CaltechAUTHORS
  A Caltech Library Service

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

Zhu, Tianyu and de Silva, Piotr and Van Voorhis, Troy (2019) Implementation of the Many-Pair Expansion for Systematically Improving Density Functional Calculations of Molecules. Journal of Chemical Theory and Computation, 15 (2). pp. 1089-1101. ISSN 1549-9618. http://resolver.caltech.edu/CaltechAUTHORS:20190128-154413574

[img] PDF - Accepted Version
See Usage Policy.

6Mb
[img] PDF (Detailed description of constructing auxiliary basis sets and the energy errors for non-v-representable densities) - Supplemental Material
See Usage Policy.

307Kb

Use this Persistent URL to link to this item: http://resolver.caltech.edu/CaltechAUTHORS:20190128-154413574

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.


Item Type:Article
Related URLs:
URLURL TypeDescription
https://doi.org/10.1021/acs.jctc.8b01127DOIArticle
https://pubs.acs.org/doi/suppl/10.1021/acs.jctc.8b01127PublisherSupporting Information
ORCID:
AuthorORCID
Zhu, Tianyu0000-0003-2061-3237
de Silva, Piotr0000-0002-4985-7350
Additional Information:© 2019 American Chemical Society. Received: November 5, 2018; Published: January 28, 2019. This work was funded by a grant from the NSF (CHE-1464804). T.V. acknowledges support from a David and Lucile Packard Foundation Fellowship. T.Z. acknowledges support from the MIT Lester Wolfe Fellowship. The authors declare no competing financial interest.
Funders:
Funding AgencyGrant Number
NSFCHE-1464804
David and Lucile Packard FoundationUNSPECIFIED
Massachusetts Institute of Technology (MIT)UNSPECIFIED
Record Number:CaltechAUTHORS:20190128-154413574
Persistent URL:http://resolver.caltech.edu/CaltechAUTHORS:20190128-154413574
Official Citation:Implementation of the Many-Pair Expansion for Systematically Improving Density Functional Calculations of Molecules. Tianyu Zhu, Piotr de Silva, and Troy Van Voorhis. Journal of Chemical Theory and Computation 2019 15 (2), 1089-1101. DOI: 10.1021/acs.jctc.8b01127
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:92503
Collection:CaltechAUTHORS
Deposited By: Tony Diaz
Deposited On:29 Jan 2019 16:08
Last Modified:19 Feb 2019 17:55

Repository Staff Only: item control page