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Related Concept Videos

Radical Reactivity: Overview01:11

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Radicals, the highly reactive species, gain stability by undergoing three different reactions. The first reaction involves a radical-radical coupling, in which a radical combines with another radical, forming a spin‐paired molecule. The second reaction is between a radical and a spin‐paired molecule, generating a new radical and a new spin‐paired molecule. The third reaction is radical decomposition in a unimolecular reaction, forming a new radical and a spin‐paired molecule. These three...
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Ring-opening radical clock reactions: many density functionals have difficulty keeping time.

Iain D Mackie1, Gino A DiLabio

  • 1National Institute for Nanotechnology, National Research Council of Canada, 11421 Saskatchewan Drive, Edmonton, Alberta, Canada T6G 2M9.

Organic & Biomolecular Chemistry
|March 30, 2011
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Summary

Density-functional theory (DFT) methods were evaluated for ring-opening reactions of cyclopropyl and cyclobutyl radicals. PBE, B971, and B3LYP accurately predicted experimental results, while other tested functionals performed poorly.

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Area of Science:

  • Computational Chemistry
  • Theoretical Chemistry
  • Quantum Chemistry

Background:

  • Ring-opening reactions of cyclopropyl and cyclobutyl radicals are important in organic chemistry.
  • Accurate theoretical methods are needed to predict the kinetics and energetics of these reactions.

Purpose of the Study:

  • To evaluate the performance of various density-functional theory (DFT) methods.
  • To determine the suitability of DFT for describing the ring-opening reactions of cyclopropyl and cyclobutyl-type radicals.

Main Methods:

  • Computational study using DFT.
  • Evaluation of PBE, B971, B3LYP, BLYP, CAM-B3LYP, BHandHLYP, B2PLYP, B2PLYP-D, MPW1K, BMK, and M06-2X functionals.
  • Comparison of calculated kinetics and energetics with experimental data for specific radical systems.

Main Results:

  • PBE, B971, and B3LYP functionals demonstrated good agreement with experimental data.
  • Other functionals, including those designed for kinetics, showed poor performance.
  • Some functionals exhibited dependency on integration grid size.

Conclusions:

  • PBE, B971, and B3LYP are recommended for studying the kinetics and energetics of cyclopropyl and cyclobutyl radical ring-opening reactions.
  • Careful selection of DFT functionals is crucial for accurate predictions in radical chemistry.
  • Further investigation into grid dependencies may be necessary for certain functionals.