Correcting the Record: DFT Confirms J Couplings Are Enantio-Insensitive
A recent study challenges claims that NMR spectroscopy can directly distinguish molecular enantiomers through differences in their spin–spin (J) coupling constants. By recomputing these couplings with ADF using high-quality integration grids, proper relativistic corrections, and—critically—true mirror-symmetric molecular geometries, the authors show that the previously reported multi-hertz differences vanish. Their investigation reveals that the original calculations were performed on structures that were not actually enantiomeric, leading to unphysical J-coupling values and a false appearance of enantiospecificity. By combining corrected DFT calculations with a symmetry-based theoretical analysis, the authors demonstrate that enantiomers must yield identical J couplings in solution. This unified computational and theoretical perspective resolves the discrepancies in earlier reports and reaffirms the long-established understanding that NMR J couplings are fundamentally enantio-insensitive.
Perras, F.A., Zwanziger, J.W. and Rossini, A.J. (2025) “DFT calculations and theory do not support enantiospecificity in NMR J-coupling constants.“ Nat Commun 16, 10032.
