Relativistic calculation of indirect NMR spin-spin couplings using the Douglas-Kroll-Hess approximation.
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 CH(4), SiH(4), GeH(4), and SnH(4). 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.
Melo
Juan I
JI
Departamento de Física, Facultad de Ciencias Exactas y Naturales, Universidad de Buenos Aires, Ciudad Universitaria, Pabellón 1, 1428 Buenos Aires, Argentina.
Ruiz de Azúa
Martín C
MC
Peralta
Juan E
JE
Scuseria
Gustavo E
GE