Biorthogonal moment expansions in coupled-cluster theory: Review of key concepts and merging the renormalized and active-space coupled-cluster methods

摘要

After reviewing recent progress in the area of the development of coupled-cluster (CC) methods for quasi-degenerate electronic states that are characterized by stronger non-dynamical correlation effects, including new generations of single- and multi-reference approaches that can handle bond breaking and excited states dominated by many-electron transitions, and after discussing the key elements of the left-eigenstate completely renormalized (CR) CC and equation-of-motion (EOM) CC methods, and the underlying biorthogonal method of moments of CC (MMCC) equations [P. Piecuch, M. W?och, J. Chem. Phys. 123 (2005) 224105; P. Piecuch, M. W?och, J.R. Gour, A. Kinal, Chem. Phys. Lett. 418 (2006) 467; M. W?och, M.D. Lodriguito, P. Piecuch, J.R. Gour, Mol. Phys. 104 (2006) 2149], it is argued that it is beneficial to merge the CR-CC/EOMCC and active-space CC/EOMCC [P. Piecuch, Mol. Phys. 108 (2010) 2987, and references therein] theories into a single formalism. In order to accomplish this goal, the biorthogonal MMCC theory, which provides compact many-body expansions for the differences between the full configuration interaction and CC or, in the case of excited states, EOMCC energies, obtained using conventional truncation schemes in the cluster operator T and excitation operator R _μ, is generalized, so that one can correct the CC/EOMCC energies obtained with arbitrary truncations in T and R _μ for the selected many-electron correlation effects of interest. The resulting moment expansions, defining the new, Flexible MMCC (Flex-MMCC) formalism, and the ensuing CC(P; Q) hierarchy, proposed in the present work, enable one to correct energies obtained in the active-space CC and EOMCC calculations, in which one selects higher many-body components of T and R _μ via active orbitals and which recover much of the relevant non-dynamical and some dynamical electron correlation effects in applications involving potential energy surfaces (PESs) along bond breaking coordinates, for the effects of higher-order, primarily dynamical, correlations missing in the active-space CC/EOMCC considerations. The Flex-MMCC corrections to the active-space CC/EOMCC energies are mathematically similar to the non-iterative energy corrections defining the existing left-eigenstate CR-CC and CR-EOMCC methods, such as CR-CC(2, 3) and CR-EOMCC(2, 3). The potential advantages of the Flex-MMCC and CC(P; Q) formalisms are illustrated by describing the initial implementation and numerical tests of the novel CC hybrid scheme, abbreviated as CC(t; 3), in which one corrects the results of the CC calculations with singles, doubles, and active-space triples, termed CCSDt, for the remaining effects due to connected triple excitations that are missing in the CCSDt considerations, but are present in the MMCC-based CR-CC(2, 3) approach. By examining bond breaking in the HF, F _2, and F2+ molecules, it is demonstrated that the CC(t; 3) method improves the CCSDt and CR-CC(2, 3) results, providing PESs that agree with those obtained with the full CC theory with singles, doubles, and triples (CCSDT) to within small fractions of a millihartree, at the fraction of the computer costs of the CCSDT calculations. Different strategies for defining active-space triples within the CC(t; 3) scheme and the underlying CCSDt method are discussed. When limited to the ground-state problem, the CC(t; 3) approach can be regarded as an improved and rigorously derived extension of the recently proposed CCSD(T)-h method [J. Shen, E. Xu, Z. Kou, S. Li, J. Chem. Phys. 132 (2010) 114115], in which triples corrections of the CCSD(T) type are replaced by their more robust CR-CC(2, 3)-style analogs.