The active-space equation-of-motion coupled-cluster methods for excited electronic states: Full EOMCCSDt

The full version of the equation-of-motion coupled-cluster (EOMCC) method w ith all singles and doubles, and a selected set of triples defined through active orbitals (EOMCCSDt) has been implemented and tested using the H-8, H 2O, N-2, C-2, and CH+ systems. It is demonstrated that the full EOMCCSDt me thod provides the results of the full EOMCCSDT (EOMCC singles, doubles, and triples) quality at the fraction of the computer effort associated with th e EOMCCSDT calculations. This includes excited states that are dominated by doubles and states that have large triexcited components. The excellent pe rformance of the EOMCCSDt approach is observed even when the ground electro nic state has a quasidegenerate character, which means that we can apply th e EOMCCSDt formalism to excited states that cannot be adequately described by the perturbative triples models. The EOMCCSDt method is equivalent to th e EOMCCSDT approach if all orbitals used in the EOMCCSDt calculations are a ctive. (C) 2001 American Institute of Physics.