Hamiltonian simulation-based quantum-selected configuration interaction for large-scale electronic structure calculations with a quantum computer

Abstract

Quantum-selected configuration interaction (QSCI) is one of the most promising approaches for quantum chemical calculations with the current pre-fault tolerant quantum computers. In the conventional QSCI, the Slater determinants used for the wave function expansion are sampled by iteratively performing approximate wave function preparation and subsequent measurement in the computational basis, and then the subspace Hamiltonian matrix is diagonalized on a classical computer. In this approach, the preparation of a high-quality approximate wave function is necessary to compute total energies accurately. In this work, we propose a Hamiltonian simulation-based QSCI (HSB-QSCI) to avoid this difficulty. In the HSB-QSCI, the Slater determinants are sampled from quantum states generated by the real-time evolution of approximate wave functions. We provide numerical simulations for the spin-singlet ground state and the first excited spin-triplet state of oligoacenes (benzene, naphthalene, and anthracene), phenylene-1,4-dinitrene, and hexa-1,2,3,4,5-pentaene molecules; these results reveal that the HSB-QSCI is applicable not only to molecules where the Hartree--Fock provides a good approximation of the ground state, but also to strongly correlated systems with multiconfigurational characteristics (i.e., the case where preparing a high-quality approximate wave function is hard). We have also numerically confirmed that the HSB-QSCI is robust to approximation errors of the Hamiltonian simulation, such as Trotter errors and the truncation errors of Hamiltonian term by maximum locality in the localized molecular orbital basis. Hardware demonstrations of the HSB-QSCI are also reported for the hexa-1,2,3,4,5-pentaene molecule using 20 qubits IBM superconducting device. The differences between the HSB-QSCI energy and the CAS-CI value are at most 0.15 kcal mol\(^{-1}\), achieving chemical precision.