The intermediate Hamiltonian Fock-space coupled-cluster method with approximate evaluation of the three-body effects.

Abstract

The exponential parametrization of the wave function used in the coupled-cluster approaches has proven very successful in the ab initio description of atomic and molecular systems. This concerns first of all the single-reference version of the method that is designed for states dominated by a single Slater determinant. Usually, the coupled-cluster methods with one- and two-body excitation operators in the exponent form the basic computational schemes. The inclusion of three-body effects in the cluster operator to increase the accuracy of the results is numerically expensive, so their approximate evaluation is rather used in practice. In the case of the single-reference coupled-cluster approach, the problem of approximate evaluation of three-body effects in the cluster operator has been well studied, and computational schemes of both noniterative and iterative nature have been proposed. The situation is different in the case of multireference coupled-cluster methods which are required to describe open shell and quasidegenerate states. The multireference approaches in their standard effective Hamiltonian formulations are more complicated and less frequently used in routine calculations; however, one of them, the so-called Fock-space coupled-cluster method, becomes very effective if reformulated within the intermediate Hamiltonian framework. Both the basic version of the method with one- and two-body clusters and the extended one that includes up to three-body operators in the exponent are implemented. The latter approach provides more accurate results, but its relatively high numerical cost limits its applicability. For this reason, going beyond the basic scheme with one- and two-body clusters through an approximate evaluation of the impact of three-body clusters is of great interest. In the paper, we investigate different ways of approximate inclusion of the three-body effects in the Fock-space coupled-cluster method designated for excitation energy calculations.