Challenging Excited States from Adaptive Quantum Eigensolvers: Subspace Expansions vs. State-Averaged Strategies (2409.11210v2)

Abstract: The prediction of electronic structure for strongly correlated molecules represents a promising application for near-term quantum computers. Significant attention has been paid to ground state wavefunctions, but excited states of molecules are relatively unexplored. In this work, we consider the ADAPT-VQE algorithm, a single-reference approach for obtaining ground states, and its state-averaged generalization for computing multiple states at once. We demonstrate for both rectangular and linear H$_4$, as well as for BeH$_2$, that this approach, which we call MORE-ADAPT-VQE, can make better use of small excitation manifolds than an analagous method based on a single-reference ADAPT-VQE calculation, q-sc-EOM. In particular, MORE-ADAPT-VQE is able to accurately describe both avoided crossings and crossings between states of different symmetries. In addition to more accurate excited state energies, MORE-ADAPT-VQE can recover accurate transition dipole moments in situations where traditional ADAPT-VQE and q-sc-EOM struggle. These improvements suggest a promising direction toward the use of quantum computers for difficult excited state problems.