Quantum Algorithm for Numerical Energy Gradient Calculations at the Full Configuration Interaction Level of Theory

Kenji Sugisaki; Hiroyuki Wakimoto; Kazuo Toyota; Kazunobu Sato; Daisuke Shiomi; Takeji Takui

doi:10.1021/acs.jpclett.2c02737

Quantum Algorithm for Numerical Energy Gradient Calculations at the Full Configuration Interaction Level of Theory

J Phys Chem Lett. 2022 Dec 8;13(48):11105-11111. doi: 10.1021/acs.jpclett.2c02737. Epub 2022 Nov 29.

Authors

Kenji Sugisaki^{1

2

3}, Hiroyuki Wakimoto¹, Kazuo Toyota¹, Kazunobu Sato¹, Daisuke Shiomi¹, Takeji Takui^{1

4}

Affiliations

¹ Department of Chemistry, Graduate School of Science, Osaka Metropolitan University, 3-3-138 Sugimoto, Sumiyoshi-ku, Osaka558-8585, Japan.
² JSTPRESTO, 4-1-8 Honcho, Kawaguchi, Saitama, 332-0012, Japan.
³ Centre for Quantum Engineering, Research and Education (CQuERE), TCG Centres for Research and Education in Science and Technology (TCG CREST), Sector V, Salt Lake, Kolkata700091, India.
⁴ Research Support Department/University Research Administrator Center, University Administration Division, Osaka Metropolitan University, 3-3-138 Sugimoto, Sumiyoshi-ku, Osaka558-8585, Japan.

Abstract

A Bayesian phase difference estimation (BPDE) algorithm allows us to compute the energy gap of two electronic states of a given Hamiltonian directly by utilizing the quantum superposition of their wave functions. Here we report an extension of the BPDE algorithm to the direct calculation of the energy difference of two molecular geometries. We apply the BPDE algorithm for the calculation of numerical energy gradients based on the two-point finite-difference method, enabling us to execute geometry optimization of one-dimensional molecules at the full-CI level on a quantum computer. Results of numerical quantum circuit simulations of the geometry optimization of the H₂ molecule with the STO-3G and 6-31G basis sets, the LiH and BeH₂ molecules at the full-CI/STO-3G level, and the N₂ molecule at the CASCI(6e,6o)/6-311G* level are given.