Economical Doubly Electron-Attached Equation-of-Motion Coupled-Cluster Methods with an Active-Space Treatment of Three-Particle-One-Hole and Four-Particle-Two-Hole Excitations.

Abstract

The previously developed active-space doubly electron-attached (DEA) equation-of-motion (EOM) coupled-cluster (CC) method with up to four-particle-two-hole (4p-2h) excitations [Shen, J.; Piecuch, P. J. Chem. Phys. 2013, 138, 194102], which utilizes the idea of applying a linear electron-attaching operator to the CC ground state of an (N - 2)-electron closed-shell system to generate ground and excited states of the N-electron open-shell species of interest, has been extended to a considerably less expensive model, in which both 3p-1h and 4p-2h terms rather than 4p-2h contributions only are selected using active orbitals. As illustrated by the calculations involving low-lying singlet and triplet states of methylene, trimethylenemethane, cyclobutadiene, and cyclopentadienyl cation and bond breaking in F2, the proposed DEA-EOMCC method with the active-space treatment of 3p-1h and 4p-2h excitations and its lower-level counterpart neglecting 4p-2h contributions are capable of accurately reproducing the results obtained using their considerably more expensive parent counterparts with a full treatment of 3p-1h and full or active-space treatment of 4p-2h excitations.