dc.contributor.author |
McIntosh, Grant |
en |
dc.contributor.author |
Russell, Douglas K |
en |
dc.date.accessioned |
2018-10-17T00:51:27Z |
en |
dc.date.issued |
2013-05-09 |
en |
dc.identifier.issn |
1089-5639 |
en |
dc.identifier.uri |
http://hdl.handle.net/2292/42323 |
en |
dc.description.abstract |
Analogues of important aromatic growth mechanisms in hydrocarbon pyrolysis and combustion systems are extended to chlorinated systems. We consider the addition of C2Cl2 to both C4Cl3 and C4Cl5 radicals at the M06-2X/6-311+G(3df,3p)//B3LYP/6-31G(d) level of theory, and we demonstrate that these reaction systems have much in common with those of nonchlorinated species. In particular, we find that these radicals appear to lead preferentially to fulvenes, and not to the observed aromatic products, as is found in nonchlorinated systems. We have therefore also considered nonradical C4/C2 channels by way of Diels-Alder cyclization of C4Cl4/C2Cl2 and C4H2Cl2/C2HCl pairs to describe aromatic formation. While the latter pair readily leads to the formation of partially chlorinated benzenes, the fully chlorinated congeners are sterically prohibited from ring closing directly; this leads to a series of novel rearrangement processes which predict the formation of hexachloro-1,5-diene-3-yne, in addition to hexachlorobenzene, in good agreement with experiment. This suggests, for the first time, that facile nonradical routes to aromatic formation are operative in partially and fully chlorinated pyrolysis and combustion systems. |
en |
dc.format.medium |
Print-Electronic |
en |
dc.language |
eng |
en |
dc.relation.ispartofseries |
The journal of physical chemistry. A |
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dc.rights |
Items in ResearchSpace are protected by copyright, with all rights reserved, unless otherwise indicated. Previously published items are made available in accordance with the copyright policy of the publisher. |
en |
dc.rights.uri |
https://researchspace.auckland.ac.nz/docs/uoa-docs/rights.htm |
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dc.subject |
Benzene |
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dc.subject |
Hydrocarbons, Chlorinated |
en |
dc.subject |
Molecular Structure |
en |
dc.subject |
Kinetics |
en |
dc.subject |
Quantum Theory |
en |
dc.title |
Molecular mechanisms in the pyrolysis of unsaturated chlorinated hydrocarbons: formation of benzene rings. 1. Quantum chemical studies. |
en |
dc.type |
Journal Article |
en |
dc.identifier.doi |
10.1021/jp3120379 |
en |
pubs.issue |
20 |
en |
pubs.begin-page |
4183 |
en |
pubs.volume |
117 |
en |
dc.rights.holder |
Copyright: The author |
en |
dc.identifier.pmid |
23597165 |
en |
pubs.end-page |
4197 |
en |
pubs.publication-status |
Published |
en |
dc.rights.accessrights |
http://purl.org/eprint/accessRights/RestrictedAccess |
en |
pubs.subtype |
Research Support, Non-U.S. Gov't |
en |
pubs.subtype |
Journal Article |
en |
pubs.elements-id |
380342 |
en |
dc.identifier.eissn |
1520-5215 |
en |
pubs.record-created-at-source-date |
2013-05-23 |
en |
pubs.dimensions-id |
23597165 |
en |