Enhancing the Accuracy of XPS Calculations: Exploring Hybrid Basis Set Schemes for CVS-EOMIP-CCSD Calculations

Abstract

Reliable computational methodologies and basis sets for modeling x-ray spectra are essential for extracting and interpreting electronic and structural information from experimental x-ray spectra. In particular, the trade-off between numerical accuracy and computational cost due to the size of the basis set is a major challenge, since molecular orbitals undergo extreme relaxation in the core-hole state. To gain clarity on changes in electronic structure induced by the formation of a core-hole, the use of sufficiently flexible basis for expanding the orbitals, particularly for the core region, has been shown to be essential. This work focuses on the refinement of core-hole ionized state calculations using the equation-of-motion coupled cluster (EOM-CC) family of methods through an extensive analysis on the effectiveness of "hybrid" and mixed basis sets. In this investigation, we utilize the CVS-EOMIP-CCSD method in combination and construct hybrid basis sets piece-wise from readily available Dunning's correlation consistent basis sets in order to calculate x-ray ionization energies for a set of small gas phase molecules. Our results provide insights into the impact of basis sets on CVS-EOMIP-CCSD calculations of K-edge ionization energies of first-row p-block elements. These insights enable us to understand more about the basis set dependence of the core IEs computed and allow us to establish a protocol for deriving reliable and cost-effective theoretical estimates for computing IEs of small molecules containing such elements.