Reducing Exact Two-Component Theory for NMR Couplings to a One-Component Approach: Efficiency and Accuracy

The self-consistent and complex spin-orbit exact two component (X2C) formalism for NMR spin-spin coupling constants [J. Chem. Theory Comput. 17, 3974-3994 (2021)] is reduced to a scalar one-component ansatz. This way, the first-order response term can be partitioned into the Fermi-contact (FC) and spin-dipole (SD) interactions as well as the paramagnetic spin-orbit (PSO) contribution. The FC+SD terms are real and symmetric, while the PSO term is purely imaginary and antisymmetric. The relativistic one-component approach is combined with a modern density functional treatment up to local hybrid functionals including the response of the current density. Computational demands are reduced by factors of 8-24 as shown for a large tin compound consisting of 137 atoms. Limitations of the current ansatz are critically assessed, i.e. the one-component treatment is not sufficient for tin compounds featuring a few heavy halogen atoms.