A Hilbert space multi-reference coupled-cluster study of the H4 model system

Abstract

Employing the Hilbert space ansatz, a fully quadratic coupled-cluster method with a multidimensional reference space is applied to a DZP basis study of the model system, H4. The reference space is described by two to four configurations at the level of single and double excitations, and single and double excitation operators are included in the expansions for the cluster and wave operator through quadratic terms. The performance of quadratic MRCCSD is investigated for the ground and three excited states of the H4 system consisting of two stretched hydrogen molecules in a trapezoidal configuration where the degree of quasidegeneracy is varied from a nondegenerate situation to a completely degenerate one. Compared to full CI, in the highly degenerate region, the MRCCSD works quite well. In less degenerate regions, the accuracy is less satisfactory.