Push it to the limit: Characterizing the convergence of common sequences of basis sets for intermolecular interactions as described by density functional theory
Abstract
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. A sense of the magnitude of the intrinsic incompleteness error of each basis set notmore »
 Authors:

 Department of Chemistry, University of California, Berkeley, California 94720 (United States)
 Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720 (United States)
 Publication Date:
 OSTI Identifier:
 22658014
 Resource Type:
 Journal Article
 Journal Name:
 Journal of Chemical Physics
 Additional Journal Information:
 Journal Volume: 144; Journal Issue: 19; Other Information: (c) 2016 Author(s); Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 00219606
 Country of Publication:
 United States
 Language:
 English
 Subject:
 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; BINDING ENERGY; COMPUTERIZED SIMULATION; CONVERGENCE; DENSITY FUNCTIONAL METHOD
Citation Formats
Witte, Jonathon, Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720, Neaton, Jeffrey B., Department of Physics, University of California, Berkeley, California 94720, Kavli Energy Nanosciences Institute at Berkeley, Berkeley, California 94720, HeadGordon, Martin, and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720. 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., 2016.
Web. doi:10.1063/1.4949536.
Witte, Jonathon, Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720, Neaton, Jeffrey B., Department of Physics, University of California, Berkeley, California 94720, Kavli Energy Nanosciences Institute at Berkeley, Berkeley, California 94720, HeadGordon, Martin, & Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720. 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, Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720, Neaton, Jeffrey B., Department of Physics, University of California, Berkeley, California 94720, Kavli Energy Nanosciences Institute at Berkeley, Berkeley, California 94720, HeadGordon, Martin, and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720. Sat .
"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.
@article{osti_22658014,
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 Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720 and Neaton, Jeffrey B. and Department of Physics, University of California, Berkeley, California 94720 and Kavli Energy Nanosciences Institute at Berkeley, Berkeley, California 94720 and HeadGordon, Martin and Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720},
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. 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},
issn = {00219606},
number = 19,
volume = 144,
place = {United States},
year = {2016},
month = {5}
}
Works referencing / citing this record:
Push it to the limit: comparing periodic and local approaches to density functional theory for intermolecular interactions
journal, June 2018
 Witte, Jonathon; Neaton, Jeffrey B.; HeadGordon, Martin
 Molecular Physics, Vol. 117, Issue 912