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

TL;DR

This paper introduces a Hamiltonian simulation-based quantum-selected configuration interaction (HSB-QSCI) method that efficiently samples important electronic configurations for large-scale quantum chemical calculations on quantum computers.

Contribution

The paper proposes a novel HSB-QSCI approach that avoids the need for high-quality wave function preparation, enabling accurate electronic structure calculations on quantum computers, including strongly correlated systems.

Findings

HSB-QSCI captures over 99.18% of correlation energies in 36-qubit systems.

Method is applicable to both weakly and strongly correlated molecules.

Hardware demonstration performed on IBM Quantum processor with up to 36 qubits.

Abstract

Quantum-selected configuration interaction (QSCI) is an approach for quantum chemical calculations using current quantum computers. In conventional QSCI, 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, preparation of a high-quality approximate wave function is necessary to accurately compute total energies. Here we propose a Hamiltonian simulation-based QSCI (HSB-QSCI) to avoid this difficulty, by sampling the Slater determinants from quantum states generated by the real-time evolution of approximate wave functions. We provide numerical simulations for the lowest spin-singlet and triplet states of oligoacenes (benzene, naphthalene, and anthracene), phenylene-1,4-dinitrene, and hexa-1,2,3,4,5-pentaene. We found 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 where preparing a high-quality approximate wave function is hard. Hardware demonstrations of the HSB-QSCI are also reported for carbyne molecules expressed by up to 36 qubits, using an IBM Quantum processor. The HSB-QSCI captures more than 99.18\% of the correlation energies in the active space by considering about 1\% of all the Slater determinants in 36 qubit systems, illustrating the ability of the proposed method to efficiently consider important electronic configurations.