Relativistic effects on the nuclear magnetic shieldings of rare-gas atoms and halogen in hydrogen halides within relativistic polarization propagator theory

Abstract

In this work an analysis of the electronic origin of relativistic effects on the isotropic dia- and paramagnetic contributions to the nuclear magnetic shielding sigma(X) for noble gases and heavy atoms of hydrogen halides is presented. All results were obtained within the 4-component polarization propagator formalism at different level of approach [random-phase approximation (RPA) and pure zeroth-order approximation (PZOA)], by using a local version of the DIRAC code. From the fact that calculations of diamagnetic contributions to sigma within RPA and PZOA approaches for HX(X=Br,I,At) and rare-gas atoms are quite close each to other and the finding that the diamagnetic part of the principal propagator at the PZOA level can be developed as a series [S(Delta)], it was found that there is a branch of negative-energy "virtual" excitations that contribute with more than 98% of the total diamagnetic value even for the heavier elements, namely, Xe, Rn, I, and At. It contains virtual negative-energy molecular-orbital states with energies between -2 mc2 and -4 mc2. This fact can explain the excellent performance of the linear response elimination of small component (LR-ESC) scheme for elements up to the fifth row in the Periodic Table. An analysis of the convergency of S(Delta) and its physical implications is given. It is also shown that the total contribution to relativistic effects of the innermost orbital (1s1/2) is by far the largest. For the paramagnetic contributions results at the RPA and PZOA approximations are similar only for rare-gas atoms. On the other hand, if the mass-correction contributions to sigma(p) are expressed in terms of atomic orbitals, a different pattern is found for 1s1/2 orbital contributions compared with all other s-type orbitals when the whole set of rare-gas atoms is considered.