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Related Concept Videos

Radical Reactivity: Overview01:11

Radical Reactivity: Overview

2.1K
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...
2.1K
Radical Formation: Abstraction00:47

Radical Formation: Abstraction

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The electron of an atom can be abstracted from a compound by a relatively unstable radical to generate a new radical of relatively greater stability. For example, an initiator which forms radicals by homolysis can abstract a suitable species like a hydrogen atom or a halogen atom from a compound to generate a new radical. This ability of radicals to propagate by abstraction is a crucial feature of radical chain reactions.
Even though homolysis produces radicals, it is different from radical...
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Radical Reactivity: Concentration Effects01:20

Radical Reactivity: Concentration Effects

1.5K
In a radical reaction, the concentration of starting materials governs the selectivity of a radical. For example, the reaction between an alkyl halide and an alkene, in the presence of tin hydride and AIBN, begins with the generation of a tin radical. The generated radical then abstracts halogen from the alkyl halide, producing an alkyl radical. This alkyl radical can either react with tin hydride, yielding an alkane, or add to an alkene, generating a nitrile-stabilized radical, eventually...
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Radical Reactivity: Intramolecular vs Intermolecular01:33

Radical Reactivity: Intramolecular vs Intermolecular

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Radical reactions can occur either intermolecularly or intramolecularly. In an intermolecular radical reaction, a nucleophilic radical adds to an electrophilic alkene or vice versa. In such reactions, the radical and generally the alkene, which is also called the radical trap, are two different molecules. Additionally, for such intermolecular reactions to occur, the radical trap must be active, present in an excess concentration, and the radical starting material must have a weak...
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Radical Anti-Markovnikov Addition to Alkenes: Mechanism01:17

Radical Anti-Markovnikov Addition to Alkenes: Mechanism

3.7K
The reaction of hydrogen bromide with alkenes in the presence of hydroperoxides or peroxides proceeds via anti-Markovnikov addition. The radical chain reaction comprises initiation, propagation, and termination steps.
The mechanism starts with chain initiation, which involves two steps. In the first chain initiation step, a weak peroxide bond is homolytically cleaved upon mild heating to form two alkoxy radicals. In the second initiation step, a hydrogen atom is abstracted by the alkoxy...
3.7K
Radical Anti-Markovnikov Addition to Alkenes: Thermodynamics01:32

Radical Anti-Markovnikov Addition to Alkenes: Thermodynamics

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The anti-Markovnikov addition of hydrogen halides to an alkene is thermodynamically feasible only with HBr. The radical addition reaction with other hydrogen halides like HCl and HI is thermodynamically unfavorable.
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Updated: Jun 14, 2025

Measurement of Ultrafast Vibrational Coherences in Polyatomic Radical Cations with Strong-Field Adiabatic Ionization
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Radical Addition Reactions: Hierarchical Ab Initio Benchmark and DFT Performance Study.

Yuman Hordijk1, Marco Dalla Tiezza1, Daniela Rodrigues Silva1

  • 1Department of Chemistry and Pharmaceutical Sciences, Amsterdam Institute for Molecular and Life Sciences (AIMMS), Vrije Universiteit Amsterdam De Boelelaan 1108, 1081, HZ Amsterdam, The Netherlands.

Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry
|September 4, 2024
PubMed
Summary

This study benchmarks ab initio methods for radical addition reactions, establishing high-accuracy reference data. It then evaluates 98 density functional theory (DFT) approximations, identifying top performers for reaction barriers and energies.

Keywords:
Benchmark studyCoupled clusterDensity functional theoryDunning basis setsRadical addition reaction

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Area of Science:

  • Computational Chemistry
  • Quantum Chemistry
  • Theoretical Chemistry

Background:

  • Accurate theoretical prediction of reaction energetics and mechanisms is crucial in chemistry.
  • Radical addition reactions to unsaturated hydrocarbons are fundamental processes with broad implications.
  • Previous studies have often relied on less rigorous computational methods, limiting predictive accuracy.

Purpose of the Study:

  • To perform a hierarchical ab initio benchmark study of gas-phase radical addition reactions.
  • To establish high-accuracy reference data for reactions involving methyl, amino, hydroxyl, and thiomethyl radicals with acetylene and ethylene.
  • To evaluate the performance of a wide range of density functional theory (DFT) approximations against this benchmark data.

Main Methods:

  • Employed a hierarchical series of ab initio methods (HF, MP2, CCSD, CCSD(T)) and Dunning basis sets ((aug)-cc-pVDZ, (aug)-cc-pVTZ, (aug)-cc-pVQZ).
  • Utilized quasi-restricted orbital (QRO) reference wavefunctions to mitigate spin contamination in HF calculations.
  • Extrapolated results to the Complete Basis Set (CBS) limit for high accuracy.
  • Assessed 98 DFT approximations for their ability to reproduce benchmark reaction barriers, energies, and geometries.

Main Results:

  • Ab initio calculations converged to within 0.0-3.4 kcal mol⁻¹ for methods and 0.0-1.0 kcal mol⁻¹ for basis sets at the QRO-CCSD(T)/CBS+ level.
  • Identified several DFT functionals with Mean Absolute Errors (MAE) as low as 0.8-1.0 kcal mol⁻¹ for reaction barriers and energies.
  • Best performing DFT functionals include MN12-SX, CAM-B3LYP, M06-2X, BMK, and OLYP.
  • These top DFT functionals accurately reproduced key geometrical parameters, with an average deviation of 2% from the reference.

Conclusions:

  • The study provides a robust benchmark dataset for radical addition reactions using high-level ab initio theory.
  • Specific DFT functionals demonstrate high accuracy for predicting reaction energetics and geometries, offering reliable alternatives for computational studies.
  • The findings guide the selection of appropriate DFT methods for future research on similar chemical systems.