A recently proposed theory of chiral discrimination in NMR spectroscopy based on the detection of a molecular electric polarization $\mathit{P}$ rotating in a plane perpendicular to the NMR magnetic field [A. D. Buckingham, J. Chem. Phys. 140, 011103 (2014)] is generalized here to paramagnetic systems. Our theory predicts new contributions to $\mathit{P}$, varying as the square of the inverse temperature. Ab initio calculations for ten ${\mathrm{Dy}}^{3+}$ complexes, at 293 K, show that, in strongly anisotropic paramagnetic molecules, $\mathit{P}$ can be more than 1000 times larger than in diamagnetic molecules, making paramagnetic NMR chiral discrimination amenable to room temperature detection.

• Received 8 November 2015

DOI:https://doi.org/10.1103/PhysRevLett.116.163001