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Title: Improving the accuracy of the variational quantum eigensolver for molecular systems by the explicitly-correlated perturbative [2] R12-correction

Abstract

We provide an integration of the universal, perturbative explicitly correlated [2] R12-correction in the context of the Variational Quantum Eigensolver (VQE). This approach is able to increase the accuracy of the underlying reference method significantly while requiring no additional quantum resources. The proposed approach only requires knowledge of the one- and two-particle reduced density matrices (RDMs) of the reference wavefunction; these can be measured after having reached convergence in the VQE. This computation comes at a cost that scales as the sixth power of the number of electrons. Here, we explore the performance of the VQE + [2] R12 approach using both conventional Gaussian basis sets and our recently proposed directly determined pair-natural orbitals obtained by multiresolution analysis (MRA-PNOs). Both Gaussian orbital and PNOs are investigated as a potential set of complementary basis functions in the computation of [2] R12. In particular the combination of MRA-PNOs with [2] R12 has turned out to be very promising – persistently throughout our data, this allowed very accurate simulations at a quantum cost of a minimal basis set. Additionally, we found that the deployment of PNOs as complementary basis can greatly reduce the number of complementary basis functions that enter the computation ofmore » the correction at a complexity.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3]
+ Show Author Affiliations
  1. Univ. of Toronto, ON (Canada); RWTH Aachen Univ. (Germany); Vector Institute for Artificial Intelligence, Toronto, ON (Canada)
  2. Univ. of Toronto, ON (Canada)
  3. Univ. of Toronto, ON (Canada); Vector Institute for Artificial Intelligence, Toronto, ON (Canada); Canadian Institute for Advanced Research (CIFAR), Toronto, ON (Canada)
Publication Date:
Research Org.:
Emory Univ., Atlanta, GA (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1978860
Alternate Identifier(s):
OSTI ID: 1870539
Grant/Contract Number:  
SC0019374
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Volume: 24; Journal Issue: 22; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Schleich, Philipp, Kottmann, Jakob S., and Aspuru-Guzik, Alán. Improving the accuracy of the variational quantum eigensolver for molecular systems by the explicitly-correlated perturbative [2] R12-correction. United States: N. p., 2022. Web. doi:10.1039/d2cp00247g.
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Schleich, Philipp, Kottmann, Jakob S., & Aspuru-Guzik, Alán. Improving the accuracy of the variational quantum eigensolver for molecular systems by the explicitly-correlated perturbative [2] R12-correction. United States. https://doi.org/10.1039/d2cp00247g
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Schleich, Philipp, Kottmann, Jakob S., and Aspuru-Guzik, Alán. Thu . "Improving the accuracy of the variational quantum eigensolver for molecular systems by the explicitly-correlated perturbative [2] R12-correction". United States. https://doi.org/10.1039/d2cp00247g. https://www.osti.gov/servlets/purl/1978860.
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@article{osti_1978860,
title = {Improving the accuracy of the variational quantum eigensolver for molecular systems by the explicitly-correlated perturbative [2] R12-correction},
author = {Schleich, Philipp and Kottmann, Jakob S. and Aspuru-Guzik, Alán},
abstractNote = {We provide an integration of the universal, perturbative explicitly correlated [2] R12-correction in the context of the Variational Quantum Eigensolver (VQE). This approach is able to increase the accuracy of the underlying reference method significantly while requiring no additional quantum resources. The proposed approach only requires knowledge of the one- and two-particle reduced density matrices (RDMs) of the reference wavefunction; these can be measured after having reached convergence in the VQE. This computation comes at a cost that scales as the sixth power of the number of electrons. Here, we explore the performance of the VQE + [2] R12 approach using both conventional Gaussian basis sets and our recently proposed directly determined pair-natural orbitals obtained by multiresolution analysis (MRA-PNOs). Both Gaussian orbital and PNOs are investigated as a potential set of complementary basis functions in the computation of [2] R12. In particular the combination of MRA-PNOs with [2] R12 has turned out to be very promising – persistently throughout our data, this allowed very accurate simulations at a quantum cost of a minimal basis set. Additionally, we found that the deployment of PNOs as complementary basis can greatly reduce the number of complementary basis functions that enter the computation of the correction at a complexity.},
doi = {10.1039/d2cp00247g},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 22,
volume = 24,
place = {United States},
year = {Thu May 19 00:00:00 EDT 2022},
month = {Thu May 19 00:00:00 EDT 2022}
}
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https://doi.org/10.1039/d2cp00247g
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