Tunnel ionization of molecules and orbital imaging

We study whether tunnel ionization of aligned molecules can be used to map out the electronic structure of the ionizing orbitals. We show that the common view, which associates tunnel ionization rates with the electronic density profile of the ionizing orbital, is not always correct. Using the example of tunnel ionization from the CO(2) molecule, we show how and why the angular structure of the alignment-dependent ionization rate moves with increasing the strength of the electric field. These modifications reflect a general trend for molecules.