Extending spin-symmetry projected coupled-cluster to large model spaces using an iterative null-space projection technique

Recently, we introduced an orbital-invariant approximate coupled-cluster (CC) method in the spin-projection manifold. The multi-determinantal property of spin-projection means that the parametrization in the spin-extended CC (ECC) ansatz is nonorthogonal and overcomplete. Therefore, the linear dependencies must be removed by an orthogonalization procedure to obtain meaningful solutions. Multi-reference methods often achieve this by diagonalizing a metric of the equation system, but this is not feasible with ECC because of the enormous size of the metric, a consequence of the incomplete active space of the spin-projected Hartree–Fock reference. As a result, the applicability of ECC has been limited to small benchmark systems, for which the ansatz was shown to be superior to the configuration interaction and linearized approximations. In this article, we provide a solution to this problem that completely avoids the metric diagonalization by iteratively projecting out its null-space from the working equations. As the additional computational cost required for this iterative projection is only marginal, it greatly expands the application range of ECC. We demonstrate the potential of approximate ECC by studying the complete basis set limit of F₂ and transition metal complexes such as NiO, Mn₂, and [Cu₂O₂]²⁺ , which have all been hindered by the prohibitively large metric size. We also identify the potential inadequacy of the molecular orbitals given by spin-projected Hartree–Fock in some cases, and propose possible solutions. © 2018 Wiley Periodicals, Inc.