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Radical Reactivity: Overview

Radical Reactivity: Overview

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...

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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...

Predicting Reaction Outcomes

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Kinetics describes the rate and path by which a reaction occurs. In contrast, thermodynamics deals with state functions and describes the properties, behavior, and components of a system. It is not concerned with the path taken by the process and cannot address the rate at which a reaction occurs. Although it does provide information about what can happen during a reaction process, it does not describe the detailed steps of what appears on an atomic or a molecular level. On the other hand,...

Energy Diagrams, Transition States, and Intermediates

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Free-energy diagrams, or reaction coordinate diagrams, are graphs showing the energy changes that occur during a chemical reaction. The reaction coordinate represented on the horizontal axis shows how far the reaction has progressed structurally. Positions along the x-axis close to the reactants have structures resembling the reactants, while positions close to the products resemble the products. Peaks on the energy diagram represent stable structures with measurable lifetimes, while...

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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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The Collision Theory
Atoms, molecules, or ions must collide before they can react with each other. Atoms must be close together to form chemical bonds. This premise is the basis for a theory that explains many observations regarding chemical kinetics, including factors affecting reaction rates.
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Related Experiment Video

Updated: Sep 26, 2025

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry

Published on: April 8, 2020

Reaction dynamics within a cluster environment.

Marc Briant¹, Jean-Michel Mestdagh¹, Marc-André Gaveau¹

¹Université Paris-Saclay, CEA, CNRS, LIDYL, 91191, Gif-sur-Yvette, France.

Physical Chemistry Chemical Physics : PCCP

|April 20, 2022

Summary

This summary is machine-generated.

Rare gas clusters and helium nanodroplets serve as nanoreactors for studying chemical dynamics. Their unique properties influence reactant mobility and the photodynamics of guest species.

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Last Updated: Sep 26, 2025

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry

Computation of Atmospheric Concentrations of Molecular Clusters from ab initio Thermochemistry

Published on: April 8, 2020

Spatial Separation of Molecular Conformers and Clusters

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Published on: January 9, 2014

Analysis of Complex Molecules and Their Reactions on Surfaces by Means of Cluster-Induced Desorption/Ionization Mass Spectrometry

Analysis of Complex Molecules and Their Reactions on Surfaces by Means of Cluster-Induced Desorption/Ionization Mass Spectrometry

Published on: March 1, 2020

Area of Science:

Physical Chemistry
Chemical Physics
Nanoscale Science

Background:

Rare gas clusters and helium nanodroplets offer unique environments for chemical reactions.
Understanding solvent effects on chemical dynamics is crucial.
Nanoreactors provide insights into molecular behavior at the nanoscale.

Purpose of the Study:

To review the use of rare gas clusters and helium nanodroplets as nanoreactors.
To explore chemical dynamics within these unique solvent environments.
To examine the influence of nanoreactor properties on guest molecule photodynamics.

Main Methods:

Review of experimental and theoretical studies.
Analysis of reactant mobility in cluster and droplet media.
Examination of dynamical responses to photoexcitation.

Main Results:

Rare gas clusters and helium nanodroplets act as effective nanoreactors.
Reactant mobility is a key factor in reaction dynamics.
Cluster/droplet degrees of freedom significantly impact guest photodynamics.

Conclusions:

Nanoreactors provide valuable platforms for studying solvent-mediated chemical dynamics.
The unique properties of rare gas clusters and helium nanodroplets enable detailed investigations.
Further research can leverage these systems to explore complex chemical processes.