Restricted magnetically balanced basis applied for relativistic calculations of indirect nuclear spin-spin coupling tensors in the matrix Dirac-Kohn-Sham framework

摘要

The relativistic four-component density functional approach based on the use of restricted magnetically balanced basis (mDKS-RMB), applied recently for calculations of NMR shielding, was extended for calculations of NMR indirect nuclear spin-spin coupling constants. The unperturbed equations are solved with the use of a restricted kinetically balanced basis set for the small component while to solve the second-order coupled perturbed DKS equations a restricted magnetically balanced basis set for the small component was applied. Benchmark relativistic calculations have been carried out for the X-H and H-H spin-spin coupling constants in the XH4 series (X = C, Si, Ge, Sn and Pb). The method provides an attractive alternative to existing approximate two-component methods with transformed Hamiltonians for relativistic calculations of spin-spin coupling constants of heavy-atom systems. In particular, no picture-change effects arise in our method for property calculations.