Geometric Optimization of Restricted-Open and Complete Active Space Self-Consistent Field Wave Functions

We explore Riemannian optimization methods for Restricted-Open-shell Hartree-Fock (ROHF) and Complete Active Space Self-Consistent Field (CASSCF) methods. After showing that ROHF and CASSCF can be reformulated as optimization problems on so-called “flag manifolds”, we review Riemannian optimization basics and their application to these specific problems. We compare these methods to traditional ones and find robust convergence properties without fine-tuning of numerical parameters. Our study suggests that Riemannian optimization is a valuable addition to orbital optimization for ROHF and CASSCF, warranting further investigation.