect anisotropy in the photoelectron angular distribution of a randomly oriented ensemble of polyatomic molecules. In order to exert full control over the anisotropy of photoelectron emission, we exploit interferences between single-photon pathways and a manifold of resonantly enhanced two-photon pathways. These are shown to outperform nonsequential (ω, 2ω) bichromatic phase control for the example of CHFClBr molecules. We are able to optimize pulses that yield anisotropic photoelectron emission thanks to a very efficient calculation of photoelectron momentum distributions. This is accomplished by combining elements of quantum chemistry, variational scattering theory, and time-dependent perturbation theory.