Accurate core-excited states via inclusion of core triple excitations in similarity-transformed EOM theory

TL;DR

This paper introduces CVS-STEOMEE-CCSD+cT, a new method that improves core-excitation energy calculations by including core triple excitations, addressing orbital relaxation issues more effectively than previous methods.

Contribution

The paper develops CVS-STEOMEE-CCSD+cT, incorporating core triple excitations within similarity-transformed EOM theory to enhance core-excitation energy accuracy.

Findings

Significantly improves core-excitation energy predictions.

Performs nearly as well as transition-potential coupled cluster methods.

Outperforms CVS-EOMEE-CCSD in accuracy.

Abstract

The phenomenon of orbital relaxation upon excitation of core electrons is a major problem in the linear-response treatment of core-hole spectroscopies. Rather than addressing relaxation through direct dynamical correlation of the excited state via equation-of-motion coupled cluster theory (EOMEE-CC), we extend the alternative similarity-transformed equation-of-motion coupled cluster theory (STEOMEE-CC) by including the core-valence separation (CVS) and correlation of triple excitations only within the calculation of core ionization energies. This new method, CVS-STEOMEE-CCSD+cT, significantly improves on CVS-EOMEE-CCSD and unmodified CVS-STEOMEE-CCSD when compared to full CVS-EOM-CCSDT for K-edge core-excitation energies of a set of small molecules. The improvement in both absolute and relative (shifted) peak positions is nearly as good as for transition-potential coupled cluster (TP-CC), which includes an explicit treatment of orbital relaxation, and CVS-EOMEE-CCSD*, which includes a perturbative treatment of triple excitations.