Determination of arrhenius parameters for propagation in free-radical polymerizations: An assessment of ab initio procedures

Heuts, J.P.A., Gilbert, R.G. and Radom, L. (1996) Determination of arrhenius parameters for propagation in free-radical polymerizations: An assessment of ab initio procedures. Journal of Physical Chemistry, 100 49: 18997-19006. doi:10.1021/jp9614097


Author Heuts, J.P.A.
Gilbert, R.G.
Radom, L.
Title Determination of arrhenius parameters for propagation in free-radical polymerizations: An assessment of ab initio procedures
Journal name Journal of Physical Chemistry   Check publisher's open access policy
ISSN 0022-3654
1541-5740
Publication date 1996-12
Sub-type Critical review of research, literature review, critical commentary
DOI 10.1021/jp9614097
Volume 100
Issue 49
Start page 18997
End page 19006
Total pages 10
Place of publication Washington, DC, United States
Publisher American Chemical Society
Language eng
Abstract Ab initio calculations have been carried out for the addition of n-alkyl radicals to ethylene, with the aim of identifying levels of theory suitable for the reliable description of the mechanism and energetics of the propagation process in the free-radical polymerization of ethylene. For the calculation of absolute barriers, use of a method such as QCISD(T)/6-311G(d,p), together with MP2 basis set corrections to 6-311+G(3df,2p) and B3-LYP/6-31G(d) zero-point vibrational energy corrections, is recommended. For the calculation of Arrhenius frequency factors, the parameters required, i.e., geometries, fundamental frequencies, and rotational barriers, can be reliably obtained at much simpler levels of theory, such as UHF/6-31G(d) or even UHF/3-21G.
Keyword Plesset perturbation-theory
Hindered internal-rotation
Absolute rate constants
Transition-state theory
Pulsed-laser
Reaction-mechanism
Substituted alkenes
Addition-reactions
Rate coefficient
Wave-functions
Q-Index Code C1
Q-Index Status Provisional Code
Institutional Status Unknown

Document type: Journal Article
Sub-type: Critical review of research, literature review, critical commentary
Collections: School of Chemistry and Molecular Biosciences
Centre for Nutrition and Food Sciences Publications
 
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Created: Mon, 07 Mar 2011, 15:47:43 EST