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Excited state hydrogen transfer dynamics in phenol–(NH3)2 studied by picosecond UV-near IR-UV time-resolved spectroscopy

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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.

Graphical abstract: Excited state hydrogen transfer dynamics in phenol–(NH3)2 studied by picosecond UV-near IR-UV time-resolved spectroscopy

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Article information


Submitted
25 Nov 2019
Accepted
07 Feb 2020
First published
10 Feb 2020

Phys. Chem. Chem. Phys., 2020, Advance Article
Article type
Paper

Excited state hydrogen transfer dynamics in phenol–(NH3)2 studied by picosecond UV-near IR-UV time-resolved spectroscopy

S. Ishiuchi, J. Kamizori, N. Tsuji, M. Sakai, M. Miyazaki, C. Dedonder, C. Jouvet and M. Fujii, Phys. Chem. Chem. Phys., 2020, Advance Article , DOI: 10.1039/C9CP06369B

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