Van der Waals forces model

Chain initiation occurs when two monomer radicals are coupled to form a dimer biradical and proceeds further." This is an endothermic reaction requiring a heat of formation of 16 kcal/mol. Because of energetic concerns, chain initiation is unlikely to happen in the gas phase at low pressure. When the monomers are adsorbed onto the surface of the substrate, it is believed that, the high local concentration of monomers promotes the formation of biradicals assisted by van der waals forces. Models developed for vapor deposition polymerization of parylene-N indicate that initiation is a third order reaction with an activation energy of 24.8 kcal/mol. 

The second coefficient of the virial was calculated by Lennard-Jones using, in relation [7.76], the potential function deduced from the van der Waals forces model, i.e. ... 

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