Theoretical Chemistry Accounts

, Volume 130, Issue 4–6, pp 851–857

An examination of density functional theories on isomerization energy calculations of organic molecules

  • Jong-Won Song
  • Takao Tsuneda
  • Takeshi Sato
  • Kimihiko Hirao
Regular Article

DOI: 10.1007/s00214-011-0997-6

Cite this article as:
Song, JW., Tsuneda, T., Sato, T. et al. Theor Chem Acc (2011) 130: 851. doi:10.1007/s00214-011-0997-6

Abstract

Long-range corrected (LC) density functional theories (DFTs) were applied to the isomerization energy calculations of organic molecules to make clear why conventional DFTs including B3LYP have given poor isomerization reaction energies. Combining with local response dispersion (LRD) method, we performed LC-DFT calculations for the benchmark set of isomerization reactions. Consequently, we found that LC-DFT + LRD methods give accurate reaction energies equivalent to up-to-date DFTs containing many semi-empirical parameters. This result indicates that long-range exchange and intramolecular dispersion correlation interactions, which have been neglected in conventional DFTs, play prominent roles in isomerization reactions. However, we also found that these interactions are not sufficient to give accurate isomerization energies especially for cyclization reactions. Considering that Gaussian-attenuated LC-DFTs (LCgau-DFTs) give better isomerization reaction energies than LC-DFTs, we suggested that the isomerization energies will be further improved by correcting the short-range part of exchange functionals in DFT with keeping the whole long-range exchange interactions.

Keywords

Density functional theory (DFT) Long-range correction (LC) Isomerization energy 

Supplementary material

214_2011_997_MOESM1_ESM.docx (41 kb)
Supplementary material 1 (DOCX 41 kb)

Copyright information

© Springer-Verlag 2011

Authors and Affiliations

  • Jong-Won Song
    • 1
    • 2
  • Takao Tsuneda
    • 2
    • 3
  • Takeshi Sato
    • 4
  • Kimihiko Hirao
    • 2
    • 3
  1. 1.Department of Chemical System Engineering, School of EngineeringThe University of TokyoTokyoJapan
  2. 2.CREST, Japan Science and Technology AgencySaitamaJapan
  3. 3.Advanced Science InstituteSaitamaJapan
  4. 4.Photon Science Center of the University of TokyoTokyoJapan

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