An “ultimate” coupled cluster method based entirely on T₂

Electronic structure methods built around double-electron excitations have a rich history in quantum chemistry. However, it seems to be the case that such methods are only suitable in particular situations and are not naturally equipped to simultaneously handle the variety of electron correlations that might be present in chemical systems. To this end, the current work seeks a computationally efficient, low-rank, “ultimate” coupled cluster method based exclusively on T₂ and its products that can effectively emulate more “complete” methods that explicitly consider higher-rank, T_2m, operators. We introduce a hierarchy of methods designed to systematically account for higher, even order cluster operators, such as T₄, T₆, …, T_2m, by invoking tenets of the factorization theorem of many-body perturbation theory (MBPT) and expectation-value coupled cluster theory. It is shown that each member within this methodological hierarchy is defined such that both the wavefunction and energy are correct through some order in MBPT and can be extended up to arbitrarily high orders in T₂. The efficacy of such approximations are determined by studying the potential energy surface of several closed and open-shell molecules. We find that the proposed hierarchy of augmented T₂ methods essentially reduces to standard CCD for problems where dynamic electron correlations dominate but offer improvements in situations where non-dynamic and static correlations become relevant. A notable highlight of this work is that the cheapest methods in this hierarchy—which are correct through fifth-order in MBPT—consistently emulate the behavior of the O ( N 10 ) CCDQ method, yet only require a O ( N 6 ) algorithm by virtue of factorized intermediates.