Phenylene coupling of methylene sites. The spin states of bis(X-methylene)-p-phenylenes and bis(chloromethylene)-m-phenylene
DSpace at IIT Bombay
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Title |
Phenylene coupling of methylene sites. The spin states of bis(X-methylene)-p-phenylenes and bis(chloromethylene)-m-phenylene
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Creator |
TRINDLE, C
DATTA, SN MALLIK, B |
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Subject |
singlet-triplet gaps
ground-state organic-molecules energy surface carbenes phenylcarbene polyradicals diradicals nitroxide violation |
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Description |
We judge the energetic sequence of spin states in substituted methylenes by ab initio multiconfigurational computations and, where feasible, density functional modeling techniques. The best of these calculations reproduce well-established singlet-triplet gaps in X-C-Y species, in which X can be phenyl and Y can be H, methyl, or chloro. Similar computations on p-phenylene-coupled Y-methylenes and meta-coupled Y-methylenes support the suggestion by Zuev and Sheridan that bis(chloromethylene)-p-phenylene has a singlet diradical ground state. However, despite the density functional computations' support for those authors' suggestion that bis (chloromethylene)-m-phenylene has a singlet ground state, we find that our best MCSCF calculations place the quintet ground state suggested by the simplest theory almost equal in energy to that singlet.
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Publisher |
AMER CHEMICAL SOC
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Date |
2011-07-14T15:18:21Z
2011-12-26T12:48:27Z 2011-12-27T05:39:27Z 2011-07-14T15:18:21Z 2011-12-26T12:48:27Z 2011-12-27T05:39:27Z 1997 |
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Type |
Article
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Identifier |
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 119(52), 12947-12951
0002-7863 http://dx.doi.org/10.1021/ja9704139 http://dspace.library.iitb.ac.in/xmlui/handle/10054/3995 http://hdl.handle.net/10054/3995 |
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Language |
en
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