Formulation of a Dressed Coupled-Cluster Method with Implicit Triple Excitations and Benchmark Application to Hydrogen-Bonded Systems

• Published in: Journal of chemical theory and computation 2020-10, Vol.16 (10), p.6317-6328
• Main Authors: Tribedi, Soumi, Chakraborty, Anish, Maitra, Rahul
• Format: Article
• Language: English
• Subjects: Basis functions; Clusters; Excitation; Hydrogen bonding; Iterative methods; Mathematical analysis; Operators (mathematics); Quantum Electronic Structure; Robustness (mathematics)
• ISSN: 1549-9618; 1549-9626
• DOI: 10.1021/acs.jctc.0c00736

In this paper, we present a coupled-cluster theory based on a double-exponential wave operator ansatz, which is capable of mimicking the effects of connected triple excitations in an iterative manner. The triply excited manifold is spanned via the action of a set of scattering operators on doubly excited determinants, whereas their action annihilates the Hartree–Fock reference determinant. The effect of triple excitations is included at a computational scaling slightly higher than that of conventional coupled-cluster singles and doubles. Furthermore, we demonstrate two approximate schemes, which arise naturally, and argue that both these schemes come equipped with certain renormalization terms capable of handling nonbonding interactions due to robust inclusion of the screened Coulomb interaction. We justify our claims from both a theoretical perspective and a number of numerical applications to prototypical water clusters, in a number of basis functions. Our methods show overall comparable performance to the canonical coupled-cluster theory with singles, doubles, and perturbative triples (CCSD­(T)) and allied methods, however, at a lower computational scaling.