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タイトル: | Jet spectroscopy of buckybowl: Electronic and vibrational structures in the S0 and S1 states of triphenylene and sumanene |
著者: | Kunishige, Sachi Kawabata, Megumi Baba, Masaaki Yamanaka, Takaya Morita, Yuki Higashibayashi, Shuhei Sakurai, Hidehiro |
著者名の別形: | 馬場, 正昭 |
キーワード: | excited states fluorescence molecular electronic states nonradiative transitions organic compounds vibrational states vibronic states |
発行日: | 28-Jul-2013 |
出版者: | American Institute of Physics |
誌名: | The Journal of chemical physics |
巻: | 139 |
号: | 4 |
論文番号: | 044313 |
抄録: | Sumanene is a typical buckybowl molecule with C3v symmetry. We observed a fluorescence excitation spectrum and a dispersed fluorescence spectrum of sumanene in a supersonic jet. Bowl effects were clarified by comparing the spectra with those of triphenylene (D3h symmetry), which is a planar prototype of nonplanar sumanene. The S1 (1)A1 ← S0 (1)A1 transition is symmetry allowed. We found the 00 (0) band in the fluorescence excitation spectrum at 357.78 nm; this band was missing in the forbidden S1 (1)A1 (') ← S0 (1)A1 (') transition of triphenylene. The transition moment was shown to be along the oblate symmetric top axis (out of plane) by the observed rotational contour. A large number of vibronic bands were observed, unlike in triphenylene. Some were considered to be out-of-plane vibrational modes, which lead to a bowl-to-bowl inversion reaction assisted by in-plane vibrations. We found that the vibronic bands were markedly weak in the high energy region of triphenylene-d12. This indicates that the fluorescence quantum yield is very low at the high vibrational levels in the S1 state due to the rapid radiationless transition. The main process is considered to be internal conversion to the S0 state. The nonplanar structural distortion may also enhance radiationless transitions. We could not, however, observe weakening of the vibronic bands in the fluorescence excitation spectrum of sumanene. |
著作権等: | © 2013 American Institute of Physics. |
URI: | http://hdl.handle.net/2433/178529 |
DOI(出版社版): | 10.1063/1.4816636 |
PubMed ID: | 23901986 |
出現コレクション: | 学術雑誌掲載論文等 |
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