Collect. Czech. Chem. Commun. 2003, 68, 105-138

Effective Hamiltonian and Intermediate Hamiltonian Formulations of the Fock-Space Coupled-Cluster Method

Leszek Meissner* and JarosłaW Gryniaków

Institute of Physics, Nicholas Copernicus University, PL-87-100 Toruń, Poland


Various aspects of the effective Hamiltonian and intermediate Hamiltonian formulations are discussed in the context of the Fock-space coupled-cluster method. Problems that occur when single-reference methods of solving the Schrödinger equation need to be generalized to the multireference (MR) cases are pointed out. These problems make the generalization nontrivial, especially in the case of the most powerful coupled-cluster (CC) method. It is shown how some specific features of one of the basic MR-CC schemes, the Fock-space CC method, can be used to obtain a simple, yet very effective version of the method. This requires, however, switching from the effective Hamiltonian to the intermediate Hamiltonian formulation. The intermediate Hamiltonian version of the Fock-space CC method is discussed in detail and all its advantages over the standard one are emphasized.

Keywords: Ab initio calculations; Multi-reference coupled-cluster; Fock-space coupled-cluster; Intermediate Hamiltonian.

References: 95 live references.