Similarity transformed equation of motion coupled cluster theory revisited: a benchmark study of valence excited states (1402.3008v2)

Abstract: The similarity transformed equation of motion coupled cluster (STEOM-CC) method is benchmarked against CC3 and EOM-CCSDT-3 for a large test set of valence excited states of organic molecules studied by Schreiber et al. [M. Schreiber, M.R. Silva-Junior, S.P. Sauer, and W. Thiel, J. Chem. Phys. $\textbf{128}$, 134110 (2008)]. STEOM-CC is found to behave quite satisfactorily and provides significant improvement over EOM-CCSD, CASPT2 and NEVPT2 for singlet excited states, lowering standard deviations of these methods by almost a factor of 2. Triplet excited states are found to be described less accurately, however. Besides the parent version of STEOM-CC, additional variations are considered. STEOM-D includes a perturbative correction from doubly excited determinants. The novel STEOM-H ($\omega$) approach presents a sophisticated technique to render the STEOM-CC transformed Hamiltonian hermitian. In STEOM-PT, the expensive CCSD step is replaced by many-body second-order perturbation theory (MBPT(2)), while extended STEOM (EXT-STEOM) provides access to doubly excited states. To study orbital invariance in STEOM, we investigate orbital rotation in the STEOM-ORB approach. Comparison of theses variations of STEOM for the large test set provides a comprehensive statistical basis to gauge the usefulness of these approaches.