Abstract
The vibrational excess energy dependence of the internal conversion of S 1 azulene in cyclohexane was measured with 50 fs resolution. The decay time decreases from 1.7 ps for the vibrationless S 1 state to 400 fs at 1300 cm −1. An upper limit of 2300 cm −1 is deduced for the energetic location of the conical intersection to the S 0 state responsible for the ultrafast decay. Further increased excess energy causes biexponential decay without significant decrease in the decay times up to 5500 cm −1. Strong oscillatory signal contributions are found due to low-frequency wavepacket motion not directly excited by the optical transition.
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