Subpicosecond pump–probe measurements of the ...
|Title||Subpicosecond pump–probe measurements of the electronic relaxation rates of the S1 states of azulene and related compounds in polar and nonpolar solvents|
|Author(s)||Brian D. Wagner, M. Szymanski, R. P. Steer|
|Journal||Journal of Chemical Physics|
|Abstract||The lifetimes of the S1 states of azulene, azulene-d8, 4,6,8-trimethylazulene, and guaiazulene (1,4-dimethyl-7-isopropylazulene) have been measured in three nonviscous solvents of different polarity and structure using a two-photon, two-color, pump-probe method with subpicosecond time resolution. A significant solvent effect is measured. The rate constants for S1 --> S0 internal conversion in all four compounds in all three solvents exhibit one common S1-S0 energy gap law correlation, indicating that variations in the electronic relaxation rates are governed exclusively by changes in the Franck-Condon factors for the transition. No effect is observed when the exciting wavelength is changed, indicating that vibrational relaxation is occurring on a time scale which is faster than that of electronic relaxation in these systems. No significant deuterium isotope effect is measured in azulene, indicating that high frequency C-H(D) stretching vibrations do not act as significant accepting modes in the radiationless transition.|
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