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Ab initio Calculations on the Structure of Pyridine in Its Lowest Triplet State
| Content Provider | Semantic Scholar |
|---|---|
| Author | Buma, Wybren Jan Groenen, E. J. J. Hemert, Marc C. Van |
| Copyright Year | 1990 |
| Abstract | Recently we have experimentally shown that pyridine-& as a guest in a single crystal of benzene-& adopts a boatlike structure upon excitation into the lowest triplet state To. Here MRDCI ab initio calculations are presented that reveal that the observed nonplanarity of the molecule is not caused by the crystal field but is an intrinsic property of pyridine in To. The origin of the distortion may be found in the nature of the Ir-electron system. In the lowest triplet state it is no longer a 6~-electron system as in the ground state but, in first approximation, a 7r-electron system, in which the extra electron occupies a A* orbital that is strongly antibonding between the nitrogen atom and the ortho carbon atoms. The lowest triplet state can not be simply interpreted as an n r * or a AT* state. |
| File Format | PDF HTM / HTML |
| DOI | 10.1002/chin.199042060 |
| Alternate Webpage(s) | https://pure.uva.nl/ws/files/1999070/28665_JACS_1990_112_14_5447.pdf |
| Alternate Webpage(s) | https://doi.org/10.1002/chin.199042060 |
| Volume Number | 21 |
| Language | English |
| Access Restriction | Open |
| Content Type | Text |
| Resource Type | Article |