Fine-Tuning of Atomic Energies in Relativistic Multiconfiguration Calculations

Ab initio calculations sometimes do not reproduce the experimentally observed energy separations at a high enough accuracy. Fine-tuning of diagonal elements Hamiltonian matrix is process which seeks to ensure that calculated states mix are in agreement with experiment. The gives more accurate measures mixing than can be obtained ab calculations. requires diagonally dominant, generally case for based on jj-coupled configuration state functions. We show this problem circumvented by method transforms jj-coupling LSJ-coupling fine-tuning applies. fine-tuned then transformed back jj-coupling. implementation into General Relativistic Atomic Structure Package described and test runs validate program operations reported. new applied computation 2s21S0−2s2p1,3P1 transitions C III Rydberg B I, 2s2p22S1/2 perturber enters 2s2ns2S1/2 series. Improved convergence patterns results found compared