Density functional calculations of electronic g-tensors using spin-orbit pseudopotentials and mean-field all-electron spin-orbit operators

被引:194
作者
Malkina, OL
Vaara, J
Schimmelpfennig, B
Munzarová, M
Malkin, VG
Kaupp, M
机构
[1] Slovak Acad Sci, Inst Inorgan Chem, SK-84236 Bratislava, Slovakia
[2] Slovak Acad Sci, Ctr Comp, SK-84236 Bratislava, Slovakia
[3] Max Planck Inst Festkorperforsch, D-70569 Stuttgart, Germany
[4] Univ Wurzburg, Inst Anorgan Chem, D-97074 Wurzburg, Germany
关键词
D O I
10.1021/ja000984s
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Modern density-functional methods for the calculation of electronic g-tensors have been implemented within the framework of the deMon code. All relevant perturbation operators are included. Particular emphasis has been placed on accurate yet efficient treatment of the two-electron spin-orbit terms. At an all-electron level, the computationally inexpensive atomic mean-field approximation is shown to provide spin-orbit contributions in excellent agreement with the results obtained using explicit one- and two-electron spin-orbit integrals. Spin-other-orbit contributions account for up to 25-30% of the two-electron terms and may thus be non-negligible. For systems containing heavy atoms we use a pseudopotential treatment, where quasirelativistic pseudopotentials are included in the Kohn-Sham calculation whereas appropriate spin-orbit pseudopotentials are used in the perturbational treatment of the g-tensors. This approach is shown to provide results in good agreement with the all-electron treatment, at moderate computational cost. Due to the atomic nature of both mean-field all-electron and pseudopotential spin-orbit operators used, the two approaches may even be combined in one calculation. The atomic character of the spin-orbit operators may also be used to analyze the contributions of certain atoms to the paramagnetic terms of the g-tensors. The new methods have been applied to a wide variety of species, including small main group systems, aromatic radicals, as well as transition metal complexes.
引用
收藏
页码:9206 / 9218
页数:13
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