CASCCD: Coupled-cluster method with double excitations and the CAS reference

A new multireference coupled-cluster method which includes double excitations and is based on the complete active space (CAS) multiconfigurational reference wave function is proposed. By partitioning the CAS orbitals into active and nonactive sets a two-component, coupled-cluster wave function involving excitations into orbitals of the different sets was constructed. The first component includes all the CAS excitations and the second component, which has the exponential form, consists of double external and semi-external excitations. The coupled-cluster equations for the energy and for the amplitudes involved in the two components of the wave function were derived and illustrated using a diagrammatic formalism. Several numerical tests were performed, and the results demonstrate a very good performance of the method as compared to the full configuration interaction results.

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