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The influence of correlation on (de)localization indices from a valence bond perspective

Guillaume Acke (UGent) and Patrick Bultinck (UGent)
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Abstract
When going beyond the Hartree-Fock level to correlated methods, one observes a significant reduction in the delocalization index. This is commonly interpreted as a weakening of electron sharing due to electron correlation, although this is rather counter-intuitive to the concomitant energy lowering. In this study, we use an analytical valence bond model and full CI calculations to show that this reduction in the delocalization index actually goes hand in hand with increased covalent contributions at the expense of ionic contributions. This suggests that we should be careful in formulating interpretations of these results in (de)localization indices.
Keywords
AVERAGED FERMI HOLES, CHEMICAL-BONDS, ELECTRON DELOCALIZATION, HYPERVALENT MOLECULES, WAVE-FUNCTIONS, HARTREE-FOCK, LOCALIZATION, AROMATICITY, DEFINITION, INSIGHTS, Valence bond theory, Chemical bonding, Delocalization index

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Citation

Please use this url to cite or link to this publication:

Chicago
Acke, Guillaume, and Patrick Bultinck. 2018. “The Influence of Correlation on (de)localization Indices from a Valence Bond Perspective.” Journal of Molecular Modeling 24 (10).
APA
Acke, G., & Bultinck, P. (2018). The influence of correlation on (de)localization indices from a valence bond perspective. JOURNAL OF MOLECULAR MODELING, 24(10).
Vancouver
1.
Acke G, Bultinck P. The influence of correlation on (de)localization indices from a valence bond perspective. JOURNAL OF MOLECULAR MODELING. 2018;24(10).
MLA
Acke, Guillaume, and Patrick Bultinck. “The Influence of Correlation on (de)localization Indices from a Valence Bond Perspective.” JOURNAL OF MOLECULAR MODELING 24.10 (2018): n. pag. Print.
@article{8574430,
  abstract     = {When going beyond the Hartree-Fock level to correlated methods, one observes a significant reduction in the delocalization index. This is commonly interpreted as a weakening of electron sharing due to electron correlation, although this is rather counter-intuitive to the concomitant energy lowering. In this study, we use an analytical valence bond model and full CI calculations to show that this reduction in the delocalization index actually goes hand in hand with increased covalent contributions at the expense of ionic contributions. This suggests that we should be careful in formulating interpretations of these results in (de)localization indices.},
  articleno    = {275},
  author       = {Acke, Guillaume and Bultinck, Patrick},
  issn         = {1610-2940},
  journal      = {JOURNAL OF MOLECULAR MODELING},
  keywords     = {AVERAGED FERMI HOLES,CHEMICAL-BONDS,ELECTRON DELOCALIZATION,HYPERVALENT MOLECULES,WAVE-FUNCTIONS,HARTREE-FOCK,LOCALIZATION,AROMATICITY,DEFINITION,INSIGHTS,Valence bond theory,Chemical bonding,Delocalization index},
  language     = {eng},
  number       = {10},
  pages        = {5},
  title        = {The influence of correlation on (de)localization indices from a valence bond perspective},
  url          = {http://dx.doi.org/10.1007/s00894-018-3808-3},
  volume       = {24},
  year         = {2018},
}

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