Electronic, vibrational, and rotational structures in the S0 1A1 and S1 1A1 states of phenanthrene.

Autor: Kowaka, Yasuyuki, Yamanaka, Takaya, Baba, Masaaki
Předmět:
Zdroj: Journal of Chemical Physics; 4/12/2012, Vol. 136 Issue 15, p154301, 9p
Abstrakt: Electronic and vibrational structures in the S0 1A1 and S1 1A1 states of jet-cooled phenanthrene-h10 and phenanthrene-d10 were analyzed by high-resolution spectroscopy using a tunable nanosecond pulsed laser. The normal vibrational energies and molecular structures were estimated by ab initio calculations with geometry optimization in order to carry out a normal-mode analysis of observed vibronic bands. The rotational structure was analyzed by ultrahigh-resolution spectroscopy using a continuous-wave single-mode laser. It has been demonstrated that the stable geometrical structure is markedly changed upon the S1 ← S0 electronic excitation. Nonradiative internal conversion in the S1 state is expected to be enhanced by this structural change. The observed fluorescence lifetime has been found to be much shorter than the calculated radiative lifetime, indicating that the fluorescence quantum yield is low. The lifetime of phenanthrene-d10 is longer than that of phenanthrene-h10 (normal deuterium effect). This fact is in contrast with anthracene, which is a structural isomer of phenanthrene. The lifetime at the S1 zero-vibrational level of anthracene-d10 is much shorter than that of anthracene-h10 (inverse deuterium effect). In phenanthrene, the lifetime becomes monotonically shorter as the vibrational energy increases for both isotopical molecules without marked vibrational dependence. The vibrational structure of the S0 state is considered to be homogeneous and quasi-continuous (statistical limit) in the S1 energy region. [ABSTRACT FROM AUTHOR]
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