Journal of Physical Chemistry, Vol.99, No.44, 16199-16209, 1995
Solvent and Temperature Effects on Dual Fluorescence in a Series of Carotenes - Energy-Gap Dependence of the Internal-Conversion Rate
Solvent and temperature effects on the dipole-allowed S-2 --> S-0 and the symmetry-forbidden Si --> S-0 transitions of all-trans-carotenes, with 5 (m-5), 7 (m-7), 8 (m-8), 9 (m-9), 11 (all-trans-beta-carotene>, 15 (decapreno-beta-carotene), and 19 (dodecapreno-beta-carotene) conjugated double bonds (N), have been investigated by steady-state and time-correlated single-photon counting (SPC) experiments. The measured fluorescence quantum yields of the S-1 --> S-0 emission (Phi(f1)) decrease from 7 x 10(-3) to about 4 x 10(-6) at room temperature when going from m-5 to beta-carotene. For the longest compounds N = 15 and 19 only the S-2 emission was observed, with fluorescence yields (Phi(f2)) of about 5 x 10(-5). The measured S-1 fluorescence lifetime of m-5, m-7, m-8, and m-9 was found to decrease with decreasing energy gap between S-1 and S-0 (Delta E(S-1-S-0)), in accordance with the energy gap law (EGL). Phi(f2) indicates that the S-2 lifetime is on the order of 100 fs for all compounds. Fluorescence emission from the S-1 state of beta-carotene in room temperature liquids was observed with the 0-0 transition located at 14 200 +/- 500 cm(-1). The intensity ratio I-2/I-1, where I-2 represents the integrated S-2 --> S-0 emission and I-1 the S-1 --> Sd emission spectrum determined by time-resolved methods, depends on the Delta E(S-1-S-0) in a similar way as Phi(f2)/Phi(f1) (=k(r2)k(1)/(k(r1)k(21))).
Keywords:INTRAMOLECULAR ELECTRON-TRANSFER;RESOLUTION OPTICAL SPECTROSCOPY;RESONANCE RAMAN-SPECTROSCOPY;EXCITED SINGLET-STATE;C=C STRETCHING MODE;BETA-CAROTENE;LONG POLYENES;POTENTIAL SURFACES;EMISSION-SPECTRA;LINEAR POLYENES