Ootani Y, Maeda H, Fukui H
Kitami Institute of Technology, 165 Koencho, Kitami 090-8507, Japan.
J Chem Phys. 2007 Aug 28;127(8):084117. doi: 10.1063/1.2759199.
A two-component relativistic theory accurately decoupling the positive and negative states of the Dirac Hamiltonian that includes magnetic perturbations is derived. The derived theory eliminates all of the odd terms originating from the nuclear attraction potential V and the first-order odd terms originating from the magnetic vector potential A, which connect the positive states to the negative states. The electronic energy obtained by the decoupling is correct to the third order with respect to A due to the (2n+1) rule. The decoupling is exact for the magnetic shielding calculation. However, the calculation of the diamagnetic property requires both the positive and negative states of the unperturbed (A=0) Hamiltonian. The derived theory is applied to the relativistic calculation of nuclear magnetic shielding tensors of HX (X=F,Cl,Br,I) systems at the Hartree-Fock level. The results indicate that such a substantially exact decoupling calculation well reproduces the four-component Dirac-Hartree-Fock results.
