Push it to the limit: Characterizing the convergence of common sequences of basis sets for intermolecular interactions as described by density functional theory
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 completebasis binding energies across the S22 set of intermolecular interactions  noncovalent interactions of small and mediumsized molecules consisting of first and secondrow atoms  with three distinct density functional approximations: SPW92, a form of localdensity approximation; B3LYP, a global hybrid generalized gradient approximation; and B97MV, a metageneralized 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 pc4. The Dunning correlationconsistent 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: counterpoisecorrected def2SVPD binding energies are better than corresponding energies computed in comparably sized Dunning and Jensen bases, and on par with uncorrected results in basis sets 34 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 incompletenessmore »
 Authors:

^{[1]}
;
^{[2]};
^{[1]}
 Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
 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)
 Publication Date:
 Grant/Contract Number:
 AC0205CH11231; FG0212ER16362
 Type:
 Accepted Manuscript
 Journal Name:
 Journal of Chemical Physics
 Additional Journal Information:
 Journal Volume: 144; Journal Issue: 19; Related Information: © 2016 Author(s).; Journal ID: ISSN 00219606
 Publisher:
 American Institute of Physics (AIP)
 Research Org:
 Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
 Sponsoring Org:
 USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC22). Chemical Sciences, Geosciences & Biosciences Division; USDOE
 Country of Publication:
 United States
 Language:
 English
 Subject:
 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
 OSTI Identifier:
 1477252
 Alternate Identifier(s):
 OSTI ID: 1253656
Witte, Jonathon, Neaton, Jeffrey B., and HeadGordon, Martin. Push it to the limit: Characterizing the convergence of common sequences of basis sets for intermolecular interactions as described by density functional theory. United States: N. p.,
Web. doi:10.1063/1.4949536.
Witte, Jonathon, Neaton, Jeffrey B., & HeadGordon, Martin. Push it to the limit: Characterizing the convergence of common sequences of basis sets for intermolecular interactions as described by density functional theory. United States. doi:10.1063/1.4949536.
Witte, Jonathon, Neaton, Jeffrey B., and HeadGordon, Martin. 2016.
"Push it to the limit: Characterizing the convergence of common sequences of basis sets for intermolecular interactions as described by density functional theory". United States.
doi:10.1063/1.4949536. https://www.osti.gov/servlets/purl/1477252.
@article{osti_1477252,
title = {Push it to the limit: Characterizing the convergence of common sequences of basis sets for intermolecular interactions as described by density functional theory},
author = {Witte, Jonathon and Neaton, Jeffrey B. and HeadGordon, Martin},
abstractNote = {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 completebasis binding energies across the S22 set of intermolecular interactions  noncovalent interactions of small and mediumsized molecules consisting of first and secondrow atoms  with three distinct density functional approximations: SPW92, a form of localdensity approximation; B3LYP, a global hybrid generalized gradient approximation; and B97MV, a metageneralized 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 pc4. The Dunning correlationconsistent 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: counterpoisecorrected def2SVPD binding energies are better than corresponding energies computed in comparably sized Dunning and Jensen bases, and on par with uncorrected results in basis sets 34 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.},
doi = {10.1063/1.4949536},
journal = {Journal of Chemical Physics},
number = 19,
volume = 144,
place = {United States},
year = {2016},
month = {5}
}
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