Relativistic calculation of indirect NMR spin-spin couplings using the Douglas-Kroll-Hess approximation

JUAN IGNACIO MELO; MARTIN C. RUIZ DE AZUA; JUAN E. PERALTA; GUSTAVO E. SCUSERIA

JOURNAL OF CHEMICAL PHYSICS

American Institute of Physics

Año: 2005 vol. 123 p. 1 - 7

0021-9606

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 incombination 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. © 2005 American Institute of Physics. [DOI: 10.1063/1.2133730]