Chirality-encoded molecular wavefunctions

Abstract

For enantiomers, the ground-state charge densities are mapped into one another by spatial reflection, yet—when spin–orbit coupling (SOC) is present—their occupied spinors need not coincide beyond a global phase. SOC encodes spatially varying, intrinsic phase textures whose gradients leave the density unchanged but enter gauge-invariant response combinations. These phases provide a general mechanism for enantiospecific contributions in response tensors. We show that isotropic pseudoscalar signatures arise only from polar-axial couplings, while same-parity couplings remain mirror-even; in oriented samples, anisotropic tensor components can also flip sign. We derive analytical bounds linking SOC-driven spinor phases and amplitude distortions to measurable tensor differences and validate them with relativistic plane wave density-functional calculations on prototypical chiral molecules. Plane waves are chosen because they faithfully represent delocalized SOC phase textures that standard localized bases struggle to capture. Experiments that couple mirror-odd operators to SOC-induced phases in chiral samples can, in principle, yield enantiospecific responses.