TOC

Top

  1. Introduction and Retrospective
  2. Structure of TSs and Intrinsic Reaction Coordinate of Radical Addition
  3. Objects of Investigation: Basic Set of Reactions
  4. Thermochemical Aspect
  5. Energy Partitioning
  6. Results of the PMO Theory Approach
  7. Alternative Form of the PMO Equation: Effective Electronegativity of Reagent
  8. Comparison of Direct TS Calculations with Indices of Reactivity
  9. Empirical Schemes of Vinyl Monomers' Relative Reactivity in Radical Addition Reactions
  10. Conclusions
  11. References

Radical addition to the vinyl C=C bond: Quantum chemistry model of the reaction

Conclusions

So, the main results of this investigation could be summed as follows:

  1. As a result of close theoretical study of the reaction path of radical addition to the C=C bond, a new computational scheme of reagents' activity is proposed for this class of reactions.
  2. The following form of dependencies is proposed for building nonlinear correlation schemes:
    where xi and xj are some parameters of reagents. This form seems to be in close relation with dependencies that give calculations by methods of perturbation theory.

A proposed recommendation arises:
Before trying some computational index of reactivity in correlations with experimental data, first check its relevance on computational reactivity (on activation energies of reactions calculated by the same method).