Electronic relaxation processes of all-trans-2,4,6,8-decatetraene vapour revealed by the measurements of the S1 and S2 fluorescence

Fluorescence and excitation spectra of all-trans-2,4,6,8-decatetraene vapour have been measured at different buffer gas pressures from 0 to 1.07 × 10⁵ Pa (800 Torr). The quantum yield of the S₁ fluorescence (Φ_F(S₁)) increases with increasing the buffer gas pressure, while that of the S₂ fluorescence (Φ_F(S₂)) decreases slightly. Φ_F(S₁) decreases significantly with increasing the excitation energy under the collision free condition, while Φ_F(S₂) decreases only slightly. The pressure dependence of the fluorescence yields is interpreted in terms of the relaxation model involving the reversible internal conversion between S₁ and S₂ and the vibrational relaxation in the S₁ manifold. The reverse S₁ → S₂ internal conversion rate is shown to be very slow compared with the forward S₂ → S₁ internal conversion rate.