Coupled Cluster Method

Jaroslav Zamastil, Tereza Uhlířová

Ramón Alain Miranda‐Quintana, Rugwed A. Lokhande, Carlos E. V. de Moura +2 more

We introduce a novel class of coupled cluster (CC) methods that leverage the seniority concept to enhance efficiency and accuracy in electronic structure calculations. While existing approaches, such as the pair coupled cluster doubles (pCCD) method, are limited to seniority-zero (Ω = 0) wavefunctions,1 we propose a more flexible framework: seniority-restricted coupled cluster (sr-CC). This new methodology selectively constrains the seniority sectors accessible through excitation operators in the cluster expansion, enabling a more systematic exploration of electron correlation effects. By balancing computational cost and accuracy, sr-CC provides a promising pathway for advancing electronic structure theory, particularly in strongly correlated systems.

Tomoko Kinoshita, Osamu Hino, Rodney J. Bartlett

We present a method for the approximate solution of the coupled-cluster (CC) equation, based upon the singular value decomposition (SVD). The key idea of this method is that we use SVD for the cluster amplitudes to exploit the physically important states in the CC equation. This method enables us to significantly reduce the computational requirements for CC calculations without losing the essence of the method. Relationships to the density matrix renormalization group theory and the local correlation methods are mentioned. We perform pilot calculations on some atoms and molecules to investigate the applicability of the method.

Giampaolo Co’

Minsik Cho, Troy Van Voorhis

Coupled Cluster (CC) theory is one of the most popular correlated wavefunction methods, yet the steep computational cost scaling of CC truncated at higher rank limits its application. Modern Selected Configuration Interaction (SCI) methods successfully exploit the sparsity of ground-state wavefunctions in the determinant space, motivating an analogous approach with the exponential CC ansatz. In this work, we introduce Selected Coupled Cluster (SCC), an arbitrary-order sparse CC method that explicitly solves the CC residual equations within a compact amplitude space guided by an SCI wavefunction. SCC optimizes the CC amplitudes in the sparse amplitude space. Using a pilot Just-in-Time (JIT) compiled implementation, we benchmark SCC against SCI, SCI+PT2, standard rank-truncated dense CC (CCSD, CCSDT), and DMRG across various chemical systems. We demonstrate that SCC exhibits fast, monotonic convergence with the SCI variational threshold, outperforming SCI and surpassing SCI+PT2 in the tight-threshold regime. SCC also provides accurate energies for high-dimensional topologies, where DMRG typically converges slowly with bond dimension. SCC thus presents an efficient drop-in enhancement for modern SCI workflows.

Piotr Piecuch B, Jeffrey R. Gour, Marta Włoch

Abstract The energy expansion defining the biorthogonal method of moments of coupled‐cluster equations (MMCC) [Piecuch and Włoch, J Chem Phys, 2005, 123, 224105 and Piecuch et al., Chem Phys Lett 2006, 418, 467], which leads to the size extensive completely renormalized (CR) coupled‐cluster (CC) approach with singles, doubles, and noniterative triples employing the left eigenstates of the similarity‐transformed Hamiltonian, termed CR‐CC(2,3), is overviewed and rederived. The rederivation of the biorthogonal MMCC expansion presented in this work is based on a direct resummation and subsequent elimination of the many‐body components of the exponential wave operator of CC theory that appear at individual moment contributions in the original MMCC energy expansion [Kowalski and Piecuch, J Chem Phys, 2000, 113, 18; Kowalski and Piecuch, J Chem Phys 2001, 115, 2966], enabling one to understand why the CR‐CC(2,3) method using the biorthogonal MMCC theory is more accurate than the earlier CR‐CCSD(T) approach. The superiority of the CR‐CC(2,3) method over the CR‐CCSD(T) and other previously developed single‐reference CC methods with a noniterative treatment of triply excited clusters, including the widely used CCSD(T) approach and the triples corrections defining the CCSD(2) schemes, is illustrated by examining the singlet–triplet gap of the (HFH)− magnetic system in which two paramagnetic centers are linked via a polarizable diamagnetic bridge. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008