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ID 37978
file
creator
Ohshimo, Keijiro
Ohno, Koichi
subject
Intracluster reaction
cluster anions
infrared spectroscopy
reaction pathway
NDC
Chemistry
abstract
A cluster anion of vinyl compounds in the gaseous phase has served as one of the simplest microscopic models of the initial stages of anionic polymerization. Herein, we describe our investigations into the initial stage mechanisms of anionic polymerization of acrylonitrile (AN; CH2=CHCN) trimer anions. While the cyclic oligomer is found in mass and photoelectron spectroscopic studies of (AN)3-, only the chain oligomer is found in the infrared photodissociation (IRPD) spectrum of Ar-tagged (AN)3-. Based on the calculated polymerization pathway of (AN)3-, we consider that the chain oligomers are the reaction intermediates in the cyclization of (AN)3-. The rotational isomerization of the (AN)3- chain oligomer is found to be the bottleneck in the cyclization of (AN)3-. To form the (AN)4- chain oligomer by chain propagation, the addition of an AN molecule to (AN)3- should occur prior to the rotational isomerization. We conclude that the rotational isomerization in the (AN)3- chain oligomer is the key branching point between cyclization (termination) or chain propagation in the anionic polymerization.
description
This is a preprint of an article published by American Chemical Society in Journal of Physical Chemistry A, 2012, available online: http://pubs.acs.org/doi/abs/10.1021/jp305291r.
journal title
Journal of Physical Chemistry A
volume
Volume 116
issue
Issue 30
start page
7937
end page
7942
date of issued
2012-08-02
publisher
American Chemical Society
issn
1089-5639
publisher doi
pubmed id
language
eng
nii type
Journal Article
HU type
Journal Articles
DCMI type
text
format
application/pdf
text version
author
rights
Copyright (c) 2012 American Chemical Society
relation is version of URL
http://dx.doi.org/10.1021/jp305291r
department
Graduate School of Science



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