Abstract:
We first test our recently developed relativistic coupled-cluster-based linear response theory (RCCLRT) by computing the principal and the shake-up ionization potentials (IP) of highly stripped atoms. Comparison is made between the IP values obtained from the relativistic and non-relativistic CCLRT calculations. The comparisons for light atoms, where the relativistic contributions are negligible, provide a test of the method, while comparisons for heavy atoms quantify the relativistic effect. For one-valence problems such as ionization processes, there is a formal equivalence between the principal IP values from the CCLRT and multi-reference coupled cluster (MRCC) theory when using the 1h-0p model space. The principal IPs obtained from the CCLRT are size-extensive, but the (2h-1p) shake-up IPs are not fully size-extensive, where the size-inextensivity error scales as the number of valence excitations. The computed valence and shake-up ionization energies via the RCCLRT approach are in excellent agreement with experimental data. The IPs computed using the non-relativistic CCLRT also match favourably well with the experiment only when the atomic number and ionic charge are small.
