Theory of Field-Dependent NMR Shifts in Paramagnetic Molecules

NMR chemical shifts depend on the magnetic flux density, which becomes more and more important when stronger and stronger magnetic fields become available. Herein, we develop a theory of the field dependence of NMR shifts of paramagnetic molecules in solution. Our derivation leads to two distinct approaches: a finite field approach that describes the shift up to infinite order in the applied field B0 but requires numerical integration for the orientational average, and a 2nd order approach that is valid up to 2nd order in B0 . In this latter approach, the orientational average can be performed analytically and the field dependence cleanly separates into two additive terms: the well-known “indirect” field dependence due to incomplete averaging in solution and the “direct” field dependence due to the nonlinear response to the external field. In analogy to the diamagnetic case, the direct field dependence depends on a fourth-order tensor τ whose elements are fourth derivatives of the electronic Helmholtz free energy. Generalizing the Van den Heuvel–Soncini equation, we provide analytical sum-over-states equations for these higher-order derivatives. Using the NiSAL-HDPT complex as an example, we demonstrate the applicability of the 2nd order approach at room temperature and the highest commercially available field strength and show that it agrees well with the field dependence measured experimentally.