Approximate second order method for orbital optimization of SCF and MCSCF wavefunctions

Abstract.

A quasi-Newton method involving a diagonal guess orbital hessian with iterative updates has been proposed recently by Almlof for the optimization of closed shell self-consistent field (SCF) wavefunctions. The technique is extended in the present work to more general wavefunctions, ranging from open shell SCF through multiconfigurational SCF. A number of examples are presented to show that convergence for closed and open shell SCF rivals conventional direct inversion in the iterative subspace (DIIS). For multiconfigurational SCF wavefunctions, the method presented here requires more iterations than an exact second order program, but since each iteration is substantially faster, leads to a more efficient overall program.