Transition-potential coupled cluster II: optimisation of the core orbital occupation number

Abstract

The issue of orbital relaxation in computational core-hole spectroscopy, specifically x-ray absorption, has been a major problem for methods such as equation-of-motion coupled cluster with singles and doubles (EOM-CCSD). The transition-potential coupled cluster (TP-CC) method is utilised to address this problem by including an explicit treatment of orbital relaxation via the use of reference orbitals with a fractional core occupation number. The value of the fractional occupation parameter λ was optimised for both TP-CCSD and XTP-CCSD methods in an element-specific manner due to the differences in atomic charge and energy scale. Additionally, TP-CCSD calculations using the optimised parameters were performed for the K-edge absorption spectra of gas-phase adenine and thymine. TP-CCSD reproduces the valence region well and requires smaller overall energy shifts in comparison to EOM-CCSD, while also improving on the relative position and intensities of several absorption peaks.