EOM-fpCCSD: An Accurate Alternative to EOM-CCSD for Doubly Excited and Charge-Transfer States.

Abstract

We introduce a new equation-of-motion coupled-cluster method based on a pair coupled-cluster doubles (pCCD) reference, termed frozen-pair EOM-CCSD (EOM-fpCCSD). This approach combines the computational efficiency of the pCCD ansatz with a dynamical correlation correction, enabling a reliable description of electronically excited states within the EOM framework. The method has been implemented in the open-source PyBEST software package. Its performance is systematically benchmarked against standard EOM-CCSD and its pair-tailored variant (EOM-ptCCSD), using both canonical Hartree–Fock and pCCD natural orbitals. For charge-transfer (CT) excitations taken from the QUEST database, EOM-fpCCSD yields excitation energies very close to those of EOM-CCSD, outperforming EOM-ptCCSD, as well as to the theoretical best estimates (TBEs). Working within the localized pCCD natural orbital basis allows us to determine the directed CT character, which quantifies the directed charge flow from one molecular domain to another. Numerical results show that EOM-fpCCSD, EOM-CCSD, and EOM-ptCCSD provide nearly identical descriptions of the directed CT character, despite changes in excitation energies. The true advantage of EOM-fpCCSD becomes evident for the challenging QUEST subset of doubly excited states. While EOM-ptCCSD performs similarly to standard EOM-CCSD, EOM-fpCCSD significantly outperforms both methods for these problematic states compared to TBEs. In addition to improving the accuracy of excitation energies, EOM-fpCCSD also converges for several states that standard EOM-CCSD and EOM-ptCCSD fail to converge. These results demonstrate that EOM-fpCCSD offers a promising and computationally efficient route toward a more accurate description of complex electronic excitations.