The form of spin orbitals for open-shell restricted Hartree-Fock reference functions

Abstract

A new set of spin orbitals is proposed for single-reference correlation procedures based on an open-shell restricted Hartree-Fock (RHF) reference function. The spatial parts of the new spin orbitals are from an open-shell RHF calculation. These spin orbitals form a complete, orthonormal set. The RHF single determinant based on these spin orbitals is an S sub 2 eigenfunction, but a linear combination of S sub z eigenfunctions. The advantage of these spin orbitals is that equations for perturbation theory or coupled-cluster theory are symmetric in the spin indices and hence the number of independent parameters to be determined is dramatically reduced.