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| Content Provider | Royal Society of Chemistry (RSC) |
|---|---|
| Author | Perrins, N. C. Smith, A. L. Simons, J. P. |
| Copyright Year | 1971 |
| Abstract | Benzene and polyhalo-alkanes containing weakly acidic protons, form intermolecular complexes in dilute solutions at low temperature. In these complexes the near u.-v. absorption and fluorescence spectra of the benzenes are shifted to higher frequencies, but there is no change in their vibrational structure. The ã1B2u→[graphic omitted]1A1g electronic transition remains symmetry forbidden in the complex and the band origin is very weak. In the phosphorescence spectrum, however, the intermolecular perturbation completely alters the vibrational structure and both the “true” origin and the progression in the totally symmetric breathing frequency ν1 based upon it, become intense. It is suggested that the intermolecular perturbation promotes a pseudo Jahn–Teller distortion of the ring in the ã3B1u state, which lowers its point symmetry to D2h. A Franck–Condon analysis of the band structure is used in an approximate partial reconstruction of the phosphorescence spectral profile and calculations of the degree of distortion are made from it. |
| Starting Page | 3415 |
| Ending Page | 3424 |
| Page Count | 10 |
| File Format | |
| ISSN | 00147672 |
| Volume Number | 67 |
| Journal | Transactions of the Faraday Society |
| DOI | 10.1039/TF9716703415 |
| Language | English |
| Publisher | Royal Society of Chemistry |
| Access Restriction | Open |
| Subject Keyword | Spectroscopy Jahn\u2013Teller effect Condon Benzene Electronic band structure Woodward\u2013Hoffmann rules Point reflection Phosphorescence Molecular electronic transition Jahn |
| Content Type | Text |
| Resource Type | Article |
| Subject | Physics and Astronomy Physical and Theoretical Chemistry Engineering |
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