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

Literature Information

Publication Date 2020-02-10
DOI 10.1039/C9CP06369B
Impact Factor 3.676
Authors

Shun-ichi Ishiuchi, Junko Kamizori, Norihiro Tsuji, Makoto Sakai, Mitsuhiko Miyazaki, Claude Dedonder


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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.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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