Quadratic response calculations of the electronic spin-orbit contribution to nuclear shielding tensors

被引:94
作者
Vaara, J [1 ]
Ruud, K
Vahtras, O
Ågren, H
Jokisaari, J
机构
[1] Linkoping Univ, Dept Phys & Measurement Technol, S-58183 Linkoping, Sweden
[2] Oulu Univ, Dept Phys Sci, NMR Res Grp, FIN-90571 Oulu, Finland
[3] Univ Oslo, Dept Chem, N-0315 Oslo, Norway
关键词
D O I
10.1063/1.476672
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The electronic spin-orbit contribution to nuclear magnetic shielding tensors, which causes the heavy-atom chemical shift of the shielding of light nuclei in the vicinity of heavy elements, is calculated as a sum of analytical quadratic response functions. We include both the one- and two-electron parts of the spin-orbit Hamiltonian and consider the interaction with both the Fermi contact and the spin-dipolar mechanisms. Ab initio calculations at the SCF and MCSCF levels are presented for the H-1 and C-13 Shielding tensors in the hydrogen and methyl halides. The applicability of different approximations to the full spin-orbit correction is discussed, and the calculated results are compared with experimental data, where available. (C) 1998 American Institute of Physics.
引用
收藏
页码:1212 / 1222
页数:11
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