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Microscopic progression in the free radical addition reaction: modeling, geometry, energy, and kinetics.

Research paper by Yun Y Zhang, Hong H Huang, Zhiling Z Liang, Houhe H Liu, Ling L Yi, Jinhong J Zhang, Zhiqiang Z Zhang, Cheng C Zhong, Yugang Y Huang, Guodong G Ye

Indexed on: 17 Feb '17Published on: 17 Feb '17Published in: Journal of Molecular Modeling



Abstract

The free radical addition reaction is very important in UV curing. The benzoyl radical is the most commonly observed radical. In the addition process, the benzoyl radical adds to an acrylate monomer, forming a primary radical that has great value for subsequent research. In this article, a quantum chemical method was used to study the microscopic progression from the reactive complex to the saddle point. The reactions of three monomers (amylene, allyl methyl ether and methyl acrylate) with a benzoyl radical were evaluated in terms of geometry and energy. The results were also interpreted with an expanded version of the Polanyi rules and the interaction/deformation theory. The deformation energy of methyl acrylate was found to be the smallest, and the bond formation index showed that the transition state in the methyl acrylate system forms early, and can easily reach the saddle point. The activity of the monomer was ascertained by charge analysis and was further confirmed by the reaction rate. Mayer bond order curves depicted the constantly changing chemical bonds during formation and dissociation. Reduced density gradient analysis showed a weak interaction between the monomer and the benzoyl radical.