New approach to the state-specific multireference coupled-cluster formalism

摘要

A new development is presented in the framework of the state-specific multireference (MR) coupled-cluster (CC) theory (MRCC). The method is based on the CASSCF (complete active space self-consistent field) wave function and it is designed specifically for calculating excited electronic states. In the proposed approach, the cluster structure of the CC wave operator and the method to determine this operator are the key features. Since the general formulation of the CASCC method is uncontracted, i.e., allows the interaction between the nondynamic and dynamic correlation effects to affect both the CAS reference function and the CC correlation wave operator, the method is expected to perform better than contracted perturbative approaches such as the CASPT2 (second-order perturbation theory based on the CAS wave function) method. Also, the CASCC method is not a perturbative approach and is not based on selection of an unperturbed Hamiltonian, which in the case of the CASPT2 method often leads to the "intruder state" problem. CASCC calculations of the lowest totally symmetric excited state of the H-8 model system using the internally contracted and uncontracted approaches reveal some interesting features of the methodology. (C) 2000 American Institute of Physics. [S0021-9606(00)31723-8]. [References: 29]