On the existence of a natural common gauge-origin for the calculation of magnetic properties of atoms and molecules via gaugeless basis sets

It is proven that, within the conventional approach using a common origin and gaugeless basis sets for the calculation of atomic magnetizability and Larmor current density induced by an external magnetic field, the natural gauge origin coincides with the nucleus. Recipes for defining an optimal gauge origin for the calculation of magnetizability and magnetic shielding at the nuclei of a molecule are given. Within the common origin approach, the paramagnetic contributions to the components of magnetic tensors of a molecule are represented by a minimum number of non-vanishing parameters if the gauge origin is chosen at a point characterized by the total molecular symmetry, e.g., the center of electronic charge for magnetizabilities. It is shown that total values of diagonal components of the magnetic shielding tensor σI at a nucleus I in a molecule, as well as separate diamagnetic σdI andparamagnetic σpI contributions, calculated via the common origin method, are origin independent for a number of local point group symmetries. The diagonal components (and the average value) of σI depend on the gauge origin only for nuclear site symmetries C1, Cs, Cn, Cnv, n = 2, 3. . . . Group theoretical methods show interesting features, e.g., for S4 local symmetry, in a coordinate transformation, the paramagnetic contribution to the zz component and to the trace of the shielding tensor is origin independent, whereas the xx and yy components mix into one another, in such a way that their sum remains constant.