Theoretical Chemistry Accounts

, Volume 130, Issue 2, pp 153–160

An examination of density functionals on aldol, Mannich and α-aminoxylation reaction enthalpy calculations

Regular Article

DOI: 10.1007/s00214-011-0944-6

Cite this article as:
Singh, R.K., Tsuneda, T. & Hirao, K. Theor Chem Acc (2011) 130: 153. doi:10.1007/s00214-011-0944-6

Abstract

The reaction enthalpies of aldol, Mannich and α-aminoxylation reactions were calculated by density functional theory (DFT) using long-range-corrected (LC), hybrid B3LYP and other up-to-date functionals to show why conventional DFT including B3LYP has given poor enthalpies for these reactions. As a result, we found that long-range exchange interactions significantly affect the reaction enthalpies. We therefore proposed that the poor enthalpies of B3LYP are due to its insufficient long-range exchange effect. On the other hand, LC functionals accurately reproduce reaction enthalpies for these reactions. However, we noticed that even LC functionals present poor reaction enthalpies for specific reactions, in which many branches are produced or very small molecules such as methane molecule participate.

Keywords

Density functional theory (DFT) Long-range correction (LC) scheme Condensation reaction enthalpies 

Supplementary material

214_2011_944_MOESM1_ESM.docx (49 kb)
Reaction enthalpies (ΔH0K) at aug-cc-pVTZ, cc-pVTZ and cc-pVDZ basis sets (DOCX 48 kb)

Copyright information

© Springer-Verlag 2011

Authors and Affiliations

  • Raman K. Singh
    • 1
    • 2
  • Takao Tsuneda
    • 1
    • 2
  • Kimihiko Hirao
    • 1
    • 2
  1. 1.Advanced Science Institute, RIKENWako, SaitamaJapan
  2. 2.CREST, Japan Science and Technology Agency (JST)TokyoJapan

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