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.

arXiv commentAdded Fig. 4, Added Table 1, shortened section 4

References in corpus (12)

• Valley Dependent Optoelectronics from Inversion Symmetry Breaking
• Photoelectron angular distributions from strong-field ionization of oriented molecules
• Attosecond-resolved photoionization of chiral molecules
• Sensitive Chiral Analysis via Microwave Three-wave Mixing
• Enantiomer-Specific State Transfer of Chiral Molecules
• Relaxation Dynamics in Photoexcited Chiral Molecules Studied by Time-Resolved Photoelectron Circular Dichroism: Toward Chiral Femtochemistry
• Generalized perspective on chiral measurements without magnetic interactions
• Observation of enhanced chiral asymmetries in the inner-shell photoionization of uniaxially oriented methyloxirane enantiomers
• Detecting chirality in molecules by linearly polarized laser fields
• Theoretical description of circular dichroism in photoelectron angular distributions of randomly oriented chiral molecules after multi-photon photoionization
• Propensity rules in photoelectron circular dichroism in chiral molecules I: Chiral hydrogen
• Emitter-site selective photoelectron circular dichroism of trifluoromethyloxirane

Cited by in corpus (12)

• Ultrafast chirality: the road to efficient chiral measurements
• Capturing electron-driven chiral dynamics in UV-excited molecules
• Fourfold Differential Photoelectron Circular Dichroism
• Propensity rules in photoelectron circular dichroism in chiral molecules I: Chiral hydrogen
• Photoelectron circular dichroism in angle-resolved photoemission from liquid fenchone
• Enantiosensitive steering of free-induction decay
• Propensity rules for photoelectron circular dichroism in strong field ionization of chiral molecules
• Chiral photoelectron angular distributions from ionization of achiral atomic and molecular species
• On the molecular information revealed by photoelectron angular distributions of isotropic samples
• Quantum control of ro-vibrational dynamics and application to light-induced molecular chirality
• Inducing enantiosensitive permanent multipoles in isotropic samples with two-color fields
• Enantiosensitive exceptional points in open chiral systems