Artículos de revistas
Relativistic effects on the nuclear magnetic shielding tensor
Fecha
2002-10Registro en:
Melo, Juan Ignacio; Ruiz de Azua, Martín César; Giribet, Claudia Gloria; Aucar, Gustavo Adolfo; Romero, Rodolfo Horacio; Relativistic effects on the nuclear magnetic shielding tensor; American Institute of Physics; Journal of Chemical Physics; 118; 2; 10-2002; 471-486
0021-9606
1089-7690
CONICET Digital
CONICET
Autor
Melo, Juan Ignacio
Ruiz de Azua, Martín César
Giribet, Claudia Gloria
Aucar, Gustavo Adolfo
Romero, Rodolfo Horacio
Resumen
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 CHȝX (X=Br,I) at both random phase and second order polarization propagator approach levels are given.