Propensity rules in photoelectron circular dichroism in chiral molecules. II. General picture

Abstract

Photoelectron circular dichroism results from one-photon ionization of chiral molecules by circularly polarized light and manifests itself in forward-backward asymmetry of electron emission in the direction orthogonal to the light polarization plane. To expose the physical mechanism responsible for asymmetric electron ejection, we first establish a rigorous relation between the responses of unaligned and partially or perfectly aligned molecules. Next, we identify a propensity field, which is responsible for the chiral response in the electric-dipole approximation, i.e. a chiral response without magnetic interactions. We find that this propensity field, up to notations, is equivalent to the Berry curvature in a two-band solid. The propensity field directly encodes optical propensity rules, extending our conclusions regarding the role of propensity rules in defining the sign of forward-backward asymmetry from the specific case of chiral hydrogen to generic chiral systems. Optical propensity rules underlie the chiral response in photoelectron circular dichroism. The enantiosensitive flux of the propensity field through the sphere in momentum space determines the forward-backward asymmetry in unaligned molecules and suggests a geometrical origin of the chiral response. This flux has opposite sign for opposite enantiomers and vanishes for achiral molecules.