Qubit Count Reduction by Orthogonally Constrained Orbital Optimization for Variational Quantum Excited-State Solvers

We propose a state-averaged orbital optimization scheme for improving the accuracy of excited states of the electronic structure Hamiltonian for use on near-term quantum computers. Instead of parameterizing the orbital rotation operator in the conventional fashion as an exponential of an antihermitian matrix, we parameterize the orbital rotation as a general partial unitary matrix. Whereas conventional orbital optimization methods minimize the state-averaged energy using successive Newton steps of the second-order Taylor expansion of the energy, the method presented here optimizes the state-averaged energy using an orthogonally constrained gradient projection method that does not require any expansion approximations. Through extensive benchmarking of the method on various small molecular systems, we find that the method is capable of producing more accurate results than fixed basis FCI while simultaneously using fewer qubits. In particular, we show that for H₂, the method is capable of matching the accuracy of FCI in the cc-pVTZ basis (56 qubits) while only using 14 qubits.