Accurate ab initio prediction of propagation rate coefficients in free-radical polymerization: Acrylonitrile and vinyl chloride

On the Use of Quantum Chemistry for the Determination of Propagation, Copolymerization, and Secondary Reaction Kinetics in Free Radical Polymerization

“…Typical models belonging to this category are COSMO (conductor-like screening model) and PCM (polarizable continuum model), particularly suitable for treating large systems [134,135]. Continuum models are considered adequate for radical thermochemistry, and have been used in the determination of the solvent effect and its relevance for various FRP systems [86,89,99,103]. Encouraging results have been obtained using the quantum mechanics/molecular mechanics (QM/MM) method [132] and the Car-Parrinello molecular dynamics (CPMD) method [136].…”

“…The first computational studies of propagation reactions of FRP have been performed for homopolymer system of small molecules. In particular, propagation reaction of alkenes that are characterized by very simple molecular structures such as ethene [84,85], vinyl chloride [86,87], and acrylonitrile [86][87][88] were studied. Gradually, the interest was turned to the study of homopolymer systems of more complex monomers such as styrene and various acrylates [66,89] and to that of monomers with larger substituent [88,90] such as α-substituted acrylates [91].…”

Benchmark Energetic Data in a Model System for Grubbs II Metathesis Catalysis and Their Use for the Development, Assessment, and Validation of Electronic Structure Methods

“…However, evidence delineating poor performance of popular density functionals in several areas in chemistry has been presented by many research groups. [36][37][38][39][40][41][42][43][44][45][46][47][48][49][50][51][52] Indeed, BP86 and B3LYP are not accurate for the description of Grubbs metathesis catalysis, as shown by Tsipis et al 23 and us; 30,53 both functionals fail to predict the trend of the phosphine binding energies between the first-and second-generation Grubbs' ruthenium precatalysts for olefin metathesis. 30,31,53 Moreover, Piacenza et al 31 assessed the performance of five density functionals against benchmark energetic data for RuCl 2 (PH 3 ) 2 CH 2 , a small model system for the firstgeneration Grubbs catalysts.…”

First Principles Prediction of the Copolymerization Process of 1,3-Butadiene and Vinyl Chloride

“…This method is effective because most of the molecule is unaffected by the polymerization process. However, these methods are still more complicated than the simple B3LYP/6-31G(d) and B3LYP/6-311+G(3df,2p)//B3LYP/6-31G(d) methods used here [9].…”

“…These qualitative results include: the geometry of the transition state (TS) [4,5], which reaction mechanisms are most likely [6,7], and whether penultimate effects are negligible [8]. Only a hand full of polymer studies has reported quantitatively accurate results [9]. The validation of the quality of these results is often a comparison between macroscopic experimental data and the experimental data predicted from the ab initio model [10].…”