Relativistic calculation of indirect NMR spin-spin couplings using the Douglas-Kroll-Hess approximation -: art. no. 204112

We have employed the Douglas-Kroll-Hess approximation to derive the perturbative Hamiltonians involved in the calculation of NMR spin-spin couplings in molecules containing heavy elements. We have applied this two-component quasirelativistic approach using finite perturbation theory in combination with a generalized Kohn-Sham code that includes the spin-orbit interaction self-consistently and works with Hartree-Fock and both pure and hybrid density functionals. We present numerical results for one-bond spin-spin couplings in the series of tetrahydrides CH4, SiH4, GeH4, and SnH4. Our two-component Hartree-Fock results are in good agreement with four-component Dirac-Hartree-Fock calculations, although a density-functional treatment better reproduces the available experimental data. (c) 2005 American Institute of Physics.