Radical Reactivity by Computation and Experiment

Research output: Chapter in Book/Report/Conference proceedingChapterpeer-review

1 Citation (Scopus)


This chapter discusses various methods for defining and measuring radical stability, including the familiar radical stabilization energy (RSE), along with some lesser-known alternatives, and explains the difference between stability and persistence. A large compilation of RSEs for carbon-centered radicals is presented and used to illustrate the principal structure-reactivity trends. Other key properties of the radicals and other reagents in free-radical polymerization reactions, including polarity, steric effects, and bond strengths, are also defined and discussed. Finally, it is shown how these factors combine to determine the kinetics and thermodynamics of the principal radical reactions in both conventional and controlled radical polymerization processes.

Original languageEnglish
Title of host publicationPolymer Science
Subtitle of host publicationA Comprehensive Reference, 10 Volume Set
Number of pages20
ISBN (Print)9780080878621
Publication statusPublished - 2012
Externally publishedYes


  • Atom transfer radical polymerization
  • Bond strength
  • Chain transfer processes
  • Curve-crossing model
  • Free-radical copolymerization
  • Free-radical polymerization
  • Halogen transfer
  • Hammett parameters
  • Hydrogen transfer
  • Kinetics
  • Linear free-energy relationships
  • Nitroxide-mediated polymerization
  • Propagation rate coefficients
  • Quantum chemistry
  • Radical addition
  • Radical reactivity
  • Radical stability
  • Radical stabilization energy
  • Reversible addition-fragmentation chain transfer (RAFT) polymerization
  • Substituent effects
  • Taft parameters
  • Thermodynamics


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