Extension of the CC($P$;$Q$) Formalism to the Electron Attachment and Ionization Potential Equation-of-Motion Coupled-Cluster Frameworks

TL;DR

This paper extends the CC($P$;$Q$) formalism to electron attachment and ionization potential EOM-CC methods, achieving high accuracy with reduced computational effort for open-shell molecules.

Contribution

It introduces active-orbital-based EA/IP-CC($P$;$Q$) approaches that improve accuracy and efficiency over previous methods for describing electronic states.

Findings

Achieves sub-millihartree accuracy compared to high-level data.

Reduces computational effort relative to previous methods.

Improves upon existing EA/IP-CR-EOMCC approaches.

Abstract

We combine the electron attachment (EA) and ionization potential (IP) equation-of-motion (EOM) coupled-cluster (CC) approaches with the CC($P$;$Q$) formalism. The resulting methodologies are used to describe the electronic states of several open-shell molecules, with the goal of approximating high-level EA/IP-EOMCC energetics corresponding to a full treatment of 3-particle-2-hole (3$p$-2$h$) and 3-hole-2-particle (3$h$-2$p$) excitations on top of CC with singles and doubles (CCSD). We show that the active-orbital-based EA/IP-EOMCC CC($P$;$Q$) approaches, abbreviated as EA/IP-CC(t;3), achieve sub-millihartree accuracies relative to the parent EA-EOMCCSD(3$p$-2$h$)/IP-EOMCCSD(3$h$-2$p$) data using reduced computational effort, while improving upon their completely renormalized EA/IP-CR-EOMCC(2,3) counterparts.