Ultrafast Investigation of Excited-State Dynamics in Trans-4-methoxyazobenzene Studied by Femtosecond Transient Absorption Spectroscopy

The ultrafast photoisomerization and excited-state dynamics of trans-4-methoxyazobenzene (trans-4-MAB) in solutions were investigated by femtosecond transient absorption spectroscopy and quantum chemistry calculations. After being excited to the Sbegin{document}$_2$end{document} state, the two-dimensional transient absorptions spectra show that cis-4-MAB is produced and witnessed by the permanent positive absorption in 400begin{document}$-$end{document}480 nm. Three decay components are determined to be 0.11, 1.4 and 2.9 ps in ethanol, and 0.16, 1.5 and 7.5 ps in ethylene glycol, respectively. The fast component is assigned to the internal conversion from the Sbegin{document}$_2$end{document} to Sbegin{document}$_1$end{document} state. The other relaxation pathways are correlated with the decay of the Sbegin{document}$_1$end{document} state via internal conversion and isomerization, and the vibrational cooling of the hot Sbegin{document}$_0$end{document} state of the cis-isomer. Comparing of the dynamics in different solvents, it is demonstrated that the photoisomerization pathway undergoes the inversion mechanism rather than the rotation mechanism.