Fast gradient-free optimization of excitations in variational quantum eigensolvers

Abstract: We introduce ExcitationSolve, a fast globally-informed gradient-free optimizer for physically-motivated ans\"atze constructed of excitation operators, a common choice in variational quantum eigensolvers. ExcitationSolve extends quantum-aware and hyperparameter-free optimizers such as Rotosolve, from parameterized unitaries with generators $G$ of the form $G^2=I$, e.g., rotations, to the more general class of $G^3=G$ exhibited by the physically-inspired excitation operators such as in the unitary coupled cluster approach. ExcitationSolve determines the global optimum along each variational parameter using the same quantum resources that gradient-based optimizers require for one update step. We provide optimization strategies for both fixed and adaptive variational ans\"atze, as well as a multi-parameter generalization for the simultaneous selection and optimization of multiple excitation operators. We demonstrate the utility of ExcitationSolve on molecular ground state energy calculations, thereby outperforming state-of-the-art optimizers commonly employed in variational quantum algorithms. Across all tested molecules in equilibrium geometry, ExcitationSolve remarkably reaches chemical accuracy in a single parameter sweep in a fixed ansatz. In addition, ExcitationSolve achieves adaptive ans\"atze consisting of fewer operators than in the gradient-based adaptive approach. Finally, ExcitationSolve shows robustness against substantial noise in real quantum hardware, retaining an advantage over other optimizers.