MCSCF optimization revisited. II. Combined first- and second-order orbital optimization for large molecules.

Abstract

A new orbital optimization for the multiconfiguration self-consistent field method is presented. This method combines a second-order (SO) algorithm for the optimization of the active orbitals with the first-order super configuration interaction (SCI) optimization of the remaining closed-virtual rotations and is denoted as the SO-SCI method. The SO-SCI method significantly improves the convergence as compared to the conventional SCI method. In combination with density fitting, the intermediates from the gradient calculation can be reused to evaluate the two-electron integrals required for the active Hessian without introducing a large computational overhead. The orbitals and CI coefficients are optimized alternately, but the CI-orbital coupling is accounted for by the limited memory Broyden-Fletcher-Goldfarb-Shanno quasi-Newton method. This further improves the speed of convergence. The method is applicable to large molecules. The efficiency and robustness of the presented method is demonstrated in benchmark calculations for 21 aromatic molecules as well as for various transition metal complexes with up to 826 electrons and 5154 basis functions.