MIT Libraries logoDSpace@MIT

MIT
View Item 
  • DSpace@MIT Home
  • MIT Open Access Articles
  • MIT Open Access Articles
  • View Item
  • DSpace@MIT Home
  • MIT Open Access Articles
  • MIT Open Access Articles
  • View Item
JavaScript is disabled for your browser. Some features of this site may not work without it.

Implementation of the Many-Pair Expansion for Systematically Improving Density Functional Calculations of Molecules

Author(s)
Zhu, Tianyu; de Silva, Piotr; Van Voorhis, Troy
Thumbnail
DownloadAccepted version (6.588Mb)
Publisher Policy

Publisher Policy

Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.

Terms of use
Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use.
Metadata
Show full item record
Abstract
Density functional theory (DFT) is the method of choice for predicting structures and reaction energies of molecular systems. However, it remains a daunting task to systematically improve the accuracy of an approximate density functional. The recently proposed many-pair expansion (MPE) [Phys. Rev. B 2016, 93, 201108] is a density functional hierarchy that systematically corrects any deficiencies of an approximate functional to converge to the exact energy, and was shown to give accurate results for lattice models. In this work, we extend MPE to molecular systems and implement it using Gaussian basis sets. The self-attractive Hartree (SAH) decomposition [J. Chem. Theory Comput. 2018, 14, 92-103] is employed to generate localized v-representable pair densities for performing MPE calculations. We demonstrate that MPE at the second order (MPE2) already predicts accurate molecular and reaction energies for a series of small molecules and hydrogen chains, with the EXX functional as its starting point. We also show that MPE correctly describes the symmetric bond breaking in hydrogen rings, indicating its ability to remove strong correlation errors. MPE thus provides a promising framework to systematically improve density functional calculations of molecules.
Date issued
2019-02
URI
https://hdl.handle.net/1721.1/129453
Department
Massachusetts Institute of Technology. Department of Chemistry
Journal
Journal of Chemical Theory and Computation
Publisher
American Chemical Society (ACS)
Citation
Zhu, Tianyu, Piotr de Silva, and Troy Van Voorhis. "Implementation of the Many-Pair Expansion for Systematically Improving Density Functional Calculations of Molecules." Journal of Chemical Theory and Computation 15, 2 (February 2019): 1089-101 doi 10.1021/ACS.JCTC.8B01127 ©2019 Author(s)
Version: Author's final manuscript
ISSN
1549-9626
1549-9618

Collections
  • MIT Open Access Articles

Browse

All of DSpaceCommunities & CollectionsBy Issue DateAuthorsTitlesSubjectsThis CollectionBy Issue DateAuthorsTitlesSubjects

My Account

Login

Statistics

OA StatisticsStatistics by CountryStatistics by Department
MIT Libraries
PrivacyPermissionsAccessibilityContact us
MIT
Content created by the MIT Libraries, CC BY-NC unless otherwise noted. Notify us about copyright concerns.