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.

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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
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article

Chirality-encoded molecular wavefunctions

Vladimiro Mújica, Julio L. Palma, Louis‐S. Bouchard, Robert N. Schwartz et al.
The Journal of Chemical Physics
Surface Chemistry and Catalysis
article

Chirality-encoded molecular wavefunctions

Vladimiro Mújica, Julio L. Palma, Louis‐S. Bouchard, Robert N. Schwartz, Thalia Georgiou
article en

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.

The Journal of Chemical PhysicsVol. 163(20)
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)
Openalex Percentile: Top 65%
Surface Chemistry and Catalysis
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Chirality-encoded molecular wavefunctions — Vladimiro Mújica, Julio L. Palma, et al. · The Journal of Chemical Physics (2025) | TGRS Research Map | TGRS