Calculation of Electronic g-Tensors for Transition Metal Complexes Using Hybrid Density Functionals and Atomic Meanfield Spin-Orbit Operators

摘要

We report the first implementation of the calcualtion of electronic g-tensors by density functional methods with hybrid functionals, Spin-orbit coupling is treated by the atomic meanfield approximation. g-Tensors for a set of small main group radicals and for a series of ten 3d and two 4d transition metal complexes have ben compared using the locla density approximation (VWN functinal), the generatlized gradient aproximation (BP86 functional), as well as B3-type (B3PW91) and BH-type (BHPW91) hybrid functionals. For main group radicals, the effect of exactexchange mixing is small. In contrast, significant differences between the various functinals arise for transition metal complexes. As has been shown previously, local and in particular gradient-corrected functionals tend to underestimate the "parameagnetic" contributions to the g-tensors in these cases and thereby recover only about 40-50% of the range of experimental g-tensor components. This is improved to ca. 60% by the B3PW91 functinal, which also gives slightly reuced standard deviations. The range incrases to almost 100% using the half-and-half functional BHPW91. However, the quality of the correlation with experimental data worsens due to a significant overestimate of some intermediate g-tensor values. The worse performance of the BHPW91 functional in these cases is accompanied by spin contamination. Although none of the functionals tested thus appears to be ideal for the treatment of electronic g-tensors in transition metal complexes, the B3PW91 hybrid functional exhibited the overall most satisfactory performance. Apart from the validation of hybrid functionals, some aspects in the treatment of spin-orbit contributions to the g-tensor are discussed.