Multidimensional derivative-free optimization. A case study on minimization of Hartree-Fock-Roothaan energy functionals

Abstract: This study presents an evaluation of derivative-free optimization algorithms for the direct minimization of Hartree-Fock-Roothaan energy functionals involving nonlinear orbital parameters and quantum numbers with noninteger order. The analysis focuses on atomic calculations employing noninteger Slater-type orbitals. Analytic derivatives of the energy functional are not readily available for these orbitals. Four methods are investigated under identical numerical conditions: Powell's conjugate-direction method, the Nelder-Mead simplex algorithm, coordinate-based pattern search, and a model-based algorithm utilizing radial basis functions for surrogate-model construction. Performance benchmarking is first performed using the Powell singular function, a well-established test case exhibiting challenging properties including Hessian singularity at the global minimum. The algorithms are then applied to Hartree-Fock-Roothaan self-consistent-field energy functionals, which define a highly non-convex optimization landscape due to the nonlinear coupling of orbital parameters. Illustrative examples are provided for closed$-$shell atomic configurations, specifically the He, Be isoelectronic series, with calculations performed for energy functionals involving up to eight nonlinear parameters.