Relativistic Quantum Chemical Investigation of Actinide Covalency Measured by Electron Paramagnetic Resonance Spectroscopy

We investigate actinide covalency effects in two AnCptt3 (An = Th, U) complexes recently studied with pulsed electron paramagnetic resonance spectroscopy, using the Hyperion package to obtain relativistic hyperfine coupling constants from relativistic multiconfigurational wave functions. 1H and 13C HYSCORE simulations using the computed parameters show excellent agreement with the experimental data, highlighting the accuracy of modern relativistic ab initio methods. The extent of covalency indicated from the calculations on ThCptt3 is in agreement with the original report based on traditional spectral fitting methods, while the covalency in UCptt3 is found to be previously overestimated. The latter is due to the paramagnetic spin–orbit effect that arises naturally in a relativistic theory of hyperfine coupling and yet was not accounted for in the original study, thus highlighting the necessity of relativistic approaches for the interpretation of magnetic resonance data pertaining to actinides.