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Issue 19, 2012
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A qualitative failure of B3LYP for textbook organic reactions

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Abstract

Depending on the selected DFT functional, two different mechanisms are found for two organic reactions (an intramolecular nucleophilic aromatic substitution and a nucleophilic addition on a carbonyl moiety). Indeed, B3LYP predicts a concerted mechanism whereas M06-2X foresees a multistep one. Calculations at the MP4(SDQ) level proved the mechanisms to be stepwise. We studied these reactions with a large panel of exchange–correlation functionals and demonstrated that the amount of exact exchange is of first importance. For some borderline cases, the form of the functional has also an impact, e.g. the Meisenheimer σ-adduct of the intramolecular nucleophilic aromatic substitution can be located with B3PW91 but not with B3LYP. These results stress the need to use recently proposed functionals to investigate chemical reactivity.

Graphical abstract: A qualitative failure of B3LYP for textbook organic reactions

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Article information


Submitted
13 Feb 2012
Accepted
19 Mar 2012
First published
20 Mar 2012

Phys. Chem. Chem. Phys., 2012,14, 7170-7175
Article type
Paper

A qualitative failure of B3LYP for textbook organic reactions

N. Chéron, D. Jacquemin and P. Fleurat-Lessard, Phys. Chem. Chem. Phys., 2012, 14, 7170
DOI: 10.1039/C2CP40438A

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