We investigated the S1 and S2 states of linear and zigzag cata-condensed hydrocarbons on the basis of the results of jet spectroscopy and theoretical calculations. The S1 states of anthracene and tetracene are represented by the HOMO → LUMO configuration (Φ(A)), whereas those of phenanthrene and chrysene are represented by HOMO-1 → LUMO and HOMO → LUMO+1 configurations (Φ(B)). We found that the fluorescence lifetime varied with different vibronic levels in the S1 states of linear cata-condensed hydrocarbons due to the mode-selective internal conversion to the S0 state. This selectivity is likely to be seen in the S1 Φ(A) state of the D(2h) molecule.
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