The formulation and performance of a perturbative correction to the perfect quadruples model

A recently published alternative hierarchy of coupled-cluster approximations is reformulated as a perturbative correction. A single variant, a model for the total electronic energy based on the perfect quadruples model, is explored in detail. The computational scaling of the method developed is the same as canonical second order Mo̸ller-Plesset perturbation theory (fifth order in the number of molecular orbitals), but its accuracy competes with the high-accuracy, high-cost standard CCSD(T), even when the latter is allowed to break spin-symmetry. The variation presented can be implemented without explicit calculation and storage of the most expensive energy contributions, thereby improving the range of systems which can be treated. The performance and scaling of the method are demonstrated with calculations on the water, fluorine, and oxirane molecules, and compared to the parent model.