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Title: Push it to the limit: Characterizing the convergence of common sequences of basis sets for intermolecular interactions as described by density functional theory

Journal Article · · Journal of Chemical Physics
DOI:https://doi.org/10.1063/1.4949536· OSTI ID:1477252
ORCiD logo [1];  [2];  [1]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States); Kavli Energy Nanosciences Institute at Berkeley, Berkeley, CA (United States)
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With the aim of systematically characterizing the convergence of common families of basis sets such that general recommendations for basis sets can be made, we have tested a wide variety of basis sets against complete-basis binding energies across the S22 set of intermolecular interactions - noncovalent interactions of small and medium-sized molecules consisting of first- and second-row atoms - with three distinct density functional approximations: SPW92, a form of local-density approximation; B3LYP, a global hybrid generalized gradient approximation; and B97M-V, a meta-generalized gradient approximation with nonlocal correlation. We have found that it is remarkably difficult to reach the basis set limit; for the methods and systems examined, the most complete basis is Jensen's pc-4. The Dunning correlation-consistent sequence of basis sets converges slowly relative to the Jensen sequence. The Karlsruhe basis sets are quite cost effective, particularly when a correction for basis set superposition error is applied: counterpoise-corrected def2-SVPD binding energies are better than corresponding energies computed in comparably sized Dunning and Jensen bases, and on par with uncorrected results in basis sets 3-4 times larger. These trends are exhibited regardless of the level of density functional approximation employed. In conclusion, a sense of the magnitude of the intrinsic incompleteness error of each basis set not only provides a foundation for guiding basis set choice in future studies but also facilitates quantitative comparison of existing studies on similar types of systems.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division
Grant/Contract Number:
AC02-05CH11231; FG02-12ER16362
OSTI ID:
1477252
Alternate ID(s):
OSTI ID: 1253656
Journal Information:
Journal of Chemical Physics, Vol. 144, Issue 19; Related Information: © 2016 Author(s).; ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 36 works
Citation information provided by
Web of Science

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Cited By (9)

The performance of Dunning, Jensen, and Karlsruhe basis sets on computing relative energies and geometries text January 2020
Correlation consistent basis sets designed for density functional theory: Second-row (Al-Ar) journal August 2019
Thirty years of density functional theory in computational chemistry: an overview and extensive assessment of 200 density functionals journal April 2017
The Performance of Dunning, Jensen and Karlsruhe Basis Sets on Computing Relative Energies and Geometries datapaper December 2019
The Performance of Dunning, Jensen and Karlsruhe Basis Sets on Computing Relative Energies and Geometries datapaper November 2019
Midbond basis functions for weakly bound complexes journal February 2018
The performance of Dunning, Jensen, and Karlsruhe basis sets on computing relative energies and geometries text January 2020
Push it to the limit: comparing periodic and local approaches to density functional theory for intermolecular interactions journal June 2018
The Performance of Dunning, Jensen and Karlsruhe Basis Sets on Computing Relative Energies and Geometries journal December 2019

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY