Double Ionization Potential Equation-of-Motion Coupled-Cluster Approach with Full Inclusion of 4-Hole-2-Particle Excitations and Three-Body Clusters

TL;DR

This paper introduces advanced coupled-cluster methods for calculating double ionization potentials that fully include complex electron correlation effects, demonstrating improved accuracy over previous truncated approaches.

Contribution

The paper formulates and implements a new DIP-EOMCC method with full 4h-2p and triply excited correlations, enhancing the accuracy of double ionization potential calculations.

Findings

The new methods improve results compared to truncated approaches.

Codes are available in the open-source CCpy package.

Methods work with both nonrelativistic and scalar-relativistic Hamiltonians.

Abstract

The double ionization potential (DIP) equation-of-motion (EOM) coupled-cluster (CC) method with a full treatment of 4-hole-2-particle (4$h$-2$p$) correlations and triply excited clusters, abbreviated as DIP-EOMCCSDT(4$h$-2$p$), and its approximate form called DIP-EOMCCSD(T)(a)(4$h$-2$p$) have been formulated and implemented in the open-source CCpy package available on GitHub. The resulting codes work with both nonrelativistic and spin-free scalar-relativistic Hamiltonians. By examining the DIPs of a few small molecules, for which accurate reference data are available, we demonstrate that the DIP-EOMCCSDT(4$h$-2$p$) and DIP-EOMCCSD(T)(a)(4$h$-2$p$) approaches improve the results obtained using the DIP-EOMCC methods truncated at 3$h$-1$p$ or 4$h$-2$p$ excitations on top of the CC calculations with singles and doubles.