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

(2011) CHEMPHYSCHEM. 12(6). p.1100-1108
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HPC-UGent: the central High Performance Computing infrastructure of Ghent University
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.
Keywords
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

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Citation

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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.
@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},
}

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