Electronic and vibrational structure in the S0 and S1 states of corannulene

• Published in: The Journal of chemical physics 2019-12, Vol.151 (23), p.234305-234305
• Main Authors: Kanaoka, Ayumi, Tohyama, Hiromi, Kunishige, Sachi, Katori, Toshiharu, Nishiyama, Akiko, Misono, Masatoshi, Nakayama, Naofumi, Sakurai, Hidehiro, Tsuge, Masashi, Baba, Masaaki
• Format: Article
• Language: English
• Subjects: Aromatic hydrocarbons; Band theory; Configuration interaction; Coriolis force; Density functional theory; Electron states; Excitation spectra; Fluorescence; Mathematical analysis; Physics; Symmetry; Time dependence
• ISSN: 0021-9606; 1089-7690
• DOI: 10.1063/1.5129852

Corannulene is a nonplanar aromatic hydrocarbon also known as a buckybowl. Its electronic and vibrational structure has been investigated by analyzing its fluorescence excitation spectrum and dispersed fluorescence spectrum in a supersonic jet. Its spectral features are in keeping with the expectation, confirmed by some previous results, that it has fivefold or C5v symmetry. The observed prominent vibronic bands in the S1 ← S0 transition have been assigned to e1 and e2 bands on the basis of theoretical calculations so that the S1 state was assigned to 1E2. The symmetry adapted cluster configuration interaction calculation supports this assignment of the S1 electronic state, although the time-dependent density functional theory calculation suggests that the S1 state is 1A2. It has also been shown that the normal coordinates for strong vibronic bands mainly include out-of-plane vibrational motion. The rotational envelopes are well explained by taking account of the Coriolis interaction between the degenerate vibrational and rotational levels. The mechanism of bowl-to-bowl inversion is also discussed with the results of theoretical calculations regarding the barrier to inversion and metastable conformation.