  Recent experiments have demonstrated highly enantioselective population
transfer among rotational states using microwave fields with non-coplanar
polarizations, a milestone in our ability to control chiral molecules.
Extending this ability to the optical domain would open the door to all-optical
enantioselective photochemistry, the next milestone in this direction. Here we
show that the spatial variation of the field presents a major challenge along
this route, limiting the interaction region to a thin layer with a thickness of
the order of a wavelength. We provide a solution to this restriction by
carefully designing the quantum pathways leading to the excited state. Our
simulations reveal that the proposed scheme can result in differences of up to
19% in the excited state populations of R and S carvone. This is a major
improvement over what is possible with circularly polarized light (~0.01%) and
brings all-optical enantioselective photochemistry within reach for practical
applications.
