Chirality-encoded molecular wavefunctions
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.
Authors
- Vladimiro Mújica (ORCID: https://orcid.org/0000-0002-5237-4851)
- Julio L. Palma (ORCID: https://orcid.org/0000-0002-2611-7560)
- Louis‐S. Bouchard (ORCID: https://orcid.org/0000-0003-4151-5628)
- Robert N. Schwartz (ORCID: https://orcid.org/0000-0003-4639-5936)
- Thalia Georgiou (ORCID: https://orcid.org/0000-0003-1502-0058)
Institutions
- Pennsylvania State University (US)
- University of California, Los Angeles (US)
- University of West Los Angeles (US)
- Charles R. Drew University of Medicine and Science (US)
- Arizona State University (US)
Publication Details
- Journal
- The Journal of Chemical Physics
- Published
- 2025-11-24
- DOI
- https://doi.org/10.1063/5.0293823
- Primary Topic
- Surface Chemistry and Catalysis
- Type
- article
- Field-Weighted Citation Impact
- 0.00