In this paper, we develop a theoretical framework that extends single-reference (SR) coupled-cluster (CC) theory beyond its conventional role of describing a single electronic state-typically the lowest-energy state within the symmetry sector defined by the reference determinant. Rather than viewing the SR-CC cluster operator solely as a device for reproducing one target state, we consider more general constructions in which different components of the cluster operator play distinct roles, ranging from encoding states of different symmetry than the reference to enabling SR-CC Ansatz to describe multiple states simultaneously. These developments lead to a new class of SR-CC downfolding formalisms in which the resulting active-space effective Hamiltonians are capable of concurrently representing multiple correlated states nonorthogonal to the reference function. We establish three theorems that formalize this extension and demonstrate that standard CC downfolding emerges as a special case of the proposed framework. Finally, we introduce a Hermitian variant based on a unitary CC representation, which enables realistic simulations of ground and excited states while reducing the quantum resources required.
In this paper, we develop a theoretical framework that extends single-reference (SR) coupled-cluster (CC) theory beyond its conventional role of describing a single electronic state-typically the lowest-energy state within the symmetry sector defined by the reference determinant. Rather than viewing the SR-CC cluster operator solely as a device for reproducing one target state, we consider more general constructions in which different components of the cluster operator play distinct roles, ranging from encoding states of different symmetry than the reference to enabling the SR-CC ansatz to describe multiple states simultaneously. These developments lead to a new class of SR-CC downfolding formalisms in which the resulting active-space effective Hamiltonians are capable of concurrently representing multiple correlated states non-orthogonal to the reference function. We establish three theorems that formalize this extension and demonstrate that standard CC downfolding emerges as a special case of the proposed framework. Finally, we introduce a Hermitian variant based on a unitary CC representation, which enables realistic simulations of ground and excited states while reducing the quantum resources required.
Coupled-cluster (CC) theory and Green's function many-body perturbation theory (MBPT) have long evolved as distinct yet complementary frameworks for describing electronic correlation. While CC methods employ exponential wavefunction parametrizations that guarantee size extensivity and systematic improvability, Green's function approaches such as the
GW approximation describe quasiparticle and optical excitations through diagrammatic resummations. Recent analyses have established a formal correspondence between these frameworks: the
GW approximation is equivalent to an equation-of-motion (EOM) treatment of the direct-ring coupled-cluster doubles (drCCD) method. Within this context, the extended CC (ECC) ansatz offers a unified framework connecting CC and MBPT. This formulation bridges CC-based and Green's function-based methods, providing novel avenues for incorporating vertex corrections within a CC framework that preserves a sum-over-state representation of the self-energy and lead to potentially systematically improvable Green's function approaches.