An efficient Fock space multi-reference coupled cluster method based on natural orbitals: Theory, implementation, and benchmark

We present a natural orbital-based implementation of the intermediate Hamiltonian Fock space coupled-cluster method for the (1, 1) sector of Fock space. The use of natural orbitals significantly reduces the computational cost and can automatically choose an appropriate set of active orbitals. The new method retains the charge transfer separability of the original intermediate Hamiltonian Fock space coupled-cluster method and gives excellent performance for valence, Rydberg, and charge-transfer excited states. It offers significant computational advantages over the popular equation of motion coupled cluster method for excited states dominated by single excitations.