A systematic improvement to UGA-SSMRCCSD equations and its implication for potential energy curves

Abstract

The Unitary Group Adaptation (UGA) offers a very compact and efficient spin adaptation strategy for any spin-free Hamiltonian in a many body framework. Our use of UGA in the context of state-specific (SS) Jeziorski–Monkhorst Ansatz based multireference coupled cluster (MRCC) theory obviates the non-commutativity between the spin-free cluster operators via a normal ordered exponential parametrization in the wave operator. A previous formulation of UGA-SSMRCC by us [R. Maitra, D. Sinha, and D. Mukherjee, J. Chem. Phys. 137, 024105 (2012)], using the same ansatz, employed certain sufficiency conditions to reach the final working equations, which cannot be improved systematically. In this article, we will present a more rigorous formulation that follows from an exact factorization of the unlinked terms of the Bloch equation, resulting in equations on which a hierarchy of approximations can be systematically performed on the emergent additional terms. This derivation was shown in our recent article [D. Chakravarti, S. Sen, and D. Mukherjee, Mol. Phys. 119, e1979676 (2021)] in the context of a single open shell CC formalism and was applied to spectroscopic energy differences where the contribution of the new terms was found to be of the order of ∼0.001 eV for ionization potential, electron affinity, and excitation energy. In the current work, we will present a comparison between the earlier and current formulations via both a theoretical analysis and a numerical demonstration of the dramatic effect of the additional terms brought in by the factorization on potential energy curves. The contribution of such terms was found to gain importance with an increase in the number of singly occupied active orbitals in the model space functions.