Gauge-origin independent formalism of two-component relativistic framework based on unitary transformation in nuclear magnetic shielding constant.

This article proposes a gauge-origin independent formalism of the nuclear magnetic shielding constant in the two-component relativistic framework based on the unitary transformation. The proposed scheme introduces the gauge factor and the unitary transformation into the atomic orbitals. The two-component relativistic equation is formulated by block-diagonalizing the Dirac Hamiltonian together with gauge factors. This formulation is available for arbitrary relativistic unitary transformations. Then, the infinite-order Douglas-Kroll-Hess (IODKH) transformation is applied to the present formulation. Next, the analytical derivatives of the IODKH Hamiltonian for the evaluation of the nuclear magnetic shielding constant are derived. Results obtained from the numerical assessments demonstrate that the present formulation removes the gauge-origin dependence completely. Furthermore, the formulation with the IODKH transformation gives results that are close to those in four-component and other two-component relativistic schemes.