Comparing Perturbative and Commutator-Rank-Based Truncation Schemes in Unitary Coupled-Cluster Theory

Abstract

Unitary coupled cluster (UCC) theory offers a promising Hermitian alternative to conventional coupled cluster (CC) theory, but its practical implementation is hindered by the non-truncating nature of the Baker-Campbell-Hausdorff (BCH) expansion of the similarity-transformed Hamiltonian ($\bar{H}$). To address this challenge, various truncation strategies have been developed to approximate $\bar{H}$ in a compact and reliable manner. In this work, we compare the numerical performance of approximate UCC with single and double excitations (UCCSD) methods that employ many-body perturbation theory (MBPT) and commutator rank based truncation schemes. Our results indicate low-order MBPT-based schemes, such as UCC(2) and UCC(3), yield reasonable results near equilibrium, but they become unreliable at stretched geometries. Higher-order MBPT-based schemes do not necessarily improve performance, as the UCCSD(4) and UCCSD(5) amplitude equations sometimes lack solutions. In contrast, commutator-rank-based truncations exhibit greater numerical stability, with the Bernoulli representation of the BCH expansion enabling more rapid convergence to the UCCSD limit compared to the standard BCH formulation.