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Updated: Dec 27, 2025

Ultrafast Time-resolved Near-IR Stimulated Raman Measurements of Functional π-conjugate Systems
Published on: February 10, 2020
Excited state hydrogen transfer dynamics in phenol-(NH3)2 studied by picosecond UV-near IR-UV time-resolved
Shun-Ichi Ishiuchi1, Junko Kamizori, Norihiro Tsuji
1Laboratory for Chemistry and Life Science, Institute of Innovative Research, Tokyo Institute of Technology, 4259-R1-15, Nagatsuta-cho, Midori-ku, Yokohama 226-8503, Japan. miyazaki.mitsuhiko@ocha.ac.jp.
Abstract:
Time-evolutions of excited state hydrogen transfer (ESHT) in phenol (PhOH)-(NH3)2 clusters have been measured by three-color picosecond (ps) ultraviolet (UV)-near infrared (NIR)-UV pump-probe ion dip spectroscopy. The formation of a reaction product, ˙NH4NH3, is detected by its NIR absorption due to a 3p-3s Rydberg transition. The ESHT reactions from all of the vibronic levels show biexponential time-evolutions, even from the S1 origin. Based on the biexponential time-evolution, it is suggested that there is a second reaction path via the triplet πσ* state, which gives the slow component. The fast time-evolution of the ESHT reaction from the S1 origin is measured to be 268 ps, which is 10-times slower than that in PhOH-(NH3)3, and a higher barrier between the ππ* and reactive πσ* states is suggested. The size dependence of the ESHT reaction rates is discussed based on a potential distortion due to the proton transferred state in the ππ* potential surface.
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