Relativistic Theory for Indirect Nuclear Spin-Spin Couplings within the Polarization Propagator Approach

GUSTAVO A. AUCAR; JENS ODDERSHEDE

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY

JOHN WILEY & SONS INC

Lugar: New York; Año: 1993 vol. 47 p. 425 - 435

0020-7608

We present a relativistic theory for the nuclear spin-spin coupling tensor within the polarization propagator approach using the particle-hole Dirac-Coulomb-Breit Hamiltonian and the full four-component wave function. We give explicit expressions for the coupling tensor in the random-phase approximation, neglecting the Breit interaction. A purely relativistic perturbative electron-nuclear Hamiltonian is used and it is shown how the single relativistic contribution to the coupling tensor reduces to Ramsey?s three second-order terms (Fermi contact, spin-dipole, and paramagnetic spin-orbit) in the nonrelativistic limit. The principal propagator becomes complex and the leading property integrals mix atomic orbitals of different parity. The well-known propagator expressions for the coupling tensor in the nonrelativistic limit is obtained neglecting terms of the order c-? (n 2 1).