skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: 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 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. A sense of the magnitude of the intrinsic incompleteness error of each basis set notmore » 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.« less

Authors:
 [1];  [2];  [1]
  1. Department of Chemistry, University of California, Berkeley, California 94720 (United States)
  2. 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 0021-9606
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, Head-Gordon, 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, Head-Gordon, 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, Head-Gordon, 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 Head-Gordon, 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 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. 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 = {0021-9606},
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