Method of Moments of Coupled-Cluster Equations: Externally Corrected Approaches Employing Configuration Interaction Wave Functions

Abstract: A new approach to the many-electron correlation problem, termed the method of moments of coupled-cluster equations (MMCC), is further developed and tested. The main idea of the MMCC theory is that of the noniterative energy corrections which, when added to the energies obtained in the standard coupled-cluster calculations, recover the exact (full configuration interaction) energy. The MMCC approximations require that a guess is provided for the electronic wave function of interest. The idea of using simple estimates of the wave function, provided by the inexpensive configuration interaction (CI) methods employing small sets of active orbitals to define higher–than–double excitations, is tested in this work. The CI-corrected MMCC methods are used to study the single bond breaking in HF and the simultaneous breaking of both O–H bonds in H₂O.