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Validation of DFT-based methods for predicting qualitative thermochemistry of large polyaromatics

Karen Hemelsoet UGent, Freija De Vleeschouwer, Veronique Van Speybroeck UGent, Frank De Proft, Paul Geerlings and Michel Waroquier UGent (2011) CHEMPHYSCHEM. 12(6). p.1100-1108
abstract
We present a validation of computationally efficient density functional-based methods for the reproduction of relative bond dissociation energies of large polyaromatic hydrocarbons. Through the calculation of intrinsic radical stabilities and the computation of spin densities, the extent of delocalization of the unpaired electron in the benzylic radicals is examined. We focus on the influence of the level of theory choice applied for the geometry optimization and the role of van der Waals corrections on thermochemical properties. The dispersion effects mainly influence the energetics, causing a small upward shift of the bond dissociation energies. The long-range corrected CAM-B3LYP functional does not improve the traditional B3LYP results for the geometry description of the large delocalized radicals, however a non-negligible influence was encountered when applied for the energetics. It is reported that the f polarization functions present in the 6-311+G(3df,2p) basis set lead to an erroneous trend when combined with the B2PLYP functional for the computation of the single point energies.
Please use this url to cite or link to this publication:
author
organization
year
type
journalArticle (original)
publication status
published
subject
keyword
polycycles, POLYCYCLIC AROMATIC-HYDROCARBONS, DENSITY-FUNCTIONAL THEORY, BOND-DISSOCIATION ENERGIES, RADICAL STABILIZATION ENERGIES, HYDROGEN ABSTRACTION REACTIONS, MAIN-GROUP THERMOCHEMISTRY, NONCOVALENT INTERACTIONS, THEORETICAL PROCEDURES, 1ST PRINCIPLES, COKE FORMATION, intrinsic radical stability, density functional calculations, bond energy, ab initio calculations
journal title
CHEMPHYSCHEM
ChemPhysChem
volume
12
issue
6
pages
1100 - 1108
Web of Science type
Article
Web of Science id
000289264400011
JCR category
PHYSICS, ATOMIC, MOLECULAR & CHEMICAL
JCR impact factor
3.412 (2011)
JCR rank
6/32 (2011)
JCR quartile
1 (2011)
ISSN
1439-4235
DOI
10.1002/cphc.201000788
project
HPC-UGent: the central High Performance Computing infrastructure of Ghent University
language
English
UGent publication?
yes
classification
A1
copyright statement
I have transferred the copyright for this publication to the publisher
id
1213455
handle
http://hdl.handle.net/1854/LU-1213455
date created
2011-04-28 09:39:21
date last changed
2013-09-17 10:46:24
@article{1213455,
  abstract     = {We present a validation of computationally efficient density functional-based methods for the reproduction of relative bond dissociation energies of large polyaromatic hydrocarbons. Through the calculation of intrinsic radical stabilities and the computation of spin densities, the extent of delocalization of the unpaired electron in the benzylic radicals is examined. We focus on the influence of the level of theory choice applied for the geometry optimization and the role of van der Waals corrections on thermochemical properties. The dispersion effects mainly influence the energetics, causing a small upward shift of the bond dissociation energies. The long-range corrected CAM-B3LYP functional does not improve the traditional B3LYP results for the geometry description of the large delocalized radicals, however a non-negligible influence was encountered when applied for the energetics. It is reported that the f polarization functions present in the 6-311+G(3df,2p) basis set lead to an erroneous trend when combined with the B2PLYP functional for the computation of the single point energies.},
  author       = {Hemelsoet, Karen and De Vleeschouwer, Freija and Van Speybroeck, Veronique and De Proft, Frank and Geerlings, Paul and Waroquier, Michel},
  issn         = {1439-4235},
  journal      = {CHEMPHYSCHEM},
  keyword      = {polycycles,POLYCYCLIC AROMATIC-HYDROCARBONS,DENSITY-FUNCTIONAL THEORY,BOND-DISSOCIATION ENERGIES,RADICAL STABILIZATION ENERGIES,HYDROGEN ABSTRACTION REACTIONS,MAIN-GROUP THERMOCHEMISTRY,NONCOVALENT INTERACTIONS,THEORETICAL PROCEDURES,1ST PRINCIPLES,COKE FORMATION,intrinsic radical stability,density functional calculations,bond energy,ab initio calculations},
  language     = {eng},
  number       = {6},
  pages        = {1100--1108},
  title        = {Validation of DFT-based methods for predicting qualitative thermochemistry of large polyaromatics},
  url          = {http://dx.doi.org/10.1002/cphc.201000788},
  volume       = {12},
  year         = {2011},
}

Chicago
Hemelsoet, Karen, Freija De Vleeschouwer, Veronique Van Speybroeck, Frank De Proft, Paul Geerlings, and Michel Waroquier. 2011. “Validation of DFT-based Methods for Predicting Qualitative Thermochemistry of Large Polyaromatics.” Chemphyschem 12 (6): 1100–1108.
APA
Hemelsoet, Karen, De Vleeschouwer, F., Van Speybroeck, V., De Proft, F., Geerlings, P., & Waroquier, M. (2011). Validation of DFT-based methods for predicting qualitative thermochemistry of large polyaromatics. CHEMPHYSCHEM, 12(6), 1100–1108.
Vancouver
1.
Hemelsoet K, De Vleeschouwer F, Van Speybroeck V, De Proft F, Geerlings P, Waroquier M. Validation of DFT-based methods for predicting qualitative thermochemistry of large polyaromatics. CHEMPHYSCHEM. 2011;12(6):1100–8.
MLA
Hemelsoet, Karen, Freija De Vleeschouwer, Veronique Van Speybroeck, et al. “Validation of DFT-based Methods for Predicting Qualitative Thermochemistry of Large Polyaromatics.” CHEMPHYSCHEM 12.6 (2011): 1100–1108. Print.