Bridging Quantum Chemistry and MaxCut: Classical Performance Guarantees and Quantum Algorithms for the Hartree–Fock Method

In quantum chemistry, self-consistent field (SCF) algorithms define a nonlinear optimization problem, with both continuous and discrete components. In this work, we derive Hartree–Fock-inspired SCF algorithms that can be exactly written as a sequence of Quadratic Unconstrained Spin/Binary Optimization problems (QUSO/QUBO). We reformulate the optimization problem as a series of MaxCut graph problems, which can be efficiently solved using semidefinite programming techniques. This procedure provides performance guarantees at each SCF step, irrespective of the complexity of the optimization landscape. We numerically demonstrate the QUBO-SCF and MaxCut-SCF methods by studying the hydroxide anion OH– and molecular Nitrogen N2. The largest problem addressed in this study involves a system comprised of 220 qubits (equivalently, spin–orbitals). Our results show that QUBO-SCF and MaxCut-SCF suffer much less from internal instabilities compared with conventional SCF calculations. Additionally, we show that the new SCF algorithms can enhance single-reference methods, such as configuration interaction. Finally, we explore how quantum algorithms for optimization can be applied to the QUSO problems arising from the Hartree–Fock method. Four distinct hybrid-quantum classical approaches are introduced: GAS-SCF, QAOA-SCF, QA-SCF and DQI-SCF.