Natural orbitals in multiconfiguration calculations of hyperfine structure parameters

Abstract

We are reinvestigating the hyperfine structure of sodium using a fully relativistic multiconfiguration approach. In the fully relativistic approach, the computational strategy somewhat differs from the original nonrelativistic counterpart used in [1]. Numerical instabilities force us to use a layer-by-layer approach that has some broad unexpected effects. Core correlation is found to be significant and therefore requires to be described in an adequate orbital basis. The natural-orbital basis provides an interesting alternative to the orbital basis from the layer-by-layer approach, allowing us to overcome some deficits of the latter, giving rise to magnetic dipole hyperfine structure constant values in excellent agreement with observations. Effort is made to assess the reliability of the natural-orbital bases and to illustrate their efficiency.