Noncollinear Relativistic Two-Component X2C Calculations of Hyperfine Couplings Using Local Hybrid Functionals. Importance of the High-Density Coordinate Scaling Limit

Abstract

Local hybrid functionals with position-dependent exact-exchange admixture have been implemented in the noncollinear spin form into a two-component X2C code and are evaluated for the hyperfine coupling tensors of a series of 3d, 4d, and 5d transition-metal complexes. One aim is to see if the potential of local hybrid functionals toward an improved balance between core-shell and valence-shell spin polarization, recently identified in nonrelativistic computations on 3d complexes (Schattenberg, C.; Maier, T. M.; Kaupp, M. J. Chem. Theory Comput. 2018, 14, 5653-5672), can be extended to the hyperfine couplings of heavier metal centers. The correctness of the two-component implementation is first established by comparison to previous computations for 3d systems with or without notable spin-orbit contributions to their hyperfine tensors, and the good performance of a standard "t-LMF" local mixing function is confirmed. However, when moving to 4d and 5d metal centers, the performance of such local mixing functions deteriorates. This is likely due to their violation of the homogeneous coordinate scaling condition in the high-density limit, which is particularly important for the core shells of heavier atoms. A local mixing function that respects this high-density limit performs notably better for heavier metal centers. However, it brings in much too high exact-exchange admixtures for the 3d systems and is too inflexible to simultaneously provide reasonable chemical accuracy in other areas. These results point to the ongoing need to develop improved local mixing functions and local hybrid functionals that exhibit favorable properties in different areas of space defined by very high and much lower electron densities.