Quantum Algorithms for the Variational Optimization of Correlated Electronic States with Stochastic Reconfiguration and the Linear Method

Abstract

Solving the electronic Schrodinger equation for strongly correlated ground states is a long-standing challenge. We present quantum algorithms for the variational optimization of wave functions correlated by products of unitary operators, such as Local Unitary Cluster Jastrow (LUCJ) ansatzes, using stochastic reconfiguration (SR) and the linear method (LM). While an implementation on classical computing hardware would require exponentially growing compute cost, the cost (number of circuits and shots) of our quantum algorithms is polynomial in system size. We find that classical simulations of optimization with the linear method consistently find lower energy solutions than with the L-BFGS-B optimizer across the dissociation curves of the notoriously difficult N 2 and C 2 dimers; LUCJ predictions of the ground-state energies deviate from exact diagonalization by 1 kcal/mol or less at all points on the potential energy curve. While we do characterize the effect of shot noise on the LM optimization, these noiseless results highlight the critical but often overlooked role that optimization techniques must play in attacking the electronic structure problem (on both classical and quantum hardware), for which even mean-field optimization is formally NP hard. We also discuss the challenge of obtaining smooth curves in these strongly correlated regimes, and propose a number of quantum-friendly solutions ranging from symmetry-projected ansatz forms to a symmetry-constrained optimization algorithm.