Relativistic effects on the nuclear magnetic shielding tensor

J. I. MELO; M. C. RUIZ DE AZUA; C. G. GIRIBET; G. A. AUCAR; R. H. ROMERO

JOURNAL OF CHEMICAL PHYSICS

Año: 2003 vol. 118 p. 471 - 486

0021-9606

A new approach for calculating relativistic corrections to the nuclear magnetic shieldings is presented. Starting from a full relativistic second order perturbation theory expression a two-component formalism is constructed by transforming matrix elements using the elimination of small component scheme and separating out the contributions from the no-virtual pair and the virtual pair part of the second order corrections to the energy. In this way we avoid a strong simplification used previously in the literature. We arrive at final expressions for the relativistic corrections which are equivalent to those of Fukui et al. [J. Chem Phys. 105, 3175 (1996)] and at some other additional terms correcting both the paramagnetic and the diamagnetic part of the nuclear magnetic shielding. Results for some relativistic corrections to the shieldings of the heavy and light nuclei in HX and CH3X (X5Br,I) at both random phase and second order polarization propagator approach levels are given.