Relativistic mass-correction to the heavy atom nuclear magnetic shieldings. Analysis of contributions in terms of localized orbitals

GOMEZ SERGIO S., RODOLFO H. ROMERO,AUCAR GUSTAVO A.

CHEMICAL PHYSICS LETTERS

Año: 2003 vol. 367 p. 265 - 269

0009-2614

The relativistic mass correction contributions to the nuclear magnetic shielding MC at the heavy nuclei X( MC(X) )  within the polarization propagator approach both at the pure zeroth-order (PZOA) and at the random phase approximation (RPA) were calculated for the heavy atoms X of a series of hydrides XHn(n=1-3). Inclusion of  this mechanism  brings the nonrelativistic nuclear magnetic shieldings to agreement with fully relativistic four-component calculations, as noted previously for the hydrogen halides. The analysis in terms of contributions from localized orbitals shows that this contribution has an inner core origin, while it remains unaffected by excitations involving bonding orbitals and lone pairs. For all thecompounds studied, the  MC(X) at PZOA level  differs from  the corresponding RPA calculation in less than 5%, although at a much lower computational cost.