Ab Initio Study of Free-Radical Polymerizations: Cost-Effective Methods to Determine the Reaction Rates

wim — Fri, 30 Sep 2011 12:51:49 +0000

V. Van Speybroeck, K. Van Cauter, B. Coussens, M. Waroquier

ChemPhysChem

6 (1), 180-189

2005

Abstract

The addition of carbon-centered radicals to ethene, which are important in free-radical polymerization processes, are studied from a theoretical point of view. Experimental data for the rate constants are only available for the addition of methyl, ethyl, propyl and butyl radicals. The latter reactions are taken as model systems to derive a cost-effective method for the addition of alkyl radicals to ethene. The proposed model must be accurate and computationally feasible for additions in which larger radicals are involved. Accuracy is validated by direct comparison of theoretical and experimental rate constants in the temperature range from 300 to 600 K. A variety of electronic-structure methods were tested ranging from Hartree–Fock and post-Hartree–Fock methods to pure and hybrid density functional theory methods. Molecular partition functions were refined by treating large amplitude vibrations beyond the harmonic oscillator approximation.

DOI

http://dx.doi.org/10.1002/cphc.200400277

Private attachment

05 chemphyschem 6(1)180 van speybroeck.pdf

Molecular Modeling of the Hydrolysis of Potent Implantable Drug Delivery Devices

wim — Fri, 06 Mar 2015 08:47:33 +0000

Ab initio kinetic parameters of free radical polymerisation reactions

wim — Tue, 18 Oct 2011 08:44:45 +0000

K. Van Cauter, V. Van Speybroeck, B. Coussens, M. Waroquier

Poster

Conference / event / venue

DFT2003 conference: "The applications of Density Functional Theory in Chemistry and Physics

Brussels, Belgium

Sunday, 7 September, 2003 to Friday, 12 September, 2003

Center for Molecular Modeling - B. Coussens