Hybrid coupled cluster methods: Combining active space coupled cluster methods with coupled cluster singles, doubles, and perturbative triples

Abstract

Based on the coupled-cluster singles, doubles, and a hybrid treatment of triples (CCSD(T)-h) method developed by us [J. Shen, E. Xu, Z. Kou, and S. Li, J. Chem. Phys. 132, 114115 (2010); and ibid. 133, 234106 (2010); and ibid. 134, 044134 (2011)], we developed and implemented a new hybrid coupled cluster (CC) method, named CCSD(T)q-h, by combining CC singles and doubles, and active triples and quadruples (CCSDtq) with CCSD(T) to deal with the electronic structures of molecules with significant multireference character. These two hybrid CC methods can be solved with non-canonical and canonical MOs. With canonical MOs, the CCSD(T)-like equations in these two methods can be solved directly without iteration so that the storage of all triple excitation amplitudes can be avoided. A practical procedure to divide canonical MOs into active and inactive subsets is proposed. Numerical calculations demonstrated that CCSD(T)-h with canonical MOs can well reproduce the corresponding results obtained with non-canonical MOs. For three atom exchange reactions, we found that CCSD(T)-h can offer a significant improvement over the popular CCSD(T) method in describing the reaction barriers. For the bond-breaking processes in F(2) and H(2)O, our calculations demonstrated that CCSD(T)q-h is a good approximation to CCSDTQ over the entire bond dissociation processes.