Quantum-Classical Hybrid Algorithm for the Simulation of All-Electron Correlation

TL;DR

This paper introduces a hybrid quantum-classical algorithm that efficiently computes all-electron energies and properties of molecules by combining quantum simulations of static correlation with classical density-matrix methods for dynamic correlation, achieving chemically relevant accuracy.

Contribution

The paper presents a novel hybrid algorithm that uses density-matrix methods to bypass wave function dependence, enabling all-electron calculations on classical computers from quantum-measured static correlation data.

Findings

Achieved chemically relevant accuracy for benzyne isomers.

Successfully integrated quantum ACSE with classical 2-RDM methods.

Demonstrated feasibility on current quantum hardware.

Abstract

While the treatment of chemically relevant systems containing hundreds or even thousands of electrons remains beyond the reach of quantum devices, the development of quantum-classical hybrid algorithms to resolve electronic correlation presents a promising pathway toward a quantum advantage in the computation of molecular electronic structure. Such hybrid algorithms treat the exponentially scaling part of the calculation -- the static (multireference) correlation -- on the quantum computer and the non-exponentially scaling part -- the dynamic correlation -- on the classical computer. While a variety of such algorithms have been proposed, due to the dependence on the wave function of most classical methods for dynamic correlation, the development of easy-to-use classical post-processing implementations has been limited. Here we present a novel hybrid-classical algorithm that computes a molecule's all-electron energy and properties on the classical computer from a critically important simulation of the static correlation on the quantum computer. Significantly, for the all-electron calculations we circumvent the wave function by using density-matrix methods that only require input of the statically correlated two-electron reduced density matrix (2-RDM), which can be efficiently measured in the quantum simulation. Although the algorithm is completely general, we test it with two classical 2-RDM methods, the anti-Hermitian contracted Schr\"odinger equation (ACSE) theory and multiconfiguration pair-density functional theory (MC-PDFT), using the recently developed quantum ACSE method for the simulation of the statically correlated 2-RDM. We obtain experimental accuracy for the relative energies of all three benzyne isomers and thereby, demonstrate the ability of the quantum-classical hybrid algorithms to achieve chemically relevant results and accuracy on currently available quantum computers.