Quantum Solvers for Plane-Wave Hamiltonians: Abridging Virtual Spaces Through the Optimization of Pairwise Correlations

TL;DR

This paper introduces correlation optimized virtual orbitals (COVOs), a new method to efficiently define virtual spaces that capture significant electron correlation with fewer orbitals, enhancing quantum many-body calculations.

Contribution

The authors develop a novel algorithm to optimize virtual orbitals using small pairwise CI Hamiltonians, enabling accurate correlation with fewer orbitals in plane-wave basis methods.

Findings

Achieved good agreement with FCI/cc-pVTZ results using only 4 virtual orbitals for H₂.

Derived virtual spaces that capture significant correlation energy with minimal orbitals.

Applicable to various many-body methods including CC and perturbation theories.

Abstract

For many-body methods such as MCSCF and CASSCF, in which the number of one-electron orbitals are optimized and independent of basis set used, there are no problems with using plane-wave basis sets. However, for methods currently used in quantum computing such as select configuration interaction (CI) and coupled cluster (CC) methods, it is necessary to have a virtual space that is able to capture a significant amount of electron-electron correlation in the system. The virtual orbitals in a pseudopotential plane-wave Hartree--Fock calculation, because of Coulomb repulsion, are often scattering states that interact very weakly with the filled orbitals. As a result, very little correlation energy is captured from them. The use of virtual spaces derived from the one-electron operators have also been tried, and while some correlation is captured, the amount is quite low. To overcome these limitations, we have been developing new classes of algorithms to define virtual spaces by optimizing orbitals from small pairwise CI Hamiltonians, which we term as correlation optimized virtual orbitals with the abbreviation COVOs. With these procedures we have been able to derive virtual spaces, containing only a few orbitals, that are able to capture a significant amount of correlation. Besides, using these derived basis sets for quantum computing calculations targeting full CI (FCI) quality-results, they can also be used in other many-body approaches, including CC and M{\o}ller--Plesset perturbation theories, and open up the door to many-body calculations for pseudopotential plane-wave basis set methods. For the H$_2$ molecule, we were able to obtain good agreement with FCI/cc-pVTZ results with just 4 virtual orbitals, for both FCI and quantum simulations.