skip to main content

DOE PAGESDOE PAGES

Title: 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 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 incompletenessmore » 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.« less
Authors:
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)
Publication Date:
Grant/Contract Number:
AC02-05CH11231; FG02-12ER16362
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 0021-9606
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) (SC-22). 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 Head-Gordon, 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., & Head-Gordon, 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 Head-Gordon, 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 Head-Gordon, 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 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.},
doi = {10.1063/1.4949536},
journal = {Journal of Chemical Physics},
number = 19,
volume = 144,
place = {United States},
year = {2016},
month = {5}
}

Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996
  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Benchmark database of accurate (MP2 and CCSD(T) complete basis set limit) interaction energies of small model complexes, DNA base pairs, and amino acid pairs
journal, January 2006
  • Jure?ka, Petr; �poner, Ji?�; ?ern�, Ji?�
  • Physical Chemistry Chemical Physics, Vol. 8, Issue 17, p. 1985-1993
  • DOI: 10.1039/B600027D

Self?consistent molecular orbital methods. XXIII. A polarization?type basis set for second?row elements
journal, October 1982
  • Francl, Michelle M.; Pietro, William J.; Hehre, Warren J.
  • The Journal of Chemical Physics, Vol. 77, Issue 7, p. 3654-3665
  • DOI: 10.1063/1.444267

Self-Consistent Equations Including Exchange and Correlation Effects
journal, November 1965

Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy
journal, January 2005
  • Weigend, Florian; Ahlrichs, Reinhart
  • Physical Chemistry Chemical Physics, Vol. 7, Issue 18, p. 3297-3305
  • DOI: 10.1039/b508541a

Density?functional thermochemistry. III. The role of exact exchange
journal, April 1993
  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913

A new local density functional for main-group thermochemistry, transition metal bonding, thermochemical kinetics, and noncovalent interactions
journal, November 2006
  • Zhao, Yan; Truhlar, Donald G.
  • The Journal of Chemical Physics, Vol. 125, Issue 19, Article No. 194101
  • DOI: 10.1063/1.2370993

Inhomogeneous Electron Gas
journal, November 1964

Accurate and simple analytic representation of the electron-gas correlation energy
journal, June 1992

The calculation of small molecular interactions by the differences of separate total energies. Some procedures with reduced errors
journal, October 1970

Ab Initio Calculation of Vibrational Absorption and Circular Dichroism Spectra Using Density Functional Force Fields
journal, November 1994
  • Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.
  • The Journal of Physical Chemistry, Vol. 98, Issue 45, p. 11623-11627
  • DOI: 10.1021/j100096a001

Self�Consistent Molecular Orbital Methods. XII. Further Extensions of Gaussian�Type Basis Sets for Use in Molecular Orbital Studies of Organic Molecules
journal, March 1972
  • Hehre, W. J.; Ditchfield, R.; Pople, J. A.
  • The Journal of Chemical Physics, Vol. 56, Issue 5, p. 2257-2261
  • DOI: 10.1063/1.1677527