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

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.

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Acknowledgments

This research was supported in part by the Core Research for Evolutional Science and Technology Program, and ‘High Performance Computing for Multi-Scale and MultiPhysics Phenomena’ of the Japan Science and Technology Agency (JST). We thank the RIKEN Integrated Cluster of Clusters (RICC) at RIKEN for the computer resources used for the calculation.

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Correspondence to Takao Tsuneda.

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Dedicated to Professor Shigeru Nagase on the occasion of his 65th birthday and published as part of the Nagase Festschrift Issue.

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Reaction enthalpies (ΔH0K) at aug-cc-pVTZ, cc-pVTZ and cc-pVDZ basis sets (DOCX 48 kb)

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Singh, R.K., Tsuneda, T. & Hirao, K. An examination of density functionals on aldol, Mannich and α-aminoxylation reaction enthalpy calculations. Theor Chem Acc 130, 153–160 (2011). https://doi.org/10.1007/s00214-011-0944-6

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Keywords

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