Multi-reference Fock space coupled-cluster method in the intermediate Hamiltonian formulation for potential energy surfaces

Abstract

The effective and intermediate Hamiltonian multi-reference coupled-cluster (CC) method with singles and doubles for the doubly ionized (0,2) sector of Fock space (FS) is formulated and implemented. The intermediate Hamiltonian realization of the (0,2) FS problem provides a robust computational scheme for solving the FS-CC equations free from the intruder state problem. By introducing an efficient factorization strategy, we obtain a very efficient tool that can be used for computing double ionization potentials but more significantly to describe multi-reference problems in CC theory, illustrated by twisted ethylene and the potential energy curve for F(2). The latter separates smoothly to two F atoms, while the former avoids the cusp behavior at the 90° dihedral. We also explore the double ionization potentials for several small molecules, H(2)O, CO, C(2)H(2), and C(2)H(4).