Interfacing relativistic and nonrelativistic methods. III. Atomic 4-spinor expansions and integral approximations

摘要

Two approximations to the normalized elimination of the small component are presented which enable the work of a relativistic calculation to be substantially reduced. The first involves fixing the ratio of the large and small components in atomic calculations, which corresponds to a basis set expansion in terms of positive energy atomic 4-spinors. The second involves the definition of a local, i. e., center-dependent, fine structure constant, which has the effect of making atoms with #alpha# = 0 nonrelativistic. A series of test calculations on a variety of molecules and properties indicates that the errors incurred in the first approximation are negligible. In the second approximation, the errors are dependent on the property, the chemical environment and the atomic number. For the second period elements the errors in the approximation are for chemical purposes negligible. In the third period this is true for many properties, but for some, such as ligand-metal binding energies, there are discrepancies which may be a cause for concern in more accurate calculations. Beyond the third period it is usually necessary to treat atoms relativistically.