Analysis of fourth-, fifth-, and infinite-order triple excitations in unitary coupled cluster theory

Abstract: In this work, we introduce a correction to the unitary coupled cluster method with single and double excitations (UCCSD) that incorporates the effects of missing triple excitations through a treatment that is correct through fifth-order in many-body perturbation theory (MBPT), which we refer to as UCCSD[T-5]. We then benchmark the performance of UCCSD[T-5] alongside the previously developed fourth-order UCCSD[T], comparing both against the infinite-order treatment of triples in UCCSDT as well as full configuration interaction (FCI). Two key findings emerge from this analysis. First, the fourth-order correction in UCCSD[T] consistently provides the closest agreement with FCI in estimating ground state energies, outperforming both UCCSD[T-5] and UCCSDT. Second, the inclusion of fifth-order corrections as in UCCSD[T-5] largely recovers the infinite-order triples limit in UCCSDT. With the growing interest in UCC ans\"atze for quantum computing and the constraints imposed by current quantum hardware, these results underscore the potential of using classically computed perturbative corrections within UCC theory to salient triple excitation effects without requiring the additional quantum resources as would be demanded by the UCCSDT ansatz.