The optimization of molecular orbitals for coupled cluster wavefunctions

The purpose of this work is to make the coupled cluster (CC) energy stationary with respect to molecular-orbital (MO) variations in the reference configuration. To achieve this, we have used the Z vector, the solution of a set of perturbation-independent CPHF-like equations, to rotate the MOs. A new energy and gradient calculation is carried out with these non-SCF orbitals to obtain a new Z vector. The process is repeated until the orbitals are optimized (Z = 0), i.e. the contribution to the analytic CC gradient coming from orbital relaxation (CPHF) is zero. At the CCD level the orbitals thus obtained are approximate Brueckner orbitals. At the CCSD level, convergence problems were found in the iterative procedure to optimize the orbitals. Results obtained for several molecules show that CCD wavefunctions constructed from these optimized orbitals are of CCSD quality. We conclude that the presence of exp( t 1 ) in the CCSD model accounts for most relaxation effects and there is not much to gain by orbital optimization in CCSD wavefunctions.