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