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research article

Hydrogen bonding described using dispersion-corrected density functional theory

Arey, J. Samuel  
•
Aeberhard, P. C.
•
Lin, I.-C.  
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2009
The Journal of Physical Chemistry B

In recent works, dispersion-corrected atom-centered potentials (DCACPs) were developed as a method to account for long-range dispersion forces between molecules in density functional theory calculations within the generalized gradient approximation (GGA). Here, we test the ability of DCACPs to improve the GGA treatment of hydrogen-bonded systems. We assessed both BLYP and dispersion-corrected BLYP with respect to benchmark calculations for the hydrogen bond lengths and binding energies of 20 complexes containing the elements C, H, N, O, and S. Benchmark data included geometries calculated using MP2 and CCSD(T) and binding energies using W2, W1, CBS-QB3, and other CCSD(T) extrapolation schemes. With respect to benchmark methods, dispersion-corrected BLYP exhibited a mean signed error of 0.010 Å in the hydrogen bond length and a mean relative error of 5.1% in the hydrogen bond binding energy. By comparison, uncorrected BLYP exhibited error statistics of 0.036 Å and 15.9%, respectively. We conclude that DCACPs robustly improve the BLYP description of hydrogen-bonded systems at small additional computational cost. New benchmark geometries (MP2/aug-cc-pVTZ) and new benchmark binding energies (W1) are presented for seven complexes, and the remaining benchmark data were taken from previous literature.

  • Details
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Type
research article
DOI
10.1021/jp810323m
Web of Science ID

WOS:000264805600031

Author(s)
Arey, J. Samuel  
Aeberhard, P. C.
Lin, I.-C.  
Rothlisberger, U.  
Date Issued

2009

Published in
The Journal of Physical Chemistry B
Volume

113

Issue

14

Start page

4726

End page

4732

Subjects

Ab-Initio

•

Noncovalent Interactions

•

Thermochemical Kinetics

•

Bonded Complexes

•

Interaction Energies

•

Molecular-Dynamics

•

Weak-Interactions

•

Water

•

Dft

•

Decomposition

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

EPFL units
LMCE  
LCBC  
Available on Infoscience
April 11, 2009
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/37079
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