Applications of core-valence extensive multi-reference coupled cluster theory and core-extensive coupled cluster-based linear response theory

Abstract

The single reference coupled cluster based linear response theory (CCLRT) and valence-universal multi-reference coupled cluster (VU-MRCC) theory for direct difference energy calculations have been presented. The similarities and differences in the structure of these two formalisms have also been addressed. The core-extensive CCLRT is applied to compute the ionization potentials (IPs) of HCl and excitation energies of CuH using Hartree–Fock (HF) orbitals. We further report the relativistic applications of the VU-MRCC theory through the computation of the ground and excited/ionized state energies and related properties of Ag and Hg atoms using Dirac–Hartree–Fock (DHF) orbitals. The IPs, excitation energies, and the spectroscopic constants reported here are in favorable agreement with experiment and with other correlated calculations.