Room temperature chiral discrimination in paramagnetic NMR spectroscopy

Abstract

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

arXiv commentPhysical Review Letters, in press (2016). The paper has 5 pages, no figures. Supplementary Material file has 24 pages

References in corpus (4)

• NMR chemical shift as analytical derivative of the Helmholtz free energy
• Theory of NMR chemical shift in an electronic state with arbitrary degeneracy
• Dynamic method to distinguish between left- and right-handed chiral molecules
• Paramagnetic NMR chemical shift in a spin state subject to zero-field splitting

Cited by in corpus (1)

• Zero- to Ultralow-field Nuclear Magnetic Resonance