Issue 13, 2023

Accurate non-covalent interaction energies on noisy intermediate-scale quantum computers via second-order symmetry-adapted perturbation theory

Abstract

The calculation of non-covalent interaction energies on noisy intermediate-scale quantum (NISQ) computers appears to be challenging with straightforward application of existing quantum algorithms. For example, the use of the standard supermolecular method with the variational quantum eigensolver (VQE) would require extremely precise resolution of the total energies of the fragments to provide for accurate subtraction to the interaction energy. Here we present a symmetry-adapted perturbation theory (SAPT) method that may provide interaction energies with high quantum resource efficiency. Of particular note, we present a quantum extended random-phase approximation (ERPA) treatment of the SAPT second-order induction and dispersion terms, including exchange counterparts. Together with previous work on first-order terms (Chem. Sci., 2022, 13, 3094), this provides a recipe for complete SAPT(VQE) interaction energies up to second order, which is a well established truncation. The SAPT interaction energy terms are computed as first-level observables with no subtraction of monomer energies invoked, and the only quantum observations needed are the VQE one- and two-particle density matrices. We find empirically that SAPT(VQE) can provide accurate interaction energies even with coarsely optimized, low circuit depth wavefunctions from a quantum computer, simulated through ideal statevectors. The errors of the total interaction energy are orders of magnitude lower than the corresponding VQE total energy errors of the monomer wavefunctions. In addition, we present heme-nitrosyl model complexes as a system class for near term quantum computing simulations. They are strongly correlated, biologically relevant and difficult to simulate with classical quantum chemical methods. This is illustrated with density functional theory (DFT) as the predicted interaction energies exhibit a strong sensitivity with respect to the choice of functional. Thus, this work paves the way to obtain accurate interaction energies on a NISQ-era quantum computer with few quantum resources. It is the first step in alleviating one of the major challenges in quantum chemistry, where in-depth knowledge of both the method and system is required a priori to reliably generate accurate interaction energies.

Graphical abstract: Accurate non-covalent interaction energies on noisy intermediate-scale quantum computers via second-order symmetry-adapted perturbation theory

Supplementary files

Article information

Article type
Edge Article
Submitted
25 Oct 2022
Accepted
22 Feb 2023
First published
23 Feb 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2023,14, 3587-3599

Accurate non-covalent interaction energies on noisy intermediate-scale quantum computers via second-order symmetry-adapted perturbation theory

M. Loipersberger, F. D. Malone, A. R. Welden, R. M. Parrish, T. Fox, M. Degroote, E. Kyoseva, N. Moll, R. Santagati and M. Streif, Chem. Sci., 2023, 14, 3587 DOI: 10.1039/D2SC05896K

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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