Multireference Mukherjee’s coupled cluster method with triexcitations in the linked formulation: Efficient implementation and applications

摘要

We have formulated the multireference Mukherjee’s coupled clusters method with triexcitations MR MkCCSDT in the linked version and implemented it in the ACES II program package. The assessment of the new method has been performed on the first three electronic states of the oxygen molecule, on studies of singlet-triplet gap in methylene and twisted ethylene, where a comparison with other multireference CC treatments and with experimental data is available. The MR MkCCSDT results show accuracy comparable to which can be achieved with CCSDT in single reference cases. Comparison of the previously developed MkCCSDT method with MkCCSDT as a reference suggests, that MkCCSDT might be a promising candidate for an accurate treatment of systems where the static correlation plays an important role, at least for situations where small model spaces are sufficient.