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First-Principles Calculation of Transition Metal Hyperfine Coupling Constants with the Strongly Constrained and Appropriately Normed (SCAN) Density Functional and its Hybrid Variants

Max-Planck-Institut für Kohlenforschung, Kaiser-Wilhelm-Platz, 1, 45470 Mülheim an der Ruhr, Germany
Magnetochemistry 2019, 5(4), 69; https://doi.org/10.3390/magnetochemistry5040069
Received: 27 October 2019 / Revised: 6 December 2019 / Accepted: 10 December 2019 / Published: 12 December 2019
(This article belongs to the Special Issue Electron Paramagnetic Resonance II)
Density functional theory (DFT) is used extensively for the first-principles calculation of hyperfine coupling constants in both main-group and transition metal systems. As with many other properties, the performance of DFT for hyperfine coupling constants is of variable quality, particularly for transition metal complexes, because it strongly depends on the nature of the chemical system and the type of approximation to the exchange-correlation functional. Recently, a meta-generalized-gradient approximation (mGGA) functional was proposed that obeys all known exact constraints for such a method, known as the Strongly Constrained and Appropriately Normed (SCAN) functional. In view of its theoretically superior formulation a benchmark set of complexes is used to assess the performance of SCAN for the challenging case of transition metal hyperfine coupling constants. In addition, two global hybrid versions of the functional, SCANh and SCAN0, are described and tested. The values computed with the new functionals are compared with experiment and with those of other DFT approximations. Although the original SCAN and the SCAN-based hybrids may offer improved hyperfine coupling constants for specific systems, no uniform improvement is observed. On the contrary, there are specific cases where the new functionals fail badly due to a flawed description of the underlying electronic structure. Therefore, despite these methodological advances, systematically accurate and system-independent prediction of transition metal hyperfine coupling constants with DFT remains an unmet challenge. View Full-Text
Keywords: hyperfine coupling; density functional theory; spectroscopy; hybrid functionals hyperfine coupling; density functional theory; spectroscopy; hybrid functionals
MDPI and ACS Style

Pantazis, D.A. First-Principles Calculation of Transition Metal Hyperfine Coupling Constants with the Strongly Constrained and Appropriately Normed (SCAN) Density Functional and its Hybrid Variants. Magnetochemistry 2019, 5, 69.

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