Second-order Rayleigh-Schrödinger Perturbation Theory for the {\sc Grasp}2018 Package: Core-valence Correlations

RESUMO

The General Relativistic Atomic Structure package [{\sc Grasp}2018, C. Froese Fischer, G. Gaigalas, P. Jönsson, J. Bieroń, Comput. Phys. Commun. (2019), DOI: https://doi.org/10.1016/j.cpc.2018.10.032 ], is based on multiconfiguration Dirac-Hartree-Fock and relativistic configuration interaction (RCI) methods for energy structure calculations. Atomic state function used in the program is built from the set of configuration state functions (CSFs). The valence-valence, core-valence and core-core correlations are explicitly included through expansions over CSFs in RCI. We present a combination of RCI and the stationary second-order Rayleigh-Schrödinger many-body perturbation theory in irreducible tensorial form to account for electron core-valence correlations when an atom or ion has any number of valence electrons. This newly developed method, which offers two ways of use, allows a significant reduction of the CSF space for complex atoms and ions. We also demonstrate how the method and program works for energy structure calculation of Cl III element.