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arxiv: 1212.3830 · v1 · pith:UKSJCFPVnew · submitted 2012-12-16 · ⚛️ physics.chem-ph · physics.atm-clus

Paramagnetic NMR chemical shift in a spin state subject to zero-field splitting

classification ⚛️ physics.chem-ph physics.atm-clus
keywords paramagneticspinstateformulapreviousshiftsplittingsubject
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We derive a general formula for the paramagnetic NMR nuclear shielding tensor of an open-shell molecule in a pure spin state, subject to a zero-field splitting (ZFS). Our findings are in contradiction with a previous proposal. We present a simple application of the newly derived formula to the case of a triplet ground state split by an easy-plane ZFS spin Hamiltonian. When $kT$ is much smaller than the ZFS gap, thus a single non-degenerate level is thermally populated, our approach correctly predicts a temperature-independent paramagnetic shift, while the previous theory leads to a Curie temperature dependence.

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