title: Microscopic progression in the free radical addition reaction: modeling, geometry, energy, and kinetics.
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.
authors.affiliation: Department of Chemistry, School of Pharmaceutical Sciences, Guangzhou Medical University, Guangzhou, 511436, People's Republic of China.
authors.forename: Yun
authors.initials: Y
authors.lastname: Zhang
authors.affiliation: Department of Chemistry, School of Pharmaceutical Sciences, Guangzhou Medical University, Guangzhou, 511436, People's Republic of China.
authors.forename: Hong
authors.initials: H
authors.lastname: Huang
authors.affiliation: Department of Chemistry, School of Pharmaceutical Sciences, Guangzhou Medical University, Guangzhou, 511436, People's Republic of China.
authors.forename: Zhiling
authors.initials: Z
authors.lastname: Liang
authors.affiliation: Department of Chemistry, School of Pharmaceutical Sciences, Guangzhou Medical University, Guangzhou, 511436, People's Republic of China.
authors.forename: Houhe
authors.initials: H
authors.lastname: Liu
authors.affiliation: Department of Chemistry, School of Pharmaceutical Sciences, Guangzhou Medical University, Guangzhou, 511436, People's Republic of China.
authors.forename: Ling
authors.initials: L
authors.lastname: Yi
authors.affiliation: Department of Medical Genetics and Cell Biology, Guangzhou Medical University, Guangzhou, 511436, People's Republic of China.
authors.forename: Jinhong
authors.initials: J
authors.lastname: Zhang
authors.affiliation: Department of Material and Engineering, Zhengzhou University of Light Industry, Zhengzhou, 450002, People's Republic of China.
authors.forename: Zhiqiang
authors.initials: Z
authors.lastname: Zhang
authors.affiliation: College of Chemistry and Molecular Sciences, Wuhan University, Wuhan, 430072, People's Republic of China.
authors.forename: Cheng
authors.initials: C
authors.lastname: Zhong
authors.affiliation: Department of Chemistry, School of Pharmaceutical Sciences, Guangzhou Medical University, Guangzhou, 511436, People's Republic of China. hyug@gzhmu.edu.cn.
authors.forename: Yugang
authors.initials: Y
authors.lastname: Huang
authors.affiliation: Department of Chemistry, School of Pharmaceutical Sciences, Guangzhou Medical University, Guangzhou, 511436, People's Republic of China. gzhygd@gzhmu.edu.cn.
authors.forename: Guodong
authors.initials: G
authors.lastname: Ye
keywords: Benzoyl radical; Photopolymerization; Radical addition